PREPARATION OF FIXING AGENTS FOR ANIONIC DYES

A THESIS SUBMITTED TO THE DIVISION OF SCIENCE AND TECHNOLOGY OF THE UNIVERSITY OF EDUCATION LAHORE BY

SAIMA SHARIF ROLL NO. 03-138 REGISTRATION NO. 0499056

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY

JUNE 2007

APPROVAL OF THE DIVISION OF SCIENCE AND TECHNOLOGY/ UNIVERSITY OF EDUCATION, LAHORE

-------------------------------------Director I certify that this thesis satisfies all the requirements as a thesis for the award of the degree of Doctor of Philosophy.

-------------------------------------Head of Department This is to certify that we have read this thesis and that in our opinion it is fully adequate, in scope and quality, as a thesis for the degree of Doctor of Philosophy.

-----------------------------------------------Dr. Mian Muhammad Izhar-ul-Haq (Co-Supervisor)

------------------------------------Dr. Saeed Ahmad (Supervisor)

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ABSTRACT

The selection of dyes and dyeing auxiliaries is a crucial factor in optimising dyeing processes. Dyeings often show unsatisfactory wet fastness properties. This is usually encountered with direct dyes and to a lesser extent with reactive dyes also. Different cationic fixing agents have been used as pretreatment or aftertreatment to improve the wet fastness properties of these dyes but none has proved to be totally satisfactory. Therefore, there is still a need for novel dyeing processes that improve properties in respect of application and fastness properties of the dyeings. The present work is therefore concerned with the synthesis of new cationic fixing agents and their evaluation as fixing agents in improving the wet fastness properties of anionic dyes on cellulose fibres. Eight mono-reactive (28a-d and 29a-d) and four bis-reactive (30a-b and 31a-b) 2,3-epoxy / 3chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride have been synthesised and their structures have been characterised using IR and 1HNMR spectroscopy. Purity of these compounds has been checked by thin layer chromatography (TLC). One mono-reactive (28c) and two bis-reactive (30a and 30b) 2,3epoxypropyl derivatives have been used for the cationisation of cellulosic

iv

fabrics under different pretreatment conditions. Pretreated fabrics were then dyed with a variety of direct, reactive and acid dyes under neutral and alkaline conditions in the absence of salt. A bis-reactive derivative compound 30b was also applied as an aftertreatment to the conventional direct dyeings under neutral and alkaline conditions. The reflectance values and the corresponding CIE L*, a*, b*, C* and ho colour coordinates of the samples were measured. From the reflectance values at the max. of the dyeings, colour strength (K/S) values of the dyeings were calculated using Kubelka-Munk equation. Fastness properties of the dyeings have been determined by following standard methods for the determination of colour fastness of textiles and leather. Pretreatment with mono- and bis-reactive cationic fixing agents (30a, 30b, 28c) has enabled the dyeing of cotton fabrics with anionic (direct, reactive and acid) dyes under neutral conditions in the absence of salt. Higher colour strength (K/S) and good wash fastness properties were obtained with the pretreated fabrics as compared to the untreated fabrics dyed with the same direct and reactive dyes. Bis-reactive derivatives showed better wet fastness properties as compared to the mono-reactive derivative. In addition, pretreatment has significantly reduced the dyeing time, thus becoming a more environmentally friendly method for the direct and reactive dyeing of cotton fabrics. Aftertreatment with cationic agents has shown a slight change in the colour of the direct dyeings but has beneficial effects on the wash fastness results.

DEDICATION

Dedicated to

My Beloved Parents
Whose prayers and affections are the source of strength for me in every step of life and a sign of success for my bright future.

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ACKNOWLEDGEMENT

I would like to express deep appreciation to my supervisor Prof. Dr. Saeed Ahmad, Chairman, Department of Chemistry, University of Science and Technology, Bannu for his inspiring guidance, encouraging attitude and valuable suggestions throughout my research work. I also express sincere appreciation to my co-supervisor Prof. Dr. Mian Muhammad Izhar-ul-Haq, Principal, University of Education, Township Campus, Lahore for his guidance and suggestions throughout the research work. I would like to thank Muhammad Fauz-ul-Azeem and Mr. HamoodurRehman, Scientific Officers, PCSIR Laboratories complex, Lahore for providing instrumental facilities. Thanks to Muhammad Naeem Khan and Mr. Farooq Arif for their cooperation. Thanks to Mr. Islam, Mr. Muhammad Iqbal, other laboratory staff and the library staff (PCSIR, Lahore) for their cooperation during my research work. I also acknowledge the cooperation of Sandal Dyestuff Industries Limited, Pakistan for providing dyes. Special thanks to my uncle and Dr. Shahina Waheed, Head (Retd.) /ACRC PCSIR Laboratories Complex, Lahore.

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TABLE OF CONTENTS

Page ABSTRACT -----------------------------------------------------------------------------iii DEDICATION ---------------------------------------------------------------------------v ACKNOWLEDGEMENT -------------------------------------------------------------vi TABLE OF CONTENTS -------------------------------------------------------------vii LIST OF TABLES --------------------------------------------------------------------xiv LIST OF FIGURES -------------------------------------------------------------------xix LIST OF SYMBOLS / ABBREVIATIONS -------------------------------------xxiii CHAPTER 1. INTRODUCTION ------------------------------------------------------------------1 1.1 Dyes and dyeing -----------------------------------------------------------------1 1.2 Classification of dyes -----------------------------------------------------------2 1.3 Anionic dyes ---------------------------------------------------------------------3 1.3.1 Direct dyes ---------------------------------------------------------------3 1.3.2 Reactive dyes ------------------------------------------------------------4 1.3.3 Acid dyes ---------------------------------------------------------------- 5 1.4 The need for auxiliaries -------------------------------------------------------- 5

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1.5 Classification of auxiliaries ----------------------------------------------------6 1.5.1 Classification of surfactants -------------------------------------------7 1.6 Pretreatments and aftertreatments for anionic dyes ------------------------8 1.6.1 Cationic fixing agents --------------------------------------------------9 1.6.1.1 Quaternary ammonium salts ---------------------------------11

1.7 Problems encountered with the fixing agents ------------------------------14 1.8 Plan of work --------------------------------------------------------------------14 2. LITERATURE REVIEW ------------------------------------------------------- 17 2.1 General development ----------------------------------------------------------18 2.2 Monomeric quaternary ammonium salts ----------------------------------- 23 2.2.1 Azetidinium chloride ------------------------------------------------- 25 2.2.2 Epoxy and halohydroxy propyl derivatives ------------------------27 2.2.3 Mono- and bis- reactive haloheterocyclic derivatives ------------34 2.3 Polymeric quaternary ammonium salts -------------------------------------38 3. EXPERIMENTAL WORK -----------------------------------------------------49 3.1 General information -----------------------------------------------------------50 3.2 Synthesis of mono- and bis-reactive 2,3-epoxy / 3-chloro-2hydroxy propyl derivatives of quaternary ammonium chloride ---------52 3.2.1 General procedure for the synthesis of mono- and bis-reactive 2,3-epoxypropyl derivatives (28a-d and 30a-b) -------------------55 N-Cyanomethyl-N-(2,3-epoxypropyl)-N,N-dimethyl ammonium chloride (28a) --------------------------------------------55

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N-Carboxymethyl-N-(2,3-epoxypropyl)-N,N-dimethyl ammonium chloride (28b) --------------------------------------------56 N-Cyanoethyl-N-(2,3-epoxypropyl)-N,N-dimethyl ammonium chloride (28c) --------------------------------------------57 N-Carboxyethyl-N-(2,3-epoxypropyl)-N,N-dimethyl ammonium chloride (28d) --------------------------------------------57 Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethyl ammonium chloride] (30a) -------------------------------------------58 Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethyl ammonium chloride] (30b) -------------------------------------------59 3.2.2 General procedure for the synthesis of mono- and bis-reactive 3-chloro-2-hydroxypropyl derivatives (29a-d and 31a-b) -------59 N-Cyanomethyl-N-(3-chloro-2-hydroxypropyl)-N,Ndimethylammonium chloride (29a) ---------------------------------60 N-Carboxymethyl-N-(3-chloro-2-hydroxypropyl)-N,Ndimethylammonium chloride (29b) ---------------------------------61 N-Cyanoethyl-N-(3-chloro-2-hydroxypropyl)-N,Ndimethylammonium chloride (29c) ---------------------------------62 N-Carboxyethyl-N-(3-chloro-2-hydroxypropyl)-N,Ndimethylammonium chloride (29d) ---------------------------------62 Methylene bis-[N-(3-chloro-2-hydroxypropyl)-N,Ndiethylammonium chloride] (31a) ----------------------------------63

Ethylene bis-[N-(3-chloro-2-hydroxypropyl)-N,Ndimethylammonium chloride] (31b) --------------------------------64 3.3 Applications --------------------------------------------------------------------64 3.3.1 Application of cationic fixing agents as pretreatment ------------65 3.3.1.1 Pretreatment of cotton fabrics -------------------------------65

3.3.2 Dyeing conditions for untreated cotton fabrics --------------------66 3.3.2.1 Dyeing of untreated cotton fabrics with direct dyes by conventional method -----------------------------------------66 3.3.2.2 Dyeing of untreated cotton fabrics with reactive dyes by conventional method --------------------------------------66 3.3.2.3 Dyeing of wool fabrics with acid dyes ---------------------67

3.3.3 Dyeing conditions for pretreated cotton fabrics -------------------67 3.3.3.1 3.3.3.2 3.3.3.3 Dyeing of pretreated cotton fabrics with direct dyes -----67 Dyeing of pretreated cotton fabrics with reactive dyes --68 Dyeing of untreated and pretreated cotton fabrics with acid dyes --------------------------------------------------------69 3.3.4 Application of cationic fixing agents as an aftertreatment -------70 3.3.4.1 3.3.4.2 Dyeing with direct dyes --------------------------------------70 Aftertreatment with cationic fixing agent (30b) ----------71

3.4 Colour measurement ----------------------------------------------------------71 3.5 Fastness testing ----------------------------------------------------------------72 3.5.1 Wash fastness ----------------------------------------------------------72

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3.5.1.1

Test procedure -------------------------------------------------73

3.5.2 Light fastness ----------------------------------------------------------73 4. RESULTS AND DISCUSSION ------------------------------------------------74 4.1 Synthesis of mono- and bis-reactive 2,3-epoxy and 3-chloro-2hydroxy propyl derivatives ---------------------------------------------------75 4.2 Applications --------------------------------------------------------------------77 4.2.1 Pretreatment with cationic fixing agents ---------------------------78 4.2.1.1 Effect of temperature and time on the cationisation of cotton fabrics --------------------------------------------------78 4.2.1.2 Effect of cationic agent (owf) and sodium hydroxide (ow cationic agent) concentrations on the cationisation of cotton fabrics -----------------------------------------------81 4.2.2 Dyeing of untreated and pretreated cotton fabrics with direct dyes --------------------------------------------------------------84 4.2.2.1 4.2.2.2 4.2.2.3 4.2.2.4 Effect of dyeing temperature --------------------------------84 Effect of dyeing time -----------------------------------------87 Effect of dye concentration ----------------------------------89 Effect of cationic agent concentration ----------------------91 Shades of direct dyes on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics ----------------97 4.2.3 Dyeing of untreated and pretreated cotton fabrics with reactive dyes -----------------------------------------------------------99

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4.2.3.1 4.2.3.2 4.2.3.3 4.2.3.4 4.2.3.5

Effect of dyeing temperature --------------------------------99 Effect of dyeing time ----------------------------------------102 Effect of dye concentration --------------------------------104 Effect of cationic agent concentration --------------------106 Effect of alkali (anhydrous Na2CO3) ----------------------108 Shades of reactive dyes on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics -114

4.2.4 Dyeing of untreated and pretreated cotton fabrics with acid dyes --------------------------------------------------------------117 Shades of acid dyes on wool, untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics -----------------------121 4.2.5 Aftertreatment of direct dyes with a bis-reactive cationic fixing agent -----------------------------------------------------------122 4.2.5.1 4.2.5.2 Effect of pH on the aftertreatment of direct dyeings ----122 Effect of cationic agent concentration on the aftertreatment of direct dyeings ---------------------------126 Shade change of direct dyeings by aftertreatment with a bis-reactive derivative (30b) -----------------------127 5. CONCLUSIONS -----------------------------------------------------------------128 REFERENCES ----------------------------------------------------------------------132 VITA -----------------------------------------------------------------------------------144

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Appendix A Colour strength (K/S) curves of untreated (C) and pretreated (C-1, C-2 and C-3) cotton fabrics dyed with direct dyes (Table 25) ---------146 Appendix B Colour strength (K/S) curves of untreated cotton fabrics dyed with direct dyes by conventional method (Table 26) --------------------------150 Appendix C Colour strength (K/S) curves of untreated (C) and pretreated (C-1, C-2 and C-3) cotton fabrics dyed with reactive dyes in the absence of salt and alkali (Table 32) -------------------------------------------------152 Appendix D Colour strength (K/S) curves of untreated (C) and pretreated (C-1, C-2 and C-3) cotton fabrics dyed with reactive dyes in the presence of alkali (Table 33) -----------------------------------------------------------157 Appendix E Colour strength (K/S) curves of untreated cotton fabrics dyed with reactive dyes by conventional method (Table 34) -----------------161 Appendix F Colour strength (K/S) curves of wool, untreated (C) and pretreated (C-1, C-2 and C-3) cotton fabrics dyed with acid dyes -----------------163 Appendix G Publications----------------------------------------------------165

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LIST OF TABLES

Page Table 1 Table 2 General classification of surfactants ---------------------------------8 Properties of acid dyes with cationic cotton using no salt at pH 7 ------------------------------------------------------------------26 Table 3 Fastness properties of direct, reactive and acid dyes with nylon, conventional cotton and cationised cotton ----------------30 Table 4 Fastness properties of acid dye on cotton cationised with different quaternary salts ---------------------------------------------31 Table 5 Fastness properties of direct dyes on untreated and treated cotton fabrics -----------------------------------------------------------34 Table 6 Fastness properties of direct dyes on untreated (C) and pretreated cotton fabrics with mono (C-1) and bis-reactive (C-2) cationic agents --------------------------------------------------37 Table 7 Fastness properties of direct dyes on untreated and treated (poly epichlorohydrin-dimethylamine) cotton ---------------------41 Table 8 Colour strength and fastness properties of 1:2 metal complex acid dyes on untreated and pretreated cotton (PT) ----------------43

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Table 9 Table 10

Fastness properties of acid dyes on cotton -------------------------45 Fastness properties of direct dyes on cotton aftertreated with cationic fixing agents / syntan ---------------------------------------46

Table 11

Fastness properties of direct dyeings aftertreated with Fixogene CXF and Matexil FC-ER under neutral and alkaline conditions ----------------------------------------------------47

Table 12 Table 13 Table 14 Table 15

Pretreatment conditions ----------------------------------------------65 Dyeing conditions with direct dyes ---------------------------------68 Dyeing conditions with reactive dyes ------------------------------69 Reaction conditions and yields of salts 28a-d, 29a-d, 30a-b and 31a-b ---------------------------------------------------------------76

Table 16 Table 17

max. values of the dyes ---------------------------------------------77 Effect of temperature on the chlorine content of cationised fabric -------------------------------------------------------79

Table 18

Effect of pretreatment time on the chlorine content of cationised fabric ------------------------------------------------------80

Table 19

Effect of cationic agent concentration on the chlorine content of cationised fabric ------------------------------------------81

Table 20

Effect of NaOH concentration on the chlorine content of cationised fabric ------------------------------------------82

Table 21

% Reflectance (at max. 510 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and

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C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) under different temperature conditions -------------85 Table 22 % Reflectance (at max. 510 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) at 100 oC for different time periods ---------------------88 Table 23 % Reflectance (at max. 510 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 at 100 oC for 30 minutes using different dye concentrations ----90 Table 24 % Reflectance (at max. 510 nm) and the colour strength (K/S) values of cotton fabrics pretreated with different conc. of cationic agents (C-1, C-2 and C-3) and dyed with C.I. Direct Orange 26 (2% owf) at 100 oC for 30 minutes ------------92 Table 25 Colour strength (K/S) and fastness properties of direct dyes (2% owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics -----------------------------------------94 Table 26 Colour strength (K/S) and fastness properties of untreated cotton fabrics dyed with direct dyes (2% owf) by conventional method --------------------------------------------------96 Table 27 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and

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C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at different temperature conditions ----------------100 Table 28 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at 80 oC for different time periods -----------------103 Table 29 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with different conc. of C.I. Reactive Orange 13 at 80 oC for 30 minutes -------------------105 Table 30 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of cotton fabrics pretreated with different conc. of cationic agents (C-1, C-2 and C-3) and dyed with C.I. Reactive Orange 13 (2% owf) at 80 oC for 30 minutes ---------107 Table 31 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of pretreated cotton fabrics (C-1, C-2 and C-3; 2% owf) dyed with C.I. Reactive Orange 13 (2% owf) at 80
o

C for 30 minutes using different amounts of alkali ------------109

Table 32

Colour strength (K/S) and fastness properties of reactive dyes (2% owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics in the absence of salt and alkali --------111

Table 33

Colour strength (K/S) and fastness properties of reactive

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dyes (2% owf) on pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics in the presence of alkali (anhydrous Na2CO3; 20g/L) -----------------------------------------------------------------112 Table 34 Colour strength (K/S) and fastness properties of reactive dyes (2% owf) on untreated cotton fabrics dyed by conventional method ------------------------------------------------113 Table 35 % Reflectance (at max. 400 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with different concentrations of C.I. Acid Yellow 23 at 100 oC for 60 minutes ----------------118 Table 36 Colour strength and wash fastness properties of acid dyes on wool, untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics ----------------------------------------------120 Table 37 Colorimetric data for untreated and aftertreated direct dyeings before wash fastness testing ------------------------------123 Table 38 Wash fastness data for untreated and aftertreated direct dyeings ----------------------------------------------------------------124 Table 39 Colorimetric data for untreated and aftertreated direct dyeings after wash fastness testing --------------------------------125

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LIST OF FIGURES

Page Figure 1 Figure 2 Figure 3 Figure 4 Classification of auxiliaries --------------------------------------------7 Fixing agents showing various degrees of functionality ---------10 Modes of reaction of the various fixing agents --------------------11 General scheme for the synthesis of bis-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride ---------------------------------------------------15 Figure 5 General scheme for the synthesis of mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride ---------------------------------------------------16 Figure 6 Figure 7 Figure 8 Figure 9 Modification of cotton with N-methylolacrylamide --------------24 Reaction of epoxypropyl derivatives with cellulose --------------27 Reaction of halohydroxy propyl derivatives with cellulose -----28 Synthesis of mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride -----------53 Figure 10 Synthesis of bis-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride -----------54

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Figure 11 Figure 12 Figure 13

Dyeing profile of untreated cotton fabric with direct dyes ------66 Dyeing profile of untreated cotton fabric with reactive dyes ----67 Dyeing profile of untreated and pretreated cotton fabrics with acid dyes ----------------------------------------------------------------70

Figure 14

Aftertreatment of direct dyed cotton fabrics with cationic fixing agent (30b) -----------------------------------------------------71

Figure 15

Effect of temperature on the chlorine content of cationised fabric --------------------------------------------------------------------79

Figure 16

Effect of pretreatment time on the chlorine content of cationised fabric -------------------------------------------------------80

Figure 17

Effect of cationic agent concentration on the chlorine content of cationised fabric ------------------------------------------83

Figure 18

Effect of NaOH concentration on the chlorine content of cationised fabric -------------------------------------------------------83

Figure 19

Effect of temperature on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) -------86

Figure 20

Effect of dyeing time on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) ------89

Figure 21

Effect of dye conc. on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2, C-3; 2% owf) cotton fabrics

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dyed with C.I. Direct Orange 26 ------------------------------------91 Figure 22 Effect of cationic agent concentration on the colour strength (K/S) of pretreated cotton fabrics (C-1, C-2 and C-3) dyed with C.I. Direct Orange 26 (2% owf) -------------------------------93 Figure 23 Colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 ------------------------------------------------------95 Figure 24 Effect of temperature on the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) --101 Figure 25 Effect of dyeing time on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) --104 Figure 26 Effect of dye conc. on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 ---------------106 Figure 27 Effect of cationic agent concentration on the colour strength (K/S) of pretreated (C-1, C-2 and C-3) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) -----------108

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Figure 28

Effect of alkali conc. on the colour strength (K/S) of pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) --------------------------110

Figure 29

Effect of dye conc. on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Acid Yellow 23 ---------------------------119

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LIST OF SYMBOLS / ABBREVIATIONS

AATCC Review

American Association of Textile Chemists and Colorists Review

Adv. Color. Sci. Tech. Am. Dyestuff Rep. C C-1 C-2 C-3 Chem. Abs. Color. Technol. Conc. Conf. Dyeings J.A.O.C.S. J.S.D.C. K/S

Advances in Colour Science and Technology American Dyestuff Reporter Untreated cotton fabric Cotton pretreated with compound 30a Cotton pretreated with compound 30b Cotton pretreated with compound 28c Chemical Abstract Coloration Technology Concentration Conference dyed textile fibres Journal of the American Oil Chemists' Society Journal of the Society of Dyers and Colourists Colour strength

xxiv

owf Rev. Prog. Color. SAWTRI. Tech. Rep. Temp. Text. Chem. Colorist Text. Res. J. max.

of weight of fibre Review of Progress in Coloration South African Wool Textile Research Institute, Technical Report Temperature Textile Chemist and Colorist Textile Research Journal Absorbance at the wavelength of maximum absorption

INTRODUCTION

Chapter 1 INTRODUCTION

1.1 DYES AND DYEING

Dyes are intensely coloured substances used for the coloration of various substrates including paper, leather, fur, hair, foods, drugs, plastics and textile materials. They are retained in these substrates by physical adsorption, salt or metal complex formation or by the formation of covalent chemical bonds [1]. Until the middle of nineteenth century all dyes were natural products, extracted in most cases from a variety of plants, but also from a few animal sources. Plant sources include roots, stems, leaves, flowers and fruits while animal sources include certain dried insects. At present practically all dyes are coloured organic chemicals synthesised from products of the petro-chemical and coal-tar industries [2].

Dyeing is a process of colouring textile fibres and other materials so that colouring matter becomes an integral part of the material rather than a surface coating. The mechanism of dyeing must differ with the nature of the material, that is, whether it is protein, cellulose or some synthetic substance [3]. The appropriate dye class for the fibre must be used along with specific dyeing conditions in order to gain an optimum result [4].

1.2 CLASSIFICATION OF DYES

Dyes are usually classified in two ways [5]: 1. According to the chemical constitution of the dye molecules e.g. azo dyes, triphenylmethane dyes, stilbene dyes, anthraquinoid dyes etc. or 2. According to the method of application of the dye e.g. direct dyes, acid dyes, reactive dyes, disperse dyes, vat dyes, sulphur dyes, mordant dyes, metal complex dyes, basic dyes and azoic dyes. Dyes are organic molecules and can also be classified as [5]: 1. Anionic dyes-------- in which the colour is caused by the anionic part of the dye molecule e.g. direct, reactive and acid dyes 2. Cationic dyes------- in which the colour is caused by the cationic part of the dye molecule e.g. basic dyes 3. Non-ionic dyes----- in which the colour is caused by the whole dye molecule e.g. disperse dyes

1.3 ANIONIC DYES

Textile fibres may be dyed with anionic dyes including direct dyes, acid dyes and reactive dyes or with cationic dyes. The term anionic dyes is intended to mean dyes in which coloured ion is anionic in character containing sulphonic or carboxylic groups. These dyes have long been known for the dyeing of natural fibres such as wool and cotton as acid and direct dyes [6]. Amongst anionic dyes, direct and reactive dyes are the most popular dye classes used for the dyeing of cellulosic fibres which comprise over 40% of world textile consumption.

1.3.1 DIRECT DYES All direct dyes are substantive to cellulosic fibres. Substantivity means the affinity of the dye with the fibre to which it is applied. The substantivity of direct dyes for cotton is due to the linear and planar structure of the dye molecules, which enables close alignment with chains of cellulose molecules resulting in significant hydrogen bonding. However, the wet fastness properties of direct dyes are inadequate for many end uses and these dyes have been replaced to a great extent by reactive dyes which have better wet fastness and exceptional brightness in many hues but the prime advantages of direct dyes are ease of application, wide range of shade and economy compared with dyes of higher fastness (reactive, sulphur or vat) [7]. There are still many applications in the textile industry for goods dyed with direct dyes, particularly

where a high standard of wet fastness is not required. The development of specialised crosslinking aftertreating agents for use with selected direct dyes of high light fastness has enabled direct dyes to compete more effectively with reactive dyes in meeting severe wet fastness requirements. In fact, direct dyes are second only to sulphur dyes in their textile usage worldwide with vat and fibre reactive dyes well behind [8].

1.3.2 REACTIVE DYES Reactive dyes are regarded as being substantive as well as reactive to the textile fibres. These dyes are also widely used for the dyeing of cellulosic fibres because of their wide shade range and excellent wet fastness which arises from a covalent bond formed between dye and the fibre. However, reactive dyeing process requires high salt and alkali concentrations, even then the dyeing process results in strongly coloured effluents. The fundamental problem of reactive dyeing is that the reaction of reactive dye with water (hydrolysis) competes with the formation of the desired covalent bond between the dye and textile substrates (fixation reaction) and up to 40% of the reactive dye may hydrolyse in the dyeing process. As this hydrolysed dye cannot react with the fibre it should be washed off thoroughly in order to achieve the desired superior wet fastness of the reactive dyeing. This involves expensive washing off procedures and the treatment of the effluents. Thus, reactive dyes have both economic and environmental drawbacks [9,10].

1.3.3 ACID DYES Acid dyes, which are primarily used for the dyeing of nitrogenous fibres such as wool, silk and nylon, are also anionic in nature. The relatively nonlinear structure of these acid dyes does not facilitate close alignment with the molecular chains in cellulose, which in turn prevents hydrogen bonding. Therefore, these dyes are not substantive to cellulosic fibres. However, cationised cellulosic fibres can be dyed with acid dyes of both the nonmetallised and pre-metallised types. This increase in substantivity is due to the interaction of anionic sulphonic groups in the dye molecules with the cationic groups in the modified cellulose [11]. Generally, the dyed cellulosic fibres have a fastness to washing that does not meet the requirements of today's consumers. This is particularly the case not only for many direct dyes but to a lesser extent for reactive dyes also [12].

1.4 THE NEED FOR AUXILIARIES

The practice of dyeing has recently led to increased requirements in terms of quality of dyeings and profitability of the dyeing process. There is hardly a dyeing or printing process of commercial importance that can be adequately operated by the use of dyes and water alone. Practically every colorantsubstrate system requires the use of additional products known as auxiliaries. An auxiliary has been defined [13] as:

"A chemical or formulated chemical product which enables a processing operation in preparation, dyeing, printing or finishing to be carried out more effectively or which is essential if a given effect is to be obtained." The selection of dyes and dyeing auxiliaries is a crucial factor in optimising dyeing processes. Different auxiliaries improve the application characteristics and performance in terms of penetration, levelling, fixation and shade deepening to provide brilliant intense dyeings. The class of auxiliaries which is used to improve the retention of dye by the fibre is traditionally called fixing agents. These chemicals function by forming a dye-fixing agent complex of large molecular size and reduced aqueous solubility and therefore higher wet fastness [14].

1.5 CLASSIFICATION OF AUXILIARIES

It is much harder to device a classification system for auxiliaries than it is for dyes. The broadest classification of auxiliaries is achieved simply by dividing them into non-surfactants and surfactants. Non-surfactants include simple electrolytes, acids and bases, both inorganic and organic whereas surfactants are defined [13] as: "An agent, soluble or dispersible in a liquid, which reduces the surface tension of the liquid"

Auxiliaries

Non-surfactants

Surfactants

Simple electrolytes

Anionic surfactants Cationic surfactants

Acids and bases, both inorganic and organic

Non-ionic surfactants

Amphoteric surfactants

Figure 1

Classification of auxiliaries

1.5.1 CLASSIFICATION OF SURFACTANTS Surfactants owe their properties to their molecular structure, which contains both hydrophobic and hydrophilic parts. The surfactants used as textile auxiliaries can be divided into four major groups (Table 1) depending on the type and distribution of the polar forces [15].

8 Table 1 General classification of surfactants

Degree of ionic charge on the _____________________________________________ hydrophobe Anionic surfactants Cationic surfactants Non-ionic surfactants Amphoteric surfactants Weakly negative Weakly positive Uncharged hydrophile (associated ion) Strongly positive Strongly negative Uncharged

Class of surfactant

These possess balanced negative and positive charges, one or other of which dominates in solution depending on pH

1.6 PRETREATMENTS ANIONIC DYES

AND

AFTERTREATMENTS

FOR

The use of pretreatments or aftertreatments to improve the fastness properties of dyeings has a long and prolific history. Notable improvements in the wet fastness properties of anionic dyes can be brought about by pretreatment or aftertreatment of textile fibres [16]. Three main approaches which were adopted for the pretreatment of cellulose fibres include: 1. 2. 3. Vinyl grafting Reaction with cationic molecules Application of cationic polymers Different aftertreatment processes include: 1. 2. Diazotization and development Metal salt treatments

3. 4. 5.

Formaldehyde treatment Cationic fixing agents Crosslinking agents and resin treatments Amongst various pretreatment and aftertreatment systems cationic fixing

agents are most widely used.

1.6.1 CATIONIC FIXING AGENTS Cationic fixing agents were initially applied as aftertreatments to the dyed textile fibres to improve their wet fastness properties [17,18]. However, the improved fastness was related only to non-detergent agencies. Later on, this limitation of mono-functional cationic fixing agents has been overcome by the development of polyfunctional crosslinking fixing agents which carry reactant groups capable of forming more permanent bonds with other suitable groups in the dye or fibre [19,20]. The basic mechanism of multifunctional fixing agents has been well described by Robinson [21] as shown in Figure 2 and 3. During 1980's there was a great revival of interest in the techniques for enhancing the dyeability of cellulosic fibres with reactive or direct dyes by pretreatment with a great variety of cationic products usually based on nitrogen. This modification of cellulosic fibres with cationic agents resulted in increased substantivity of anionic dyes for cellulosic fibres by introducing new cationic sites. Lewis and Lei reviewed numerous chemicals that can be used to provide cationic charges to cotton fibres [22]. Pretreatment of cellulosic fibres

10

with cationic agents has been reported to enhance the uptake of anionic dyes and facilitate the fixation of reactive dyes in the absence of either salt or alkali [23,24]. The cationised fibre not only has improved substantivity for direct and reactive dyes, but could also be dyed with acid dyes [11]. Amines [25], quaternary ammonium [26], phosphonium [27] and tertiary sulphonium [28] compounds can be used as dye fixing agents. By far the most important type of cationic fixing agents used in textile processing is quaternary ammonium salt.

Monofunctional type

Bifunctional type

Trifunctional type

Tetrafunctional type

Figure 2

Fixing agents showing various degrees of functionality

11

Cellulose + 3OS-D

Monofunctional type

+ -

3OS-D

o HO

Bifunctional type

(OH -) + 3OS-D

O HO Trifunctional type

O + 3OS-D

Tetrafunctional type O HO

(H+)

Figure 3

Modes of reaction of the various fixing agents

1.6.1.1 QUATERNARY AMMONIUM SALTS Quaternary ammonium salts have widespread applications in different fields and are used as surfactants [29], phase transfer catalysts [30,31], solvents, drugs, herbicides [32], antimicrobials [33-35] and disinfectants [36]. Being surfactants these compounds are used as softeners for textile and paper

12

products, as emulsifiers [37,38], as washing agents for textile materials dyed or printed with cationic dyes [39] and as fixing agents for cellulose-containing materials dyed with anionic dyes [40,41]. The positive charge in these compounds imparts antistatic properties to wool, cotton and other cellulosic fibres as well as certain synthetic fibres [38,42]. Amongst the manifold applications, one of the primary functions of these compounds is their use as cationic fixing agents. Different quaternary ammonium salts [40,43,44] have been applied to the fibres either as pretreatment or aftertreatment to improve the wet fastness properties of anionic dyes. These include monomeric or polymeric quaternary ammonium salts having different reactive groups. The most commonly used quaternary ammonium salts are: 1. 2. 3. 4. dialkyl azetidinium chloride (1) (2, 3) (4)

epoxy / halohydroxy propyl derivatives

mono- and bis-reactive haloheterocyclic derivatives poly-epichlorohydrin dialkyl derivatives (5)

The anions in these fixing agents are usually chloride or bromide.

Cl R1 R2 N
+

OH
O

N
+

R1

X Cl N OH R3
+

R1 R2

R3

R2

13
Cl N R N N NH R1 X
+

O
R2

n X H N
+

R1

R3

R2

Many of the attempts to fix quaternary ammonium salts to cellulose via ether linkage have included the use of epoxy / halohydroxy propyl derivatives [45,46]. Amongst these derivatives, 2,3-epoxypropyl trimethyl ammonium chloride [47,48] and 3-chloro-2-hydroxy propyl trimethyl ammonium chloride [49] have been reported to improve the dye exhaustion and fastness properties but the results left scope for further work. Mono- and bis-reactive haloheterocyclic derivatives usually based on cyanuric chloride have also been reported to improve the wet fastness properties of anionic dyes [50]. However, the reactivity of mono-reactive haloheterocyclic derivatives to the textile fibres is low and these compounds are also expensive. So the practical utility of these compounds is low. Polymeric cationic agents have also been reported in this regard. These compounds usually show poor penetration and distribution of dyes [22] resulting in poor light fastness properties of the dyed textile fibres as compared to fabrics pretreated with lower molecular weight compounds.

14

1.7 PROBLEMS ENCOUNTERED WITH THE FIXING AGENTS

Although a variety of fixing agents have been used to improve the fastness properties of anionic dyes but to date none has achieved significant commercial success. All these treatments enhanced the uptake of the dye yet there are practical drawbacks to all these treatments including hue changes, poor penetration into the fibre [51] and light fastness limitations [22]. These areas require further investigations and there is still a need for novel dyeing processes that improve properties in respect of application and fastness properties of the dyeings.

1.8 PLAN OF WORK

Although mono-reactive epoxy / halohydroxy propyl derivatives improved the wet fastness properties of anionic dyes but to the best of our knowledge, no significant work has been done on bis-reactive epoxy / halohydroxy propyl derivatives or mono-reactive epoxy / halohydroxy propyl derivatives of quaternary ammonium salts containing some other reactive groups. Keeping this in view and due to our interest in the synthesis of cationic fixing agents, this research is proposed that pertains to the synthesis of new bisreactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride (Figure 4). We expect that these compounds will bind to the fibre more permanently and provide more cationic dye sites for anionic

15

dyes, thus showing a higher affinity and reactivity with the fibre than the mono-reactive epoxy / halohydroxy propyl derivatives. This will not only enhance the uptake of the dye but also improve the general fastness properties. In addition, mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives containing cyano and carboxylic groups will also be synthesised (Figure 5). It is expected that these additional groups may further enhance the exhaustion and fixation ability of these compounds by forming a linkage with the fibre and /or the dye.

R N R

R N (CH2)n O R

Cl

Cl R + R N R + N (CH2)n R O

Cl

Conc. HCl O

Cl

Cl Cl HO R + N

R R

Cl

OH Cl

+ (CH2)n N R

Figure 4

General scheme for the synthesis of bis-reactive 2,3-epoxy / 3chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride

16
-

Cl R N R (CH2)n X O O

Cl

+ N (CH2)n R X

Conc. HCl O

Cl

R Cl OH

Cl

+ (CH2)n N R X

Figure 5

General scheme for the synthesis of mono-reactive 2,3-epoxy / 3chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride

Reaction parameters for the synthesis of these compounds will be optimised. The newly synthesised compounds will be purified by different purification techniques and the purified compounds will be characterised using different spectroscopic techniques. These newly synthesised mono- and bis-reactive quaternary ammonium compounds will be used as pretreatments and aftertreatments to the cotton fabrics dyed with anionic dyes (direct, reactive and acid dyes). The colour strength (K/S) values and fastness properties of the dyeings will be determined and the effect of fixation on shade change and fastness properties will be evaluated.

LITERATURE REVIEW

18

Chapter 2 LITERATURE REVIEW

2.1 GENERAL DEVELOPMENT

Most early dyeing processes used naturally occurring coloured compounds e.g. dye woods [52], which had no significant affinity for cotton and silk. These processes required a metal salt mordant before dyeing and after dyeing, fixation with tannin. The major growth and establishment of the synthetic dye industry was initiated with the discovery of Congo Red, the first direct dye for cotton, in1884 [53]. Although some early direct dyeings were claimed to be fast to soaping [54] it was soon appreciated that fastness to light and wet treatments left much to be desired. From 1930 onwards, complexing of direct dyes, present on the fibre, with aqueous solutions of cationic fixing agents began to be fully exploited. The importance and use of these agents was greatly extended by the

19

development of products rising from the condensation of cyanamide (6) or similar compounds with formaldehyde. These resin fixatives [55] of which Fibrofix (7) was a classical example [56], could be applied by a simple, finishing technique to cellulosic fibres dyed or printed with direct dyes. This resin fixative class was rapidly extended to provide a large number of agents based on the condensation products of formaldehyde with cyanamide derivatives [57], which were suitable for aftertreatment of direct dyes on cellulose fibres. Later on, the reaction products of cyanamide or cyanamide derivatives with monofunctional or polyfunctional amines and the condensates of these amines with formaldehyde or N-methylol derivatives were used as an aftertreatment to improve the wet fastness properties of anionic dyes on cellulose fibres [58,59]. Other relevant developments in this area have been reviewed in detail [60].

H2N HN N
H2N C N

nX n

NH

Extensive research work has shown that formaldehyde based resin finished products release formaldehyde into the atmosphere directly or during processing, handling, garment manufacturing and subsequent wearing of

20

textiles due to the hydrolysis of unreacted or partially crosslinked N-methylol derivatives present on the fibre. Direct release of formaldehyde into the working environment causes severe irritation to eyes, nasal passages and respiratory tract while an unreacted or partially crosslinked resin causes an allergenic response of the skin upon continuous handling of textiles [61]. For reasons of these health problems associated with formaldehyde, there was an increasing demand for non-formaldehyde fixing agents. It has also been reported that formaldehyde containing fixing agents for direct dyeing could be substituted by nitrogen containing non-formaldehyde fixatives without sacrificing the performance properties of the finished goods. Selection of suitable non-formaldehyde fixatives could actually produce better products than using the formaldehyde fixative [8]. Nitrogenous-based dye fixing agents have also been reported to improve overall fastness properties, without affecting the tone and depth of shades of reactive dyes on cotton substrates. The results indicated that commercial non-formaldehyde and formaldehydebased dye fixing agents could be replaced by laboratory developed nitrogenous-based dye fixing agents [62]. After the discovery of reactive dyes, dyeing with reactive dyes became the most versatile method for the coloration of cellulosic fabrics. These dyes were used instead of aftertreated direct dyes but they have both economic and environmental drawbacks because of high salt usage and insufficient fixation caused by hydrolysis leading to pollution of the effluent [9]. However, if an

21

aftertreatment is given prior to the rinsing stage, hydrolysed dye also gets fixed showing improved wet fastness. Therefore, aftertreatment still remained an extremely useful way of improving the wet fastness properties of a deep dyeing that failed to meet the necessary standards. Developments taking place during the recent decade have enabled direct dyes to compete with reactive dyes in the field of severe wet fastness requirements. The production, in the 1960s, of polyfunctional cross-linking fixing agents [19,20,63,64] capable of reacting with both dye and fibre was a significant development. These agents were used to aftertreat dyes on cellulosic, polyamide and wool fibres. The use of anionic dyes (acid, direct and reactive dyes) and cationic fixing agents is widespread in dyeing processes. Many studies have been devoted to improve the fastness properties of anionic dyes by pretreating or aftertreating the fibres with amines or reactive cationic agents. Most of these studies have used monomeric or polymeric quaternary ammonium salts having different reactive groups. These include dialkyl azetidinium chloride, epoxypropyl / halohydroxy propyl trialkyl derivatives of ammonium chloride, mono- and bis-reactive haloheterocyclic compounds and poly-epichlorohydrin dimethylamine derivatives. The mechanisms of dyeing cotton textiles pretreated with quaternary compounds of mono-reactive epoxypropyl type and mono- and bis-reactive chlorotriazine type were studied. The high reactivity and better thermal

22

stability of chlorotriazine type agents than epoxypropyl type agents made them suitable for pad-batch or exhaust applications rather than the more costly padbake process and gave effective enhancement of reactive dye uptake [51]. Later on, it was found that the pretreatment of cotton fabric with bis-reactive cationic agent promoted higher extents of dye exhaustion and fixation than that with mono-reactive cationic agent [50]. The low substantivity and poor thermal stability of mono-reactive epoxypropyl agents made them unsuitable for exhaust application and was also responsible for the poor dye penetration due to significant migration of agent during the thermal reaction step of pad-bake process leading to non-uniform distribution of cationic dye sites on the fibre [51]. The reactivity of cotton with such type of compounds has been studied under a variety of conditions [48,65,66] but no best procedure has yet been established. Recent work has shown that cotton cationised through a pad-batch process gave excellent dye penetration indicating the uniform distribution of cationic dye sites through this process. Thus, a pad-batch process seems to be good for achieving high yields of cationically modified cotton with uniform distribution of dye sites [67]. The pad-batch dyeing technique has now become an important dyeing method for its simplicity, low consumption of energy and water, and excellent reproducibility [68]. Recently, a new method based on the sol-gel process has proved to be an effective way to improve the wash fastness of direct dyes on cotton without essential loss of properties such as handle and strength of the fabric [69]. This

23

process involves the fixation of dyes through hydrogen bonding, van der Waal's forces and covalent bonding. It was also found that a sol prepared from an epoxy containing precursor exhibited the best results as a fixing agent on dyed cotton [70].

2.2 MONOMERIC QUATERNARY AMMONIUM SALTS

The use of cationic agents in the form of primary, secondary, tertiary and quaternary amine residues has been known since 1926 [25,26]. Pretreatment of cotton fabrics with Katamin AB (alkylbenzyldimethyl ammonium chloride; 8) has been reported to increase the uptake of reactive dyes and reduce the amount of dye and alkali required for dyeing [71].

H3C

Cl N

R
HO NH O CH2

CH3

To investigate systematically the effect of attaching a variety of amines to the cellulose fibre, cotton was modified by pretreatment with Nmethylolacrylamide (9; Allied Colloids) to introduce pendant-activated double bond (Figure 6). By introducing amino residues at these new sites good colour yield and high fixation values of reactive dyes were achieved at pH 5-7 in the absence of electrolyte but light fastness was lowered. Cellulose modified with

24

only N-methylolacrylamide (9) also gave high colour yields with dyes containing pendant aliphatic amino residues in the presence of electrolyte under alkaline conditions [23].

O Cell OH

O CH2 ZnCl 2 / 150 C

o

HO

NH

Cell O NH

CH2

H2O

Figure 6

Modification of cotton with N-methylolacrylamide

Recently, a new fibre-reactive quaternary compound containing an acrylamide residue was synthesised and applied to cotton fabrics using a pad bake process. It was found that the treated fibre could be dyed with reactive dyes without the addition of salt or alkali. The reactive dyes were almost completely exhausted and showed a high degree of covalent bonding with the pretreated cellulose [72]. A fibre-reactive chitosan derivative, propyl] O-

acrylamidomethyl-N-[(2-hydroxy-3-trimethylammonium)

chitosan

chloride, was used for the modification of cotton. Dyeing of this modified fibre with direct and reactive dyes gave higher colour yields and better wash fastness properties without the addition of salt but reduced the light fastness as compared to the untreated cotton [73]. Cationic starch had also been used for the modification of cotton fabrics. Dyeing of this modified fibre with reactive dyes using a continuous dyeing method gave improved dye fixation and level

25

dyeing without the presence of salt compared with untreated cotton. The dyeings also showed good wash and rub fastness [74].

2.2.1 AZETIDINIUM CHLORIDE An investigation of the direct dyeing of cotton cationised with 1,1dimethyl-3-hydroxy azetidinium chloride (10), 1,1-diethyl-3-hydroxy

azetidinium chloride (11) or Sandene 8425 (aliphatic polyamine derivative; Clariant) showed improved dye absorption and firmness of colour in the absence of salt in a neutral medium [41,75]. The above-modified fibre also enhanced the exhaustion and fixation of acid (Table 2) [11] and reactive dyes [76] on cotton in the absence of salt in a neutral medium. The effect of alkali pretreatment followed by 1,1-dimethyl-3-hydroxyazetidinium chloride

(DMAC) treatment on the dyeability of cotton yarn with reactive dyes has been reported to produce a much stronger colour yield than by DMAC treatment without alkali pretreatment [77].

Cl H3C H3C N
+

OH

H 5C 2

Cl N
+

OH

H 5 C2

10

11

26 Table 2 Properties of acid dyes with cationic cotton using no salt at pH 7

K/S _____________ After Dye C.I. Acid Red 73 Treatment I II III C.I. Acid Orange 7 I II III C.I. Acid Yellow 36 I II III C.I. Acid Green 12 I II III C.I. Acid Red 183 I II III C.I. Acid Red 214 I II III
b

Fastness properties ____________________________ Washinga After DMF 0.95 4.02 0.39 0.50 0.98 0.35 0.35 0.37 0.21 2.03 4.76 0.41 2.66 5.88 0.43 3.20 7.55 0.68
c

_________________ A 4 2-3 2-3 2-3 2 2 2 2 3 2 4 2 3-4 4 3 2 3-4 2 C 4 2 4 2 2-3 4-5 3-4 4 3-4 3-4 4 4 2-3 4-5 4-5 4 3-4 2 W 3-4 2 3-4 2-3 2-3 4-5 2 3 4-5 2 3 3 2-3 4 4-5 2-3 3-4 3 Light 4 6 5-6 2-3 6 3 5 4-5 4 5 5 6 6 6 6 6 6 6

wash 3.62 9.34 1.04 2.51 6.18 1.05 1.23 3.25 0.64 3.87 7.14 1.95 2.72 12.14 2.51 4.63 12.51 3.25

a. A, change in colour; C, staining on cotton; W, staining on wool b. I, Sandene 8425; II, 1,1-dimethyl-3-hydroxy azetidinium chloride (DMA-AC); III, 1,1-diethyl-3hydroxy azetidinium chloride (DEA-AC) c. DMF, dimethylformamide

27

2.2.2 EPOXY AND HALOHYDROXY PROPYL DERIVATIVES Several patents have covered the preparation of epoxy and halohydroxy propyl derivatives of ammonium chloride [78-82]. Many attempts have been made to fix epoxy and halohydroxy propyl derivatives to cellulose via an ether linkage. Epoxypropyl derivatives of ammonium chloride react with cellulose under alkaline conditions to form ethers (Figure 7).

R1 N R2
+

Cl

+
R3 O

Cell

OH

OH

R1 N R2
+

Cl

Cell O OH

R3

Figure 7

Reaction of epoxypropyl derivatives with cellulose

However, when halohydroxy propyl derivatives have been used for the cationisation of cellulosic fabrics under alkaline conditions, an epoxide ring is first formed in the cationising agent by the action of alkali and it then reacts with the hydroxyl group of cellulose under alkaline conditions (Figure 8). Alkali is required both for the formation of epoxide ring and for its reaction with cellulose. Thus, both epoxy and halohydroxy propyl derivatives have the same reactive group.

28
Cl N R2 +

R1

Cl OH

OH

R1 N R2
+

Cl

R3

R3 R1 N R2
+

O Cl Cell O OH

R1 N R2
+

Cl

+
R3 O

Cell

OH

OH

R3

Figure 8

Reaction of halohydroxy propyl derivatives with cellulose

The first product of this type was Glytac A (Protex; 12), which reacted with cellulose via the epoxy group at alkaline pH [83]. The use of 2,3epoxypropyl trimethylammonium chloride (12) as pretreatment, a simultaneous treatment or an aftertreatment increased the fixation and fastness properties (except rubbing fastness) of direct dyes on cotton textiles. It has been observed that a pretreatment generally produced better results than an aftertreatment. An increase in the number of solubilising groups on the direct dye molecules generally resulted in a deterioration of the rubbing fastness of pretreated fabrics and an improvement in case of aftertreated fabrics [84]. This treatment has also been reported to increase the fixation of various reactive dyes on cotton but reduced the fastness properties of dyed fabrics [85]. A comparative study of the reactive dyeing of unmodified cotton and cotton cationised with compound (12) with dyes having four different reactive groups showed that cationic cotton gave the same colorfastness as the unmodified cotton, but usually with higher colour yields [47]. Cotton modified

29

with this agent through a cold pad-batch process has been reported to show excellent colour yields and fastness properties for a number of direct (Crompton & Knowles), reactive and acid dyes (Dystar), without the use of electrolytes or multiple rinses, which are normally employed in cotton dyeing (Table 3) [67].

Cl

CH3

Cl Cl N OH R3
+

R1 R2

N O H3C

CH3

12

13
R1 = R 2 = R 3 = CH3, C2H5, C3H7, C5H11

3-chloro-2-hydroxypropyltrialkyl derivatives of ammonium chloride (13) were synthesised through the reaction of various trialkylamines with epichlorohydrin and were used for the cationisation of cellulosic fibres under alkaline conditions. Cationised fibres showed slightly better light fastness than those on nylon or wool dyed with the same acid dye (Ciba) but their wash fastness decreased with increasing length of hydrocarbon chain (Table 4). The cationised fibres also showed excellent antimicrobial activity in spite of the small amount of cationic agent introduced into the fibre. It was also found that antimicrobial activity increased with the increase in the hydrocarbon chain [86].

30 Table 3 Fastness properties of direct, reactive and acid dyes with nylon, conventional cotton and cationised cotton
Colour fastness _______________________ Change Dye Cotton fabric K/S in colour Staining
a

Light fastnessb

Conventional cotton and cationised cotton C.I. Direct Blue 78 C.I. Direct Blue 86 C.I. Direct Red 80 C.I. Direct Yellow 106 Untreated Cationic Untreated Cationic Untreated Cationic Untreated Cationic C.I. Reactive Blue 21 C.I. Reactive Blue 203 C.I. Reactive Red 239 Untreated Cationic Untreated Cationic Untreated Cationic C.I. Reactive Orange107 Untreated Cationic Nylon and cationised cotton C.I. Acid Black 172 C.I. Acid Blue 221 C.I. Acid Red 260 C.I. Acid Yellow 79 Nylon Cationic cotton Nylon Cationic cotton Nylon Cationic cotton Nylon Cationic cotton 4-5 2-3 4-5 3-4 5 3-4 4-5 4-5 4-5 4-5 4-5 4-5 4-5 3-4 4-5 4-5 5 5 5 4-5 5 5 5 5 8.67 13.99 8.76 44.74 14.16 20.11 10.29 14.46 15.08 53.34 16.37 24.24 8.24 12.40 6.91 18.24 2 4-5 1 5 2 4-5 3 5 4-5 4 4-5 4-5 5 5 4-5 4 2-3 4 2-3 4-5 2 5 3-4 5 5 5 4-5 4-5 4-5 4-5 5 5 5 5 5 5 3-4 4-5 5 5 5 4-5 5 4-5 4-5 4-5 5 4-5

a. Staining of nylon fabric during laundering and staining on cotton

b. 20h

31 Table 4 Fastness properties of acid dye on cotton cationised with different quaternary salts
Wash fastness ___________________ Cationic Dye C.I. Acid Red 127 Substrate Cotton agent
a

Change in colour 4-5 4 3 3 1-2 4-5 4-5 ammonium Staining 3 3 2-3 2-3 2 2-3 2-3 chloride; CEAC,

Light fastness 4-5 4-5 4-5 4-5 4-5 4 4 3-chloro-2-

CMAC CEAC CPAC CP5AC CDTAC

Nylon Wool a. CMAC,

3-chloro-2-hydroxypropyltrimethyl

hydroxypropyltriethyl ammonium chloride; CPAC, 3-chloro-2-hydroxypropyltripropyl ammonium chloride; CP5AC, 3-chloro-2-hydroxypropyltripentyl ammonium chloride; CDTAC, 3-chloro-2hydroxypropyldimethyltetradecyl ammonium chloride

The

dyeing

behavior

of

cotton,

cationised

with

3-chloro-2-

hydroxypropyl trimethyl ammonium chloride (14; Fisher Scientific), with direct dyes was investigated. Findings revealed that cationised cotton could be dyed without salt and required less rinsing to remove unfixed dye than cotton dyed by conventional methods [49]. Dyeing of this cationised cotton with fibre-reactive dyes showed deeper shades. Moreover, nonlinear colour behaviour occurred with cationised cotton at lower concentrations than with unmodified cotton, suggesting that predicting shades on cationised cotton requires caution [87]. Significant differences in dyeing rates and dye uptake of acid dyes on this cationic cotton were observed over untreated cotton. Fastness

32

to laundering and light was greatly improved for cationic cotton over untreated cotton, but remained somewhat lower than the values for nylon [88].

Cl Cl OH

CH3
+

CH3

CH3

14

The printing properties of cationised cotton that had been pretreated with compound (12) were examined and cationisation was found to be very effective in reducing fixation (steaming) times and washing off processes, and in increasing colour yield and wet fastness properties for a number of reactive [89] and direct dyes [90]. Printing on this cationic cotton with acid dyes could be carried out at neutral pH because of the presence of cationic charges on the fibers at all pH values, avoiding the need for a pH regulator in the print paste and for neutralisation during washing. This technique did not need an intensive washing procedure, and thus appeared to be a more environmentally friendly printing process [91]. The effect of cationisation on the quality of ink-jet printing on cotton fabrics was also investigated. Ink-jet printing with reactive dyes [92] and reactive inks [93] on cationised cotton was found to have good potential as a cost-effective and more environmentally friendly printing method using less dye, less thickener and less alkali without relinquishing outline sharpness.

33

Epoxy and halohydroxy propyl derivatives of diallylamine (15 and 16) have also been reported in this regard. Different epoxy and halohydroxy propyl derivatives of diallylamine were synthesised and applied to cotton fabrics before dyeing or during dyeing. Cotton fabrics treated with these agents showed improved fastness properties for a number of direct dyes (Table 5) [45].

N
+

CH3

X Cl OH
CH2

CH3 N
+

O H2C

CH2 H2C

15

16

X = OSO 3CH3, OSO 3C2H5, SO 3C6H4CH3

The effect of cationisation on the performance of cotton finishes has also been investigated. Cationisation of cotton with 2,3-epoxypropyl trimethyl ammonium chloride (12) [94] and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (14) [95] has been reported not to affect adversely the finishes. However, the alkali required for the process improved the wrinkle recovery angles of the treated fabrics.

34 Table 5 Fastness properties of direct dyes on untreated and treated cotton fabrics
ISO C2S Wash fastness ________________________ Cationic Dye C.I. Direct Red 80 agent I
a

Cotton fabric Without With

Change in colour 4 5 4 5 4-5 5 4-5 5

Staining on cotton 2 3-4 2 5 4 5 3-4 5

C.I. Direct Blue 71

Without With

C.I. Direct Violet 66

Without With

C.I. Direct Green 26

Without With

a. I, N- (3-chloro-2-hydroxypropyl)-N-methyl-N, N-diallyl ammonium p-toluenesulphonate

2.2.3 MONODERIVATIVES Mono-

AND

BIS-REACTIVE

HALOHETEROCYCLIC

and

bis-reactive

haloheterocyclic

compounds

having

monochlorotriazine as the reactive group have also been used for the cationisation of cellulose. Although these treatments enhanced the uptake of dye, there are practical drawbacks to all these treatments, including hue changes, poor penetration into the fibre [51] and light fastness limitations [22]. Monofunctional cationic agents of monochlorotriazine type (17) were evaluated on cotton yarn in the production of differential dyeing effects. Yarn pretreated with these cationic agents showed better uptake of acid and direct

35

dyes than does untreated yarn [96]. The stoichiometry of interaction of both acid and direct dyes with cotton modified with a reactive cationic agent (18) was examined. The results showed that the presence of the cationic sites enhanced the amount of dye taken up by diffuse adsorption [97].

Cl N NH N N NH H 5C 2 N
+

X R

C2 H 5

17

Cl N NH N N NH H5 C2 N
+

Cl

C2 H 5

18

Recent developments revealed that cotton fabrics pretreated with monoand bis-reactive cationic agents (19 and 20) showed fairly high degrees of exhaustion and fixation of direct dyes under neutral conditions in the absence of salt. Improved fastness was achieved for this modified fibre when compared with untreated samples. Results also indicated that cotton pretreated with the

36

bis-reactive cationic agent showed higher degrees of dye exhaustion and fixation relative to cotton pretreated with mono-reactive agent (Table 6) [50].

Cl N NH N N NH H 5C 2 N
+

C2 H 5

C2 H 5

19

NH N I H 5C 2 N
+

NH N C2 H 5

NH N

N N

NH

I N

Cl C2 H5

Cl H 5 C2

H 5C 2

C2 H5

20

Reactive cationic agents, phenylmonochlorotriazinyl and epoxypropyl, were used for cotton pretreatment using a paddrycuring technique. The dyeability of cationised cotton fabrics using CI Acid Red 1 was found to be dependent on the cationic agent concentration and the appropriate mixture used [98]. More complex multifunctional structures (21 and 22) have also been evaluated by exhaust applications and these gave effective enhancement of dye uptake [99,100].

37 Table 6 Fastness properties of direct dyes on untreated (C) and pretreated cotton fabrics with mono- (C-1) and bis-reactive (C-2) cationic agents
Wash fastnessa __________________________ Cotton Dye C.I. Direct Yellow 50 fabric C C-1 C-2 C.I. Direct Orange 61 C C-1 C-2 C.I. Direct Blue 71 C C-1 C-2 C.I. Direct Green 26 C C-1 C-2
b

Change F (%) 32 75 3 45 83 1 28 68 2 29 58 in colour 3-4 4 4-5 3-4 4 4-5 3 4 4 3-4 4-5 4-5 SC 3-4 4 4-5 3 4 4-5 2 4 4 3 4-5 4-5 SW 3 4 4-5 3-4 4 4-5 1-2 3-4 4 3 4-5 4-5

Light fastness 4-5 5 4-5 4-5 4-5 4-5 4 4 2 4 3-4 2

a. SC, staining on cotton; SW, staining on wool b. C-1, Cotton cationised with monochlorotriazine mono-reactive cationic agent; C-2, Cotton cationised with bischlorotriazine bis-reactive cationic agent

NH N NH N Cl H3C H3C N
+

NH N N N NH -

Cl

Cl
+

Cl N

CH3

CH3

H3C

CH3

21

38

NH N Cl HO CH3 N
+

NH N

NH N

N N

NH

OH CH3 Cl N
+

H3C

Cl

Cl

CH3

CH3

CH3

22

2.3 POLYMERIC QUATERNARY AMMONIUM SALTS

Many cationic polymers have been applied to cellulose with a view to enhance the uptake of anionic dyes and it is considerably more difficult in these instances to interpret the precise mechanism of the interactions involved, apart from the obvious participation of electrostatic forces between the dye anions and the basic groups (often quaternary nitrogen atoms) in the polymer. Polyamide-epichlorohydrin resin (Hercosett 125; Hercules Powder Corpn.), having azetidinium cation (23) as the reactive group, was applied to cotton with a view to produce a modified fibre suitable for the absorption and fixation of reactive dyes at neutral pH in the absence of salt. Selected highly reactive dyes gave good colour yield and fixation but lower fixation values were obtained when dyes of low reactivity were applied to the pretreated cotton [101].

39
Cl N
+

OH

23

A comparative study of the reactive dyeing of cellulosic fibres modified with Hercosett 125, 1,1-dimethyl-3-hydroxyazetidinium chloride (10) or Glytac A (12) revealed that fixation of reactive dyes, even under neutral or slightly acidic conditions, was attributed to the presence of highly nucleophilic secondary, tertiary or quaternary amino groups. Light fastness of the fibres pretreated with polymeric compound was poor because of poor penetration and distribution of dyes. However, pretreatment with lower molecular weight compound resulted in improved light fastness [22]. It was thought that better fixation of both high and low reactivity dyes might be achieved by introducing more highly nucleophilic sites into the cotton. Incorporation of thiourea and ethylenediamine into the polymer Hercosett 125, during the application process has beneficial effects on the results obtained. Thiourea addition inhibits the crosslinking of the resin, leaving more nucleophilic NH groups as sites for dye reaction [102]. Ethylenediamine promotes crosslinking of the resin but itself provides extra NH groups as dye reactive sites [103]. Pretreatment of cotton with a cationic / nucleophilic polymer facilitates the dyeing of cotton with a variety of reactive dyes in the absence of salt and alkali at neutral pH [104]. The dyeings thus produced were level and of

40

comparable depths to those obtained using the appropriate standard methods. Pretreated dyeings showed excellent wash fastness but reduction in light fastness. This pretreatment has also reduced the time and water required for dyeing, thus becoming a more environmentally friendly method for the reactive dyeing of cotton [10]. Derivatives of poly-epichlorohydrin, instead of epichlorohydrin were prepared and used as new cationic agents. Polyepichlorohydrin-dimethylamine derivative (24) was applied to cotton under alkaline conditions by the exhaustion method. Pretreatment of cotton with this agent not only reduced the amount of salt needed, but also increased the exhaustion efficiency and perspiration fastness of direct dyes (BAY; Table 7) [105].

O n Cl H N
+

CH3

CH3

24

41 Table 7 Fastness properties of direct dyes on untreated and treated (poly epichlorohydrin-dimethylamine) cotton
Wash fastness ________________________ Cotton Dye C.I. Direct Blue 78 fabric Untreated Treated C.I. Direct Orange 39 Untreated Treated C.I. Direct Blue 86 Untreated Treated K/S 14.02 14.26 11.58 11.90 6.06 11.74 Change in colour 3-4 3 3-4 3 3-4 2-3 Staining on cotton 3 3 3-4 3 4-5 4-5 Light fastness 4 3-4 4 3-4 4 3-4

A commercial cationic fixing agent, Solfix E (modified quaternary polyamine derivative; Ciba) was used to pretreat cotton prior to dyeing with six commercial direct dyes in the presence of electrolyte. Pretreatment enhanced the colour strength but wash fastness was similar to their untreated counterparts [106]. Pretreated fabrics also gave improved printability with pigment and anionic dyes. The prints obtained on cationised cotton showed better overall fastness properties than prints obtained on untreated cotton [107]. Three commercial cationic fixing agents, namely Matexil FC-PN (a phenol formaldehyde ammonium chloride condensate; ICI), Matexil FC-ER (poly diallyldimethyl ammonium chloride; 25, ICI) and Solfix E (Ciba), originally marketed as aftertreating agents for direct dyes, were used as pretreatments for cotton modification. Pretreatment was found to increase the colour strength of

42

the dyeings when dyeing had been carried out without electrolyte. However, when electrolyte was used, the pretreated samples exhibited generally lower colour strength than the standard dyeings. The wash fastness of the dyeings almost remained unaffected by pretreatment while light fastness was slightly lowered [108]. The study of the effect of different pretreatment agents on the uptake of 1:2 metal complex acid dyes by samples of cotton / polyamide fabrics showed excellent dye uptake by the pretreated samples compared with the untreated samples. The pretreatment using Matexil FC-ER (25, ICI) or a development cationic fixing agent gave the most uniform results [109]. Modification of cotton with a polymeric quaternary ammonium compound of 4-vinyl pyridine (26) has enabled the dyeing of cotton fibre with 1:2 metal complex acid dyes without salt at neutral or slightly acidic pH values. Pretreated dyeings displayed high colour strength, good to very good wash fastness and excellent light fastness (Table 8) [110].

n N H3C
+

Cl

N H3C

Cl

CH3

25

26

43 Table 8 Colour strength and fastness properties of 1:2 metal complex acid dyes on untreated and pretreated cotton (PT)
Wash fastness _______________________ Cotton Dye C.I. Acid Yellow 137 fabric
a

Change K/S 2.1 14.4 1.8 18.0 2.3 15.8 1.5 12.3 1.9 16.1 0.8 15.7 1.4 16.3 1.7 13.8 in colour 5 5 4-5 4-5 4-5 4 4 4

Staining on cotton 5 5 5 5 5 5 5 5

Light fastness 7 6 7 6 6 6 6 7

Untreated PT

C.I. Acid Red 182

Untreated PT

C.I. Acid Black 107

Untreated PT

C.I. Acid Orange 144

Untreated PT

C.I. Acid Blue 284

Untreated PT

C.I. Acid Brown 384

Untreated PT

C.I. Acid Violet 90

Untreated PT

C.I. Acid Blue 193

Untreated PT

a. PT, cotton pretreated with poly (4-vinyl-N-ethylpyridine) quaternised polymer

Homopolymer or copolymers of alkyl diallylamine with epichlorohydrin have also been reported to improve the wet fastness properties of anionic dyes on textile fibres [12,111]. Aftertreatment with copolymers of mono and diallylamine enhanced the colour fastness of reactive dyes on cellulosic fabrics [112,113].

44

Aftertreatment of the dyeings produced on cellulosic fibres, pretreated with fixing agent 25 and Fixogene CXF (copolymer of dimethylamine and epichlorohydrin; 27, ICI), with cationic polymers enhanced the light and wash fastness of acid (Table 9) [114] and reactive dyes [44]. The subsequent application of syntan (synthetic tanning agent) to the aftertreated dyeings enhanced the effectiveness of commercial cationic fixing agents, Matexil FCER (25) and Fixogene CXF (27), in improving the wash fastness of three commercial direct dyes (Ciba- Geigy) on cotton but the effect of syntan was both dye and fixing agent specific (Table 10) [115]. It has also been examined that wash fastness was noticeably better when these fixing agents were applied under alkaline conditions (Table 11) [116].

Cl

N(CH3)2 OH n

27

45 Table 9 Fastness properties of acid dyes on cotton

Aftertreatmentb Wash fastness ____________ Mate% rial % __________________________ Staining Cotton MateSample rial Shade ________________ change C W N K/S Light fastness

Pretreatmenta ___________

C.I. Acid Green 106 1C 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 PT1 PT1 PT1 PT1 PT2 PT2 PT2 PT2 2 2 2 2 2 2 2 2 AT1 AT2 AT3 AT1 AT2 AT3 2 2 2 2 2 2 3/3-4 3-4/4 3-4 4/4-5 2/2-3 3-4 2-3/3 4-5 4-5/5 5 5 5 4-5/5 5 5 5 0.9 5.60 5.78 5.80 5.73 6.05 6.01 6.06 5.97 6-7 -

C.I. Acid Red 315 2C.1 2.1.1 2.1.2 2.1.3 2.1.4 2.1.5 2.1.6 PTI PTI PTI PT2 PT2 PT2 2 2 2 2 2 2 AT1 AT3 AT1 AT3 2 2 2 2 3 3-4 4 2-3 3-4 4 2-3 3 3/3-4 2-3 3 3-4 4 4-5 4-5 3-4/4 4 4-5 3/3-4 3-4/4 4 3/3-4 3-4 4 1.96 9.89 10.93 5 -

C.I. Acid Yellow 235 2C.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.2.6 PT1 PT1 PT1 PT2 PT2 PT2 2 2 2 2 2 2 AT1 AT3 AT1 AT3 2 2 2 2 3 3-4 3-4/4 2/2-3 3-4/4 4 4-5 4-5 5 4-5 4-5 5 3-4 4/4-5 4-5 3/3-4 4 4-5 4/4-5 4-5 4-5 4 4-5 4-5 2.17 7.23 6.54 6-7 -

a. PT1, Matexil FC-ER; PT2, Fixogene CXF; b. AT1, Matexil FC-ER; AT2, Fixogene CXF; AT3, Copolymer of diallyldimethyl ammonium and diallyl-2-hydroxy-3-chloropropyl ammonium chloride

46 Table 10 Fastness properties of direct dyes on cotton aftertreated with cationic fixing agents / syntan
K/S ______________ Before After Dye C.I. Direct Red 89 Aftertreatments NIL 4% M FC-ER 4% M FC-ER / 2% F AXF 4% F CXF 4% F CXF / 2% F AXF C.I. Direct Yellow 106 NIL 4% M FC-ER 4% M FC-ER / 2% F AXF 4% F CXF 4% F CXF / 2% F AXF C.I. Direct Blue 85 NIL 4% M FC-ER 4% M FC-ER / 2% F AXF 4% F CXF 4% F CXF / 2% F AXF
b

Wash fastnessa _________________ S 4 4-5 4-5 4-5 4-5 3 4 4 4 4 3 4-5 4-5 4-5 4-5 C 1 2-3 2-3 1-2 2 1 2-3 3 1-2 1-2 1 2-3 2-3 1-2 2 V 1-2 3 3 2 2-3 1-2 3 3-4 2 2 1-2 3 3 2 2

wash 14.84 14.21 13.77 14.74 14.45 10.98 10.49 10.31 10.36 10.65 17.06 17.06 16.81 16.08 16.81

wash 11.13 12.75 13.34 12.72 13.26 8.01 9.94 10.11 8.81 8.73 12.42 16.94 16.14 15.79 15.96

a. S, change in shade; C, staining of adjacent cotton; V, staining of adjacent viscose b. M, Matexil; F, Fixogene

47 Table 11 Fastness properties of direct dyeings aftertreated with Fixogene CXF and Matexil FC-ER under neutral and alkaline conditions
Colour fastness __________________ Staininga Shade __________ Dye C.I. Direct Red 89 pH 7 11 7 11 C.I. Direct Yellow 106 7 11 7 11 C.I. Direct Blue 85 7 11 7 11 a. C, Cotton; V, Viscose Cationic agent NIL 4% Fixogene CXF 4% Fixogene CXF NIL 4% Matexil FC-ER 4% Matexil FC-ER NIL 4% Fixogene CXF 4% Fixogene CXF NIL 4% Matexil FC-ER 4% Matexil FC-ER NIL 4% Fixogene CXF 4% Fixogene CXF NIL 4% Matexil FC-ER 4% Matexil FC-ER K/S 14.84 14.74 14.64 14.84 14.21 13.18 10.98 10.36 10.57 10.98 10.49 10.57 17.06 16.08 16.68 17.06 17.06 17.40 change C 4 4-5 4-5 4 4-5 4-5 3 4 4 3 4 4 3 4-5 4-5 3 4-5 4-5 1 1-2 2 1 2-3 3 1 1-2 2-3 1 2-3 3-4 1 1-2 2 1 2-3 3 V 1-2 2 2-3 1-2 3 3 1-2 2 3 1-2 3 4 1-2 2 3 1-2 3 4

A new fibre modification technique based on a cationic acrylic copolymer (polymer pL) has been established. Pretreatment of cotton with this polymer increased both the substantivity and reactivity of the fibre towards reactive dyes, even under neutral or acidic conditions [117]. Recently, poly

48

(vinylamine chloride) has been investigated as a pretreatment for the salt-free dyeing of cotton with reactive dyes. Dye fixation was found to be much higher than by conventional dyeing without pretreatment, even in the presence of a large amount of salt. Dyed cotton pretreated with poly (vinylamine chloride) showed excellent wash fastness and good rub fastness [118]. Grafting reactions with cellulose by free radical polymerisation have been explored for many years but the development of modified cotton fibres with enhanced dyeability via this route has attracted particular interest recently. The direct dyeing properties of cotton grafted with 2-vinylpyridine and then quaternised with alkyl bromides or epichlorohydrin were studied under various dyeing conditions. The results indicated that grafting with 2-vinylpyridine increased the dye exhaustion markedly and quaternised grafted specimens showed a further increase in exhaustion of dyes [119]. The modification and bleaching of cotton was carried out in a single bath by graft polymerisation of the cationic monomer, methacrylolaminopropyltrimethyl ammonium chloride. This modified bleached cotton enhanced the colour strength of reactive dye in the absence of salt. However, the bleaching performance in the presence of modifying agent was slightly reduced [120].

EXPERIMENTAL WORK

50

Chapter 3 EXPERIMENTAL WORK

3.1 GENERAL INFORMATION

N,N,N',N'-tetraethylmethylenediamine was synthesised in the laboratory by the reported method [121]. Clarke's method [122] was used for the synthesis of N,N-dimethylglycine hydrochloride while 3-dimethylaminopropionic acid hydrochloride was prepared by the acidic hydrolysis of 3-

dimethylaminopropionitrile [123]. These hydrochlorides were converted to free amino acids by Galat's method [124]. Other chemicals and solvents were obtained from Merck, BDH or Acros and were used after purification through distillation. Progress of the reactions was monitored by performing chemical tests and TLC of the reaction mixture. The products were purified through various methods and vacuum dried before performing spectroscopic analysis. Purity of the products was checked by thin layer chromatography using precoated silica gel plates (Merck 60F254). Elemental analysis was performed

51

on Carto Erba MOD-1106 elemental analyser. The structures of the quaternary ammonium salts were charaterised using IR and 1HNMR spectroscopy. IR spectra were recorded on a Thermo Nicolet IR 200 spectrometer. 1HNMR spectra were recorded in MeOH-d4 solution on a Bruker DPX-400 instrument at 400 MHz. Chemical shifts are reported in ppm using TMS as an internal standard. Mass spectra were recorded on a Jeol SX-102 instrument. Scoured and bleached cotton fabric was used for dyeing. Commercial samples of C.I. Direct Orange 26, C.I. Direct Red 31, C.I. Direct Black 22, C.I. Reactive Orange 13, C.I. Reactive Red 45, C.I. Reactive Blue 5, C.I. Acid Yellow 23 and C.I. Acid Black 234 were generously supplied by Sandal Dyestuff Industries Limited, Pakistan and were used without further purification. All other chemicals used were of laboratory reagent grade. The absorption maximum ( max. values) of dyes were measured using UV-1700 Pharmaspec UV-Visible spectrophotometer. Dyeing of cotton samples was carried out in ATLAS D 400 IR Infrared laboratory dyeing machine. Datacolor SF 650X Spectraflash was used for colorimetric analysis of the dyed samples and WASHTEC-P ST 13 8TY was used for the washing of the dyed samples. Colorfastness to light of the dyed textile fabrics was determined using ATLAS Ci 3000+ Xenon Weather-Ometer. Grey scales were used for assessing change in colour and staining of adjacent fabrics.

52

3.2 SYNTHESIS OF MONO- AND BIS-REACTIVE 2,3-EPOXY / 3-CHLORO-2-HYDROXY PROPYL DERIVATIVES OF

QUATERNARY AMMONIUM CHLORIDE

Eight mono-reactive (Figure 9) and four bis-reactive (Figure 10) 2,3epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride have been synthesised by reacting epichlorohydrin with suitable tertiary amines and diamines. Mono-reactive derivatives also contain cyano and carboxylic groups in addition to 2,3-epoxy / 3-chloro-2-hydroxy propyl groups. Reaction parameters such as time and temperature have been optimised for the synthesis of these compounds.

53
CH3 Cl N H3C (CH2)n X Conc. HCl 20 C CH3
o

H3C

(CH2)n X

H2O 30-50 C
o

Cl O

H2O 30-50 C
o

Cl O

CH3 N O
+

Cl

Cl OH

CH3 N
+

Cl

(CH2)n X

(CH2)n X

CH3

CH3

28

29

X = CN, COOH n = 1, 2

Figure 9

Synthesis of mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride

28a 28b 28c 28d

n = 1, n = 1, n = 2, n = 2,

X = CN X = COOH X = CN X = COOH

29a 29b 29c 29d

n = 1, n = 1, n = 2, n = 2,

X = CN X = COOH X = CN X = COOH

54
H R

R N R

R N (CH2)n Conc. HCl R 20 C

o

H Cl R

RR N
+

Cl
+

N (CH2)n

H2O 30-50 C
o

Cl O

H2O 30-50 C
o

Cl O

O R N
+

Cl

N
+

Cl R O HO Cl R N R R Cl

N
+

Cl OH R

(CH2)n

Cl R

(CH2)n

30

31

R = CH3, C 2H5 n = 1, 2

Figure 10

Synthesis of bis-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride

30a 30b

n = 1, n = 2,

R = C2H5 R = CH3

31a 31b

n = 1, n = 2,

R = C2H5 R = CH3

55

3.2.1 GENERAL PROCEDURE FOR THE SYNTHESIS OF MONOAND BIS-REACTIVE 2,3-EPOXYPROPYL DERIVATIVES: (28a-d and 30a-b) Amine (1.0 mmol) was added dropwise to a mixture of epichlorohydrin (1.0 mmol) and water (10 ml) over a period of 1 hour with constant stirring and maintaining the temperature between 30-50 oC. The resulting mixture was stirred at this temperature for 8-10 hours. After the completion of reaction, water and unreacted reactants were distilled off under reduced pressure and the crude product was purified by extraction with chloroform or ether to obtain a yellow to brown viscous product. Due to its high moisture sensitivity, product was kept in vacuum desiccator for drying. Same procedure was followed for the synthesis of compounds 30a-b except that the mole ratio of diamine to epichlorohydrin was 1: 2 respectively. The products were identified by performing specific chemical tests for epoxy group [125], tertiary amines [126] and quaternary ammonium salts [127].

N-Cyanomethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride (28a)

Cl N O H3C
+

CH3 N C

56

Pale yellow viscous liquid, IR: 2970, 2230, 1478, 1260, 910 cm1, 1HNMR (MeOH-d4): 4.40 (2H, s, CH2-CN), 3.45 (1H, dd, J=3.1,16.5 Hz, CH2-N), 3.33 (6H, s, CH3), 3.26 (1H, dd, J=4.4,16.5 Hz, CH2-N), 3.23 (1H, m, epoxy CH), 2.75 (1H, dd, J=4.2,4.9 Hz, epoxy CH2), 2.49 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 141 [M+], 126 [M+-CH3], HRMS calcd. for C7H13ClN2O: 176.6439; found: 176.6454, Anal. calcd. for C7H13ClN2O: C, 47.59; H, 7.41; N, 15.85; found: C, 47.55; H, 7.40; N, 15.80. N-Carboxymethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride (28b)
Cl N O H3C CH3
+

O OH

Pale yellow viscous liquid, IR: 2500-3300, 1726, 1618, 1480, 1395, 1262, 937 cm1, 1H-NMR (MeOH-d4): 12.40 (1H, brs, COOH), 4.20 (2H, s, CH2-COOH), 3.45 (1H, dd, J=3.1,16.4 Hz, CH2-N), 3.31 (6H, s, CH3), 3.26 (1H, dd, J=4.4,16.4 Hz, CH2-N), 3.22 (1H, m, epoxy CH), 2.77 (1H, dd, J=4.2,4.9 Hz, epoxy CH2), 2.50 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 160 [M+], 145 [M+-CH3], HRMS calcd. for: C7H14ClNO3: 195.6440; found: 195.6457, Anal. calcd. for C7H14ClNO3: C, 42.97; H, 7.21; N, 7.15; found: C, 42.94; H, 7.17; N, 7.19.

57

N-Cyanoethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride (28c)

Cl N O H3C
+

CH3 C N

Yellow viscous liquid, IR: 2960, 2248, 1482, 1257, 920 cm1, 1H-NMR (MeOH-d4): 3.65 (2H, t, J=7.0 Hz, CH2), 3.45 (1H, dd, J=3.1,16.5 Hz, CH2N), 3.33 (6H, s, CH3), 3.26 (1H, dd, J=4.4,16.5 Hz, CH2-N), 3.23 (1H, m, epoxy CH), 2.82 (2H, t, J=6.9 Hz, CH2-CN), 2.75 (1H, dd, J=4.2,4.9 Hz, epoxy CH2), 2.49 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 155 [M+], 140 [M+-CH3], HRMS calcd. for: C8H15ClN2O: 190.6705; found: 190.6722, Anal. calcd. for C8H15ClN2O: C, 50.39; H, 7.92; N, 14.69; found: C, 50.36; H, 7.90; N, 14.72. N-Carboxyethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride (28d)
Cl N O H3C OH
+

CH3 O

Yellow viscous liquid, IR: 2500-3300, 1740, 1610, 1475, 1380, 1271, 965 cm-1, 1H-NMR (MeOH-d4): 12.40 (1H, brs, COOH), 3.53 (2H, t, J=7.0 Hz, CH2), 3.45 (1H, dd, J=3.1,16.4 Hz, CH2-N), 3.31 (6H, s, CH3), 3.26

58

(1H, dd, J=4.4,16.4 Hz, CH2-N), 3.22 (1H, m, epoxy CH), 2.77 (1H, dd, J=4.2,4.9 Hz, epoxy CH2), 2.67 (2H, t, J=7.2 Hz, CH2COOH), 2.50 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 174 [M+], 159 [M+-CH3], HRMS calcd. for: C8H16ClNO3: 209.6705; found: 209.6721, Anal. calcd. for C8H16ClNO3: C, 45.82; H, 7.69; N, 6.68; found: C, 45.85; H, 7.69; N, 6.64. Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride] (30a)

Cl O

O C 2H 5

H 5 C2 N H 5C 2 N
+

- C 2H 5 Cl

Pale yellow viscous liquid, IR: 2987, 2960, 1472, 1269, 900 cm1, 1HNMR (MeOH-d4): 5.20 (2H, s, N+-CH2-N+), 3.45 (2H, dd, J=3.1,16.5 Hz, CH2-N), 3.29 (8H, q, J=7.0 Hz, CH2-CH3), 3.26 (2H, dd, J=4.4,16.5 Hz, CH2-N), 3.23 (2H, m, epoxy CH), 2.75 (2H, dd, J=4.2,4.9 Hz, epoxy CH2), 2.49 (2H, dd, J=3.3,4.9 Hz, epoxy CH2), 1.25 (12H, t, J=7.0 Hz, CH3), MS m/z: 272 [M+], 243 [M+-C2H5], 215 [M+-2,3-epoxypropyl], HRMS calcd. for: C15H32Cl2N2O2: 343.3328; found: 343.3361, Anal. calcd. for C15H32Cl2N2O2: C, 52.47; H, 9.39; N, 8.15; found: C, 52.50; H, 9.39; N, 8.10.

59

Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride] (30b)

Cl N
3 +

H3C

H3C
+

Cl

N - CH

CH3

Reddish-brown viscous liquid, IR: 3010, 2958, 1470, 1272, 920 cm1,
1

H-NMR (MeOH-d4): 3.72 (4H, s, CH2), 3.45 (2H, dd, J=3.1,16.5 Hz, CH2-

N), 3.33 (12H, s, CH3), 3.26 (2H, dd, J=4.4,16.5 Hz, CH2-N), 3.23 (2H, m, epoxy CH), 2.75 (2H, dd, J=4.2,4.9 Hz, epoxy CH2), 2.49 (2H, dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 230 [M+], 215 [M+-CH3], 173 [M+-2,3epoxypropyl], HRMS calcd. for: C12H26Cl2N2O2: 301.2530; found: 301.2557, Anal. calcd. for C12H26Cl2N2O2: C, 47.84; H, 8.69; N, 9.29; found: C, 47.79; H, 8.65; N, 9.26.

3.2.2 GENERAL PROCEDURE FOR THE SYNTHESIS OF MONOAND BIS-REACTIVE 3-CHLORO-2-HYDROXYPROPYL

DERIVATIVES: (29a-d and 31a-b) Conc. HCl (1.0 mmol) was added to the aqueous solution of amine (1.0 mmol) over a period of 1 hour under slow stirring and maintaining the temperature below 20 oC. After complete addition of HCl, reaction mixture was stirred for half an hour at this temperature and showed a neutral pH. Then

60

epichlorohydrin was added slowly to the above reaction mixture with continuous stirring. The temperature was raised to 30-50 oC and the reaction mixture was stirred at this temperature for 8-10 hours. After the completion of reaction, water and unreacted reactants were distilled off under reduced pressure and the crude product was purified by extraction with chloroform or ether to obtain a clear to yellow viscous product. Due to its high moisture sensitivity, product was kept in vacuum desiccator for drying. Same procedure was followed for the synthesis of 31a-b except that the mole ratio of diamine to Conc. HCl and epichlorohydrin was 1: 2: 2 respectively. The products were identified by performing specific chemical tests for epoxy group [125], tertiary amines [126] and quaternary ammonium salts [127].

N-Cyanomethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium chloride (29a)

Cl Cl N OH H3C
+

CH3 N C

Pale yellow viscous liquid, IR: 3252, 2970, 2230, 1478, 1100, 735 cm1,
1

H-NMR (MeOH-d4): 4.40 (2H, s, CH2-CN), 4.37 (1H, brs, OH), 4.18

(1H, m, CH), 3.62 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), 3.55 (1H, dd, J=3.1,16.5 Hz, CH2), 3.40 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), 3.33 (6H, s, CH3), 3.27

61

(1H, dd, J=4.3,16.5 Hz, CH2), MS m/z: 177.5 [M+], 162.5 [M+-CH3], 128 [M+CH2Cl], HRMS calcd. for: C7H14Cl2N2O: 213.1049; found: 213.1065, Anal. calcd. for C7H14Cl2N2O: C, 39.45; H, 6.62; N, 13.14; found C, 39.42; H, 6.60; N, 13.10. N-Carboxymethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium chloride (29b)
Cl Cl OH H3C N
+

CH3

O OH

Yellow viscous liquid, IR: 2500-3300, 1726, 1618, 1480, 1395, 1060, 742 cm-1, 1H-NMR (MeOH-d4): 12.40 (1H, brs, COOH), 4.38 (1H, brs, OH), 4.20 (2H, s, CH2-COOH), 4.18 (1H, m, CH), 3.63 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), 3.55 (1H, dd, J=3.1,16.4 Hz, CH2), 3.42 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), 3.31 (6H, s, CH3), 3.27 (1H, dd, J=4.4,16.4 Hz, CH2), MS m/z: 196.5 [M+], 181.5 [M+-CH3], 147 [M+-CH2Cl], HRMS calcd. for: C7H15Cl2NO3: 232.1049; found: 232.1062, Anal. calcd. for C7H15Cl2NO3: C, 36.22; H, 6.51; N, 6.03; found: C, 36.18; H, 6.50; N, 6.07.

62

N-Cyanoethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium chloride (29c)

Cl Cl - CH3 N OH H3C
+

C N

Yellowish-brown viscous liquid, IR: 3240, 2960, 2248, 1482, 1100, 735 cm1, 1H-NMR (MeOH-d4): 4.37 (1H, brs, OH), 4.18 (1H, m, CH), 3.65 (2H, t, J=7.0 Hz, CH2), 3.62 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), 3.55 (1H, dd, J=3.1,16.5 Hz, CH2), 3.40 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), 3.33 (6H, s, CH3), 3.27 (1H, dd, J=4.3,16.5 Hz, CH2), 2.82 (2H, t, J=6.9 Hz, CH2-CN), MS m/z: 191.5 [M+], 176.5 [M+-CH3], 142 [M+-CH2Cl], HRMS calcd. for: C8H16Cl2N2O: 227.1314; found: 227.1329, Anal. calcd. for C8H16Cl2N2O: C, 42.30; H, 7.09; N, 12.33; found: C, 42.27; H, 7.05; N, 12.30. N-Carboxyethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium chloride (29d)
Cl Cl N OH H3C OH CH3
+

Clear viscous liquid, IR: 2500-3300, 1740, 1610, 1475, 1380, 1070, 740 cm1, 1H-NMR (MeOH-d4): 12.40 (1H, brs, COOH), 4.38 (1H, brs, OH), 4.18 (1H, m, CH), 3.63 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), 3.55 (1H, dd,

63

J=3.1,16.4 Hz, CH2), 3.53 (2H, t, J=7.0 Hz, CH2), 3.42 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), 3.31 (6H, s, CH3), 3.27 (1H, dd, J=4.4,16.4 Hz, CH2), 2.67 (2H, t, J=7.2 Hz, CH2COOH), MS m/z: 210.5 [M+], 195.5 [M+-CH3], 161 [M+-CH2Cl], HRMS calcd. for: C8H17Cl2NO3: 246.1315; found: 246.1330, Anal. calcd. for C8H17Cl2NO3: C, 39.03; H, 6.96; N, 5.69; found: C, 39.01; H, 6.90; N, 5.65. Methylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-diethylammonium chloride] (31a)
Cl +

Cl Cl

OH C 2H 5

H5 C2 N H 5C 2 N
+

HO Cl

C 2 H5

Pale yellow viscous liquid, IR: 3220, 2987, 2960, 1472, 1095, 740 cm1,
1

H-NMR (MeOH-d4): 5.20 (2H, s, N+-CH2-N+), 4.37 (2H, brs, OH), 4.18

(2H, m, CH), 3.62 (2H, dd, J=5.6,6.0 Hz, CH2-Cl), 3.55 (2H, dd, J=3.1,16.5 Hz, CH2), 3.40 (2H, dd, J=4.7,6.0 Hz, CH2-Cl), 3.29 (8H, q, J=7.0 Hz, CH2), 3.27 (2H, dd, J=4.4,16.5 Hz, CH2), 1.25 (12H, t, J=7.0 Hz, CH3), MS m/z: 345 [M+], 316 [M+-C2H5], 295.5 [M+-CH2Cl], HRMS calcd. for: C15H34Cl4N2O2: 416.2547; found: 416.2579, Anal. calcd. for C15H34Cl4N2O2: C, 43.28; H, 8.23; N, 6.72; found: C, 43.25; H, 8.19; N, 6.75.

64

Ethylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium chloride] (31b)

Cl H3C HO Cl N
+

H3C Cl N
+

Cl

- CH3

CH3 OH

Clear viscous liquid, IR: 3224, 3010, 2958, 1470, 1100, 742 cm1, 1HNMR (MeOH-d4): 4.37 (2H, brs, OH), 4.18 (2H, m, CH), 3.72 (4H, s, CH2), 3.62 (2H, dd, J=5.6,6.0 Hz, CH2-Cl), 3.55 (2H, dd, J=3.1,16.5 Hz, CH2), 3.40 (2H, dd, J=4.7,6.0 Hz, CH2-Cl), 3.33 (12H, s, CH3), 3.27 (2H, dd, J=4.4,16.5 Hz, CH2), MS m/z: 303 [M+], 288 [M+-CH3], 253.5 [M+-CH2Cl], HRMS calcd. for: C12H28Cl4N2O2: 374.1749; found: 374.1775, Anal. calcd. for C12H28Cl4N2O2: C, 38.51; H, 7.54; N, 7.48; found: C, 38.55; H, 7.51; N, 7.52.

3.3 APPLICATIONS
The synthesised compounds were applied to cotton fabrics as

pretreatments and optimum conditions for the cationisation of cotton fabric with these compounds have been determined. Dyeing properties of these pretreated fabrics with direct, reactive and acid dyes have also been investigated. These compounds were also applied to the dyed cotton fabrics as aftertreatments and the effect of different pH conditions and concentration on the effectiveness of these compounds as fixing agents has been studied.

65

Since both epoxy and halohydroxy propyl derivatives of quaternary ammonium salts react with cellulose under alkaline conditions and have the same reactive group as shown in Figure 7 and 8 therefore, epoxy derivatives have been applied to the cotton fabrics as pretreatments and aftertreatments and their effects on the colour strength (K/S) and fastness properties of dyed fabrics have been evaluated.

3.3.1 APPLICATION PRETREATMENT

OF

CATIONIC

FIXING

AGENTS

AS

3.3.1.1 Pretreatment of cotton fabrics Cotton fabrics were pretreated with compounds 30a, 30b and 28c using the exhaust method (Table 12). Pretreatment was carried out in a laboratory dyeing machine at a liquor ratio of 25:1. Afterwards, the fabrics were rinsed in tap water and then neutralised with 2% CH3COOH for 5 minutes at 40o C. Neutralised fabrics were again rinsed in tap water and dried at room temperature.
Table 12
Pretreatment method 1. 2. 3. 4.

Pretreatment conditions
Temperature ( C) 40-100 80 80 80
o

Time (min.) 30 20-50 30 30

Conc. of NaOH (% ow cationic agent) 30 30 30 10-40

Conc. of cationic agenta (% owf) 2 2 2-10 2

a. 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride]

66

3.3.2 DYEING CONDITIONS FOR UNTREATED COTTON FABRICS 3.3.2.1 Dyeing of untreated cotton fabrics with direct dyes by conventional method Untreated cotton fabrics were dyed with direct dyes in a laboratory dyeing machine at a liquor ratio of 25:1 using 15-30g/L of sodium chloride under neutral conditions. Dyeing was started at 30 oC and temperature of the dye bath was raised to 100 oC over 20 minutes. Dyeing was continued at this temperature for a further 50 minutes. Dye bath was then cooled and discarded (Figure 11). Dyed fabrics were rinsed thoroughly in tap water and dried at room temperature.

50 min. 100 oC

15-30 g/L NaCl

25: 1 30 oC

Rinsing

Figure 11

Dyeing profile of untreated cotton fabric with direct dyes

3.3.2.2 Dyeing of untreated cotton fabrics with reactive dyes by conventional method Untreated cotton fabrics were dyed with reactive dyes in a laboratory dyeing machine according to the dyeing profile shown in Figure 12. Dyed samples were rinsed in tap water, then rinsed in hot water at 60 oC for 5

67

minutes and again rinsed in tap water. Dyed samples were squeezed and dried at room temperature.

80 oC 20g/ L Na2CO3 60 g/ L NaCl 25: 1 30 oC

45 min.

Rinsing

Figure 12

Dyeing profile of untreated cotton fabric with reactive dyes

3.3.2.3 Dyeing of wool fabrics with acid dyes Wool fabrics were dyed with acid dyes (2% owf) at a liquor ratio of 30:1. The pH of the bath was adjusted to 3 with acetic acid prior to adding the fabric. The bath was then heated to 100 oC in 25 minutes and held at this temperature for 1 hour. The bath was then cooled and discarded. The fabric was rinsed in tap water and dried.

3.3.3 DYEING CONDITIONS FOR PRETREATED COTTON FABRICS 3.3.3.1 Dyeing of pretreated cotton fabrics with direct dyes Pretreated cotton fabrics were dyed with direct dyes in the absence of salt in a laboratory dyeing machine at a liquor ratio of 25:1 under neutral conditions (Table 13). Dye bath was then cooled and dyed fabrics were rinsed

68

thoroughly in tap water and dried at room temperature. The effect of temperature, time, dye concentration and fixing agent concentration on the dyeing behaviour of pretreated cotton fabrics has been investigated. For comparison, untreated cotton fabrics were also dyed under the same conditions.

Table 13
Dyeing method 1. 2. 3. 4.

Dyeing conditions with direct dyes

Temperature (oC) 60-100 100 100 100 Time (min.) 30 20-50 30 30 Conc. of dyea (% owf) 2 2 2-6 2 Conc. of cationic agent (% owf) 2 2 2 1-4
b

a. C. I. Direct Orange 26 b. 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride], 30b Ethylene bis-[N(2,3-epoxypropyl)-N,N-dimethylammonium chloride], 28c N-Cyanoethyl-N-(2,3-epoxypropyl)N,N-dimethylammonium chloride

3.3.3.2 Dyeing of pretreated cotton fabrics with reactive dyes Pretreated cotton fabrics were dyed with reactive dyes in a laboratory dyeing machine at a liquor ratio of 25:1 (Table 14). Dye bath was then cooled and dyed fabrics were rinsed thoroughly in tap water and dried at room temperature. The effect of dyeing conditions on the pretreated fabrics has been investigated in detail. For comparison, untreated cotton fabrics were also dyed with reactive dyes under the same conditions.

69

Table 14
Dyeing method 1. 2. 3. 4. 5.

Dyeing conditions with reactive dyes

Temperature ( C) 60-100 80 80 80 80
o

Time (min.) 30 15-45 30 30 30

Na2CO3 (g/L) 10-20

Conc. of dyea (% owf) 2 2 2-6 2 2

Conc. of cationic agent (% owf) 2 2 2 1-4 2

b

a. C. I. Reactive Orange 13 b. 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride], 30b Ethylene bis-[N(2,3-epoxypropyl)-N,N-dimethylammonium chloride], 28c N-Cyanoethyl-N-(2,3-epoxypropyl)N,N-dimethylammonium chloride

3.3.3.3 Dyeing of untreated and pretreated cotton fabrics with acid dyes Untreated and pretreated (2% owf) cotton fabrics were dyed with acid dyes (1-4% owf) in a laboratory dyeing machine according to the dyeing profile shown in Figure 13. Dyed samples were then rinsed in tap water, squeezed and dried at room temperature.

70
60 min. 100 C
o

Rinsing 30 oC

Dye pH Liquor ratio Figure 13

1-4% owf Neutral 30:1

Dyeing profile of untreated and pretreated cotton fabrics with acid dyes

3.3.4 APPLICATION OF CATIONIC FIXING AGENTS AS AN AFTERTREATMENT A bis-reactive derivative of quaternary ammonium salt (Compound 30b) was applied to cotton fabrics dyed with direct dyes. The effect of different pH conditions and concentration on the effectiveness of this cationic fixing agent has been investigated. 3.3.4.1 Dyeing with direct dyes Cotton fabrics were dyed with direct dyes (2% owf) in a laboratory dyeing machine at a liquor ratio of 25:1 using 15g/L of sodium chloride. Dyeing was started at 30 oC and then temperature was raised to 100 oC over 20 minutes. Dyeing was continued at this temperature for a further 50 minutes.

71

Dye bath was then cooled to 70 oC and discarded. Dyed fabrics were rinsed thoroughly and dried at room temperature. 3.3.4.2 Aftertreatment with cationic fixing agent (30b) 2% and 4% (owf) of bis-reactive cationic agent (30b) was applied to the dyed fabrics (2% owf) in a laboratory dyeing machine at a liquor ratio of 25:1. The cationic agent was applied both at pH 7 and pH 11. The method used is given in Figure 14.

30 minutes 40 C A
o

Dyed cotton fabric (2% owf) Cationic fixing agent (2% or 4% owf) Either pH 7 or pH 11 using 1% NaOH soln. Liquor ratio 25:1

Figure 14

Aftertreatment of direct dyed cotton fabrics with cationic fixing agent (30b)

3.4 COLOUR MEASUREMENT

The reflectance values and the corresponding CIE L*, a*, b*, C* and ho colour coordinates of the samples were measured using Datacolor SF 650X

72

Spectraflash attached to a personal computer under illuminant D65 using a 10o standard observer. From the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the samples were calculated using KubelkaMunk equation (Eqn. 1).

(1 R) 2 K/S = 2R

Eqn. 1

3.5 FASTNESS TESTING

Colour fastness is the fundamental requirement of dyed textile materials. It is defined [128] as "Resistance to the change in colour of the dyed textile material when subjected to a particular set of conditions." Colour fastness is usually assessed with respect to change in colour of the fabric in the test and with respect to staining of adjacent fabrics.

3.5.1 WASH FASTNESS Wash fastness of the dyeings was determined according to standard ISO methods [129]. Samples were subjected to ISO 105: C06/C2S wash test (60
o

C).

73

3.5.1.1 Test procedure The composite specimen (fabric under test stitched with adjacent fabric) along with 25 steel balls was placed in each container and necessary amount of detergent solution, previously heated to 60 2 oC, was added to give a liquor ratio of 50:1. The specimen was run at this temperature for 30 minutes. The composite specimen was removed, rinsed twice for a period of 1 minute in separate 100 ml portions of water at 40 oC. The specimen was squeezed, unstitched and dried at room temperature. After drying, samples were visually assessed for shade change and staining on adjacent fabric using grey scale. The grey scale ranges from 5 for no shade change (or no stain on adjacent fiber) down to 1 for a severe shade change (or staining) with half points in between.

3.5.2 LIGHT FASTNESS Colour fastness to light of the dyeings was tested according to AATCC test method 16-2003 [130]. The dyed samples were exposed to xenon arc using AATCC Blue Wool Light Fastness Standards as a reference. The colourfastness to light of the specimens was evaluated by comparison of the colour change of the exposed portion to the masked portion of the test specimen or unexposed original material using grey scale for colour change.

RESULTS AND DISCUSSION

75

Chapter 4 RESULTS AND DISCUSSION

4.1 SYNTHESIS OF MONO- AND BIS-REACTIVE 2,3-EPOXY AND 3-CHLORO-2-HYDROXY PROPYL DERIVATIVES
It has been found that below 30 oC either little or no product is formed even after stirring for long hours. High temperature was avoided due to the cleavage of epoxy ring of epichlorohydrin and the synthesised products. In addition high temperature may lead to the polymerisation of product. A temperature range of 3050 oC was found to be most suitable to get the products using stoichiometric ratio of reactants. Reaction conditions and yields of these compounds are given in Table 15. Reactions were monitored by performing specific chemical tests for epoxy group [125], tertiary amines [126] and quaternary ammonium salts [127]. Epoxy compounds (28a-d and 30a-b) gave negative test for tertiary amines and positive test for quaternary amines whereas halohydroxy compounds (29a-d and 31a-b) showed positive test for

76

quaternary amines and negative test for tertiary amines and epoxy group. The IR and 1HNMR data, which have been given in experimental section, also confirmed the identity of the compounds.

Table 15
Salt 28a 28b 28c 28d 30a 30b

Reaction conditions and yields of salts 28a-d, 29a-d, 30a-b and 31a-b
Yield (%) 57 72 75 65 53 86 Salt 29a 29b 29c 29d 31a 31b Reaction conditions 40-50 oC, 8 hrs. 40-50 C, 8 hrs. 40-50 C, 8 hrs. 40 C, 7 hrs. 40-50 C, 10 hrs. 30-40 C, 8 hrs.
o o o o o

Reaction conditions 30 oC, 9 hrs. 40-50 C, 8 hrs. 30 C, 9 hrs. 40 C, 8 hrs. 40-50 C, 10 hrs. 40-50 C, 9 hrs.
o o o o o

Yield (%) 59 69 78 73 40 84

Solubility of these compounds has been checked in different solvents. All the compounds were soluble in methanol, DMSO and water while they were insoluble in ether and chloroform. Purity of these compounds has been checked by thin layer chromatography using precoated silica gel plates (Merck 60F254) and following the method of Bluhm and Li [131]. It has further been verified by elemental analysis and results of elemental analysis have been given in experimental section. The products obtained were in the form of viscous liquid due to their hygroscopic nature. However under anhydrous conditions using chloroform as a solvent, products were obtained as white crystalline solid. These crystalline products again turned into viscous liquid on exposure to air/ atmosphere after a

77

short while. Therefore, the products were dried before elemental analysis by keeping in vacuum desiccator for several days.

4.2 APPLICATIONS
The synthesised quaternary ammonium chlorides have been applied to the cotton fabrics as pretreatments and aftertreatments and promising results have been obtained. The absorption maximum ( max.) values of the dyes (used in this work) in aqueous solution were measured by UV-Visible Spectrophotometer and the max. values of the cotton fabrics dyed with these dyes were measured by datacolor. The max. values of the dyes in aqueous solution and on the dyed fabrics are given in Table 16.

Table 16

max. values of dyes

max. (nm) max. (nm) of fabrics dyed under neutral conditions max. (nm) of fabrics dyed under alkaline conditions 500 540 610 -

Dye

in water

C. I. Direct Orange 26 C. I. Direct Red 31 C. I. Direct Black 22 C. I. Reactive Orange 13 C. I. Reactive Red 45 C. I. Reactive Blue 5 C. I. Acid Yellow 23 C. I. Acid Black 234

507 524 658 492 520 598 416 608

510 540 630 500 520 600 400 610

78

4.2.1 PRETREATMENT WITH CATIONIC FIXING AGENTS Cotton fabrics were cationised by pretreatment with mono-reactive (compound 28c) and bis-reactive derivatives (compound 30a and 30b) under alkaline conditions using the exhaust method. A bis-reactive derivative, compound 30b was used to determine the optimum conditions for the pretreatment of cotton fabrics. The amount of cationic agent (compound 30b) introduced into the cotton fabric was evaluated from the chlorine content of the fabric. The chlorine content of the cationised fabrics under different pretreatment conditions have been given in Table 17-20 and graphically represented in Figure 15-18.

4.2.1.1 Effect of temperature and time on the cationisation of cotton fabrics As shown in Table 17, chlorine content of the fabric increased with the increase in temperature up to 80 oC and then decreased rapidly. From Table 18, it can also be observed that chlorine content of the fabric increased with time up to 30 minutes and then decreases rapidly. The decrease in chlorine content may be due to the partial hydrolysis of the cationic agent that occurs at high temperature prior to its reaction with cellulose. Therefore, further study of the pretreatment conditions was carried out at 80o C for 30 minutes.

79

Table 17

Effect of temperature on the chlorine content of cationised fabric

Temperature ( C) 40 60 80 100
o

Chlorine content of the fabric (%) 0.2838 0.2950 0.3308 0.2662

0.4 Chlorine content (%) 0.3 0.2 0.1 0 0 20 40 60 Temp. ( C)

o

80

100

120

Figure 15

Effect of temperature on the chlorine content of cationised cotton fabric [Cationisation conditions: Compound 30b; 2% (owf), NaOH 30% (ow cationic agent), Liquor ratio 25:1, Time 30 min.]

80

Table 18

Effect of pretreatment time on the chlorine content of cationised fabric

Time (min.) 20 30 40 50

Chlorine content of the fabric (%) 0.2844 0.3308 0.2917 0.2623

0.4 Chlorine content (%) 0.3 0.2 0.1 0 0 10 20 30 Time (min.) 40 50 60

Figure 16

Effect of pretreatment time on the chlorine content of cationised cotton fabric [Cationisation conditions: Compound 30b; 2% (owf), NaOH 30% (ow cationic agent), Liquor ratio 25:1, Temp. 80 oC]

81

4.2.1.2 Effect of cationic agent (owf) and sodium hydroxide (ow cationic agent) concentrations on the cationisation of cotton fabrics The effect of cationic agent concentration (based on the weight of the fabric) and sodium hydroxide concentration (based on the weight of cationic agent) on the chlorine content of the cationised fabric has also been investigated. It was found that chlorine content of the fabric increases with the increase in the conc. of the cationic agent (Table 19). However, the rate of increase of chlorine content decreases with the increase in the conc. of the cationic agent above 2% (owf).

Table 19

Effect of cationic agent concentration on the chlorine content of cationised fabric

Conc. of cationic agent (% owf) 2 4 6 8 10 Chlorine content of the fabric (%) 0.3308 0.3459 0.3678 0.3806 0.3986

From Table 20, it can also be seen that chlorine content of the fabric increases with the increase in the conc. of sodium hydroxide up to 30% (ow cationic agent). A further increase in the conc. of sodium hydroxide decreases

82

the chlorine content of the fabric suggesting that a conc. of 30% (ow cationic agent) was sufficient for the fixation of cationic agent with the fabric.

Table 20

Effect of NaOH concentration on the chlorine content of cationised fabric

Conc. of NaOH (% ow cationic agent) 10 20 30 40 Chlorine content of the fabric (%) 0.2741 0.2844 0.3308 0.2940

The use of high concentration of alkali or the fixing agent increases the rate of hydrolysis of the cationic agent which in turn decreases the chlorine content of the fabric. Thus, cationic agent 2% (owf) and sodium hydroxide 30% (ow cationic agent) were chosen as optimum conditions for the pretreatment of cotton fabrics. The effect of cationic agent and NaOH concentration on the chlorine content of cationised cotton fabric has been graphically represented in Figure 17 and 18. Under the above mentioned conditions, cotton fabrics were cationised by pretreatment with bis-reactive derivatives 30a (C-1) and 30b (C-2). A mono-reactive derivative, 28c was also used for the cationisation of cotton fabrics under the same conditions (C-3). This compound contains cyano group, hydrolysis of which might take place during pretreatment.

83

0.5 Chlorine content (%) 0.4 0.3 0.2 0.1 0 0 2 4 6 8 10 12 Conc. of cationic agent (% owf)

Figure 17

Effect of cationic agent concentration on the chlorine content of cationised cotton fabric [Cationisation conditions: Compound 30b; NaOH 30% (ow cationic agent), Liquor ratio 25:1, Temp. 80 oC, Time 30 min.]

0.4 Chlorine content (%) 0.3 0.2 0.1 0 0 10 20 30 40 50

Conc. of NaOH (% ow cationic agent)

Figure 18

Effect of NaOH conc. on the chlorine content of cationised cotton fabric [Cationisation conditions: Compound 30b; 2% (owf), Temp. 80 oC, Time 30 min., Liquor ratio 25:1]

84

4.2.2 DYEING OF UNTREATED AND PRETREATED COTTON FABRICS WITH DIRECT DYES Untreated cotton fabric (C) and cotton fabrics pretreated with compound 30a (C-1), 30b (C-2) and 28c (C-3) were dyed with direct dyes in the absence of salt under neutral conditions (Table 13). The effect of pretreatment on the direct dyeing properties of cotton fabrics was studied in detail. This study was carried out with C.I. Direct Orange 26 ( max. 510 nm). The % Reflectance values (%R) of the dyeings were measured using datacolor. From the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated using Kubelka-Munk equation (See Eqn.1 on page 72).

4.2.2.1 Effect of dyeing temperature The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with C.I. Direct Orange 26 (2% owf) in the absence of salt under neutral conditions at different temperature conditions. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 21.

85 Table 21 % Reflectance (at max. 510 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) under different temperature conditions
Temperature (oC) 60 Cotton fabrica C C-1 C-2 C-3 70 C C-1 C-2 C-3 80 C C-1 C-2 C-3 90 C C-1 C-2 C-3 100 C C-1 C-2 C-3 % Reflectance at max. (% R) 8.22 4.85 3.94 3.66 7.25 4.29 3.49 3.35 6.13 3.86 3.05 3.13 5.21 3.34 2.78 2.91 4.56 3.00 2.49 2.68 Reflectance R = % R / 100 0.0822 0.0485 0.0394 0.0366 0.0725 0.0424 0.0349 0.0335 0.0613 0.0386 0.0305 0.0313 0.0521 0.0334 0.0278 0.0291 0.0456 0.0300 0.0249 0.0268 Colour strength K/S = (1 - R)2 / 2R 5.12 9.33 11.71 12.67 5.93 10.67 13.34 13.94 7.18 11.97 15.40 14.99 8.62 13.98 16.99 16.19 9.98 15.68 19.09 17.67

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

86

The dyeing behaviour of untreated cotton (C) and cotton cationised with 30a (C-1), 30b (C-2) and 28c (C-3) with direct dyes has shown that an increase in temperature is accompanied by an increase in the colour strength (K/S) of the dyeings (Figure 19).

25 20 K/S C 15 K/S 10 5 0 50 60 70 80 Temp. ( C)

o

K/S C-1 K/S C-2 K/S C-3

90

100

110

Figure 19

Effect of temperature on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf)

This may be due to the increase in the disaggregation of the dye molecules and /or increase in the rate of dye penetration into the fibre. During the normal dyeing process of untreated cotton fabric, an equilibrium is established between the dye in the fibre and dye in the solution. However, during the dyeing of cationised cotton, this equilibrium is shifted towards

87

cationic cotton due to increased dye uptake as a result of interaction between the dye anions and cations in the fibre. The cationised cotton fabrics C-1 and C-2 would have higher content of cationic dye sites relative to C-3 due to their bis-reactive and bis-cationic nature. However, C-1 showed lower colour strength than C-2 and C-3 because of the steric hindrance of the cationic agent with the dye molecules. In other words, increase in the length of hydrocarbon chain attached to the ammonium group decreased the colour strength of the dyeings. Generally, higher content of the cationic dye sites in the fibre results in greater dye exhaustion and fixation, thus enhancing the colour strength of the dyeings.

4.2.2.2 Effect of dyeing time The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with C.I. Direct Orange 26 (2% owf) in the absence of salt under neutral conditions at 100 oC for different time periods. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 22.

88 Table 22 % Reflectance (at max. 510 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) at 100 oC for different time periods
Dyeing time (min.) 20 Cotton fabrica C C-1 C-2 C-3 30 C C-1 C-2 C-3 40 C C-1 C-2 C-3 50 C C-1 C-2 C-3 % Reflectance at max. (% R) 5.38 3.99 3.12 3.37 4.56 3.00 2.49 2.68 4.02 3.36 2.78 2.74 3.83 3.72 3.14 2.81 Reflectance R = % R / 100 0.0538 0.0399 0.0312 0.0337 0.0456 0.0300 0.0249 0.0268 0.0402 0.0336 0.0278 0.0274 0.0383 0.0372 0.0314 0.0281 Colour strength K/S = (1 - R)2 / 2R 8.32 11.55 15.04 13.85 9.98 15.68 19.09 17.67 11.45 13.89 16.99 17.26 12.07 12.45 14.93 16.80

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

An increase in dyeing time also results in an increase in the colour strength (K/S) of the dyeings (Figure 20). Results revealed that a dyeing time of 30 minutes was sufficient to achieve the maximum colour strength for cationised cotton fabrics (C-1, C-2 and C-3). A further increase in dyeing time

89

resulted in a decrease in the colour strength of cationised fabrics in all cases. This may be due to the deterioration of the fixing agent-fibre bonds and / or dye-fixing agent complex on prolonged heating.

25 20 K/S 15 10 5 0 0 10 20 30 40 50 60 K/S C K/S C-1 K/S C-2 K/S C-3

Time (min.)

Figure 20

Effect of dyeing time on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 (2% owf)

4.2.2.3 Effect of dye concentration The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with different concentrations (2-6% owf) of C.I. Direct Orange 26 in the absence of salt under neutral conditions at a temperature of 100 oC for 30 minutes. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 23.

90 Table 23 % Reflectance (at max. 510 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26 at 100 oC for 30 minutes using different dye concentrations
Dye conc. (% owf) 2 Cotton fabrica C C-1 C-2 C-3 3 C C-1 C-2 C-3 4 C C-1 C-2 C-3 5 C C-1 C-2 C-3 6 C C-1 C-2 C-3 % Reflectance at max. (% R) 4.56 3.00 2.49 2.68 4.23 2.98 2.46 2.57 3.90 2.94 2.42 2.47 3.53 2.61 2.37 2.19 3.20 2.31 2.18 1.97 Reflectance R = % R / 100 0.0456 0.0300 0.0249 0.0268 0.0423 0.0298 0.0246 0.0257 0.0390 0.0294 0.0242 0.0247 0.0353 0.0261 0.0237 0.0219 0.0320 0.0231 0.0218 0.0197 Colour strength K/S = (1 - R)2 / 2R 9.98 15.68 19.09 17.67 10.84 15.79 19.33 18.46 11.84 16.02 19.67 19.25 13.18 18.17 20.10 21.84 14.64 20.65 21.94 24.39

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

91

From Figure 21, it is clear that an increase in the dye concentration increases the colour strength for both the untreated (C) and pretreated fabrics (C-1, C-2 and C-3). This may be due to the excess of dye anions in the dye solution at higher conc. which form hydrogen bonds with the fabric in addition to those having electrostatic interactions with the cationic dye sites of the pretreated fabrics.

30 25 20 K/S 15 10 5 0 0 1 2 3 4 5 6 7 Dye conc. (% owf) K/S C K/S C-1 K/S C-2 K/S C-3

Figure 21

Effect of dye conc. on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2, C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26

4.2.2.4 Effect of cationic agent concentration The cotton fabrics pretreated with different concentrations of compound 30a (C-1), 30b (C-2) and 28c (C-3) were dyed with C.I. Direct Orange 26 (2% owf) in the absence of salt under neutral conditions at a temperature of 100 oC

92

for 30 minutes. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 24.

Table 24

% Reflectance (at max. 510 nm) and the colour strength (K/S) values of cotton fabrics pretreated with different conc. of cationic agents (C-1, C-2 and C-3) and dyed with C.I. Direct Orange 26 (2% owf) at 100 oC for 30 minutes

Cationic agent conc. (% owf) 1

Cotton fabric C-1 C-2 C-3

a

% Reflectance at max. (% R) 3.59 3.56 3.03 3.00 2.49 2.68 3.11 2.78 2.77 3.22 3.17 2.87

Reflectance R = % R / 100 0.0359 0.0356 0.0303 0.0300 0.0249 0.0268 0.0311 0.0278 0.0277 0.0322 0.0317 0.0287

Colour strength K/S = (1 - R)2 / 2R 12.94 13.06 15.51 15.68 19.09 17.67 15.09 16.99 17.06 14.54 14.78 16.43

C-1 C-2 C-3

C-1 C-2 C-3

C-1 C-2 C-3

a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride]; C-2, Cotton pretreated C-3, with Cotton 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N28c N-Cyanoethyl-N-(2,3dimethylammonium chloride]; pretreated with

epoxypropyl)-N,N-dimethylammonium chloride

93

The effect of cationic agent concentration on the uptake of direct dyes is shown in Figure 22. The results indicated that an increase in the concentration of cationic agent above 2% owf causes a decrease in the colour strength of the pretreated dyeings. This may be due to the partial hydrolysis of the cationic agent that occurs at higher concentrations under alkaline conditions during the pretreatment step, resulting in a decrease in the cationic dye sites in the fibre which in turn decreased the colour strength of the dyeings.

25 20 15 K/S 10 5 0 0 1 2 3 4 5 K/S C-1 K/S C-2 K/S C-3

Conc. of cationic agent (% owf)

Figure 22

Effect of cationic agent concentration on the colour strength (K/S) of pretreated cotton fabrics (C-1, C-2 and C-3) dyed with C.I. Direct Orange 26 (2% owf)

On the basis of the results obtained, untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with three direct dyes (2% owf) in the absence of salt at neutral pH. The colour strength and fastness properties of these dyeings are given in Table 25. The results indicated that

94

pretreated fabrics C-1, C-2 and C-3 have higher colour strength (K/S) values than the untreated fabrics (Figure 23). The wash fastness properties of pretreated fabrics were comparable or slightly better than the untreated fabrics but with higher colour strength. However, pretreatment has caused a slight decrease in the light fastness of the pretreated dyeings. This is common with such treatments [16].

Table 25

Colour strength (K/S) and fastness properties of direct dyes (2% owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics
Wash fastness _________________ Shade Staining Light fastness 4-5 4 4 3-4 3-4 3 3 3 5 5 5 4-5

Dye C.I. Direct Orange 26

Cotton fabric C C-1 C-2 C-3

K/S 9.98 15.68 19.09 17.67 8.94 14.58 15.83 15.68 12.56 13.67 14.96 14.64

change on cotton 3-4 3 3-4 3 2-3 2-3 3 1-2 4 3 3-4 3 3-4 3-4 4 3 4 3-4 3 2-3 3-4 4 3-4 3

C.I. Direct Red 31

C C-1 C-2 C-3

C.I. Direct Black 22

C C-1 C-2 C-3

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

95

The effect of additional group in mono-reactive cationic agent (28c) has also been investigated. The presence of additional group enhanced the colour strength of the dyeings (C-3) as a result of the interaction with other suitable groups in the dye molecules. Since these interactions still relies on electrostatic forces therefore, the wash fastness properties of the dyeings were inferior to the fabrics pretreated with bis-reactive cationic agents (C-1 and C-2).

25 20 K/S C 15 K/S 10 5 0 0 1 2 3 4 5 6 Dye conc. (% owf) K/S C-1 K/S C-2 K/S C-3

Figure 23

Colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26

A comparison of the direct dyeing of pretreated cotton fabrics (C-1, C-2 and C-3; 2% owf) (Table 25) with untreated cotton fabrics dyed by conventional method (Table 26) has indicated that pretreated fabrics showed slightly lower colour strength as compared to the untreated cotton fabrics dyed

96

by conventional method. However, the wash fastness results of pretreated fabrics were comparable or better than those of untreated fabrics. The colour strength values of the pretreated fabrics could be enhanced by increasing the dye conc. as shown in Figure 21.

Table 26

Colour strength (K/S) and fastness properties of untreated cotton fabrics dyed with direct dyes (2% owf) by conventional method
Wash fastness ________________________________ Light fastness 4-5 4 5

Dye C.I. Direct Orange 26 C.I. Direct Red 31 C.I. Direct Black 22

K/S 23.04 16.31 18.77

Shade change 3-4 2 3-4

Staining on cotton 3 3 3-4

The above findings revealed that cationised cotton fabrics could be dyed with direct dyes without salt and require less dyeing time as compared to the cotton fabrics dyed by conventional methods. Thus, high salt concentrations can be avoided in the direct dyeing of cotton fabrics which leads to the pollution of the effluents. Pretreatment of cotton fabrics with cationic fixing agents has shown good colour strength and comparable wash fastness properties without adversely affecting the light fastness of the dyeings. In short, the bis-reactive agents have proved to be more effective than the mono-reactive agent. Amongst bis-reactive derivatives, the compound with lower steric hindrance has shown superior results.

97

SHADES OF DIRECT DYES ON UNTREATED (C) AND PRETREATED (C-1, C-2 and C-3; 2% owf) COTTON FABRICS

C.I. DIRECT ORANGE 26 Untreated cotton (C)

(With salt)

(Without salt)

Pretreated cotton

C-1

C-2

C-3

C.I. DIRECT RED 31 Untreated cotton (C)

(With salt)

(Without salt)

Pretreated cotton

C-1

C-2

C-3

98

C.I. DIRECT BLACK 22 Untreated cotton (C)

(With salt)

(Without salt)

Pretreated cotton

C-1

C-2

C-3

99

4.2.3 DYEING OF UNTREATED AND PRETREATED COTTON FABRICS WITH REACTIVE DYES Untreated cotton fabric (C) and cotton fabrics pretreated with compound 30a (C-1), 30b (C-2) and 28c (C-3) were dyed with reactive dyes in the absence of salt and alkali (Table 14). The effect of pretreatment on the reactive dyeing properties of cotton fabrics was studied in detail. This study was carried out with C.I. Reactive Orange 13 ( max. 500 nm). The % Reflectance values (%R) of the dyeings were measured using datacolor. From the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated using Kubelka-Munk equation (See Eqn.1 on page 72).

4.2.3.1 Effect of dyeing temperature The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt and alkali at different temperature conditions. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 27.

100 Table 27 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at different temperature conditions
Temperature (oC) 60 Cotton fabrica C C-1 C-2 C-3 70 C C-1 C-2 C-3 80 C C-1 C-2 C-3 90 C C-1 C-2 C-3 100 C C-1 C-2 C-3 % Reflectance at max. (% R) 51.79 44.97 28.57 17.05 52.38 43.65 27.04 16.51 53.58 42.87 26.10 16.03 54.06 42.89 26.39 17.48 54.53 42.92 26.49 19.15 Reflectance R = % R / 100 0.5179 0.4497 0.2857 0.1705 0.5238 0.4365 0.2704 0.1651 0.5358 0.4287 0.2610 0.1603 0.5406 0.4289 0.2639 0.1748 0.5453 0.4292 0.2649 0.1915 Colour strength K/S = (1 - R)2 / 2R 0.2243 0.3367 0.8929 2.0178 0.2164 0.3637 0.9843 2.1110 0.2010 0.3806 1.0462 2.1993 0.1951 0.3802 1.0266 1.9478 0.1895 0.3795 1.0199 1.7067

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

101

The dyeing behaviour of untreated (C) and pretreated (C-1, C-2 and C3) cotton fabrics with reactive dyes has shown that colour strength values of pretreated cotton fabrics (C-1, C-2 and C-3) increase with the increase in temperature up to 80 oC and then decrease whereas in case of untreated cotton fabrics (C) colour strength values gradually decrease with the increase in temperature (Figure 24).

2.5 2 1.5 K/S 1 0.5 0 50 60 70 80 Temp. ( C)

o

K/S C K/S C-1 K/S C-2 K/S C-3

90

100

110

Figure 24

Effect of temperature on colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf)

The increase in colour strength with temperature in case of pretreated fabrics results from the greater exhaustion and fixation of reactive dyes due to the cationic sites present in the fibre while the deterioration of the dye molecules in case of untreated fabrics and the breaking of fixing agent-fibre

102

bonds or dye-fixing agent complex in case of pretreated fabrics at high temperature results in a decrease in the colour strength of the dyeings. However, pretreated fabrics showed higher colour strength values as compared to the untreated fabrics at all temperatures in all cases due to the greater affinity of cationic fabrics with the anionic dye molecules. Superior results were obtained when dyeing was carried out with cotton fabric pretreated with compound 28c (C-3). This may be the result of interaction between the dye molecules and the additional group in compound 28c.

4.2.3.2 Effect of dyeing time The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt and alkali at 80 oC for different time periods. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 28.

103 Table 28 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at 80
o

C for different time periods

% Reflectance at max. (% R) 54.44 43.53 28.37 17.19 53.58 42.87 26.10 16.03 51.56 46.53 29.32 18.01 Reflectance R = % R / 100 0.5444 0.4353 0.2837 0.1719 0.5358 0.4287 0.2610 0.1603 0.5156 0.4653 0.2932 0.1801 Colour strength K/S = (1 - R)2 / 2R 0.1906 0.3662 0.9042 1.9946 0.2010 0.3806 1.0462 2.1993 0.2275 0.3072 0.8519 1.8662

Time (min.) 15

Cotton fabrica C C-1 C-2 C-3

30

C C-1 C-2 C-3

45

C C-1 C-2 C-3

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

Results indicated that the colour strength (K/S) values of pretreated fabrics (C-1, C-2 and C-3) decrease with the increase in dyeing time above 30 minutes which may be the result of deterioration of dye-fixing agent complex and/or fixing agent-fibre bonds on prolonged heating at high temperature. However, the colour strength (K/S) values of untreated cotton fabrics (C) gradually increase with the increase in dyeing time (Figure 25).

104

2.5 2 1.5 K/S 1 0.5 0 0 15 30 Time (min.) 45 60 K/S C K/S C-1 K/S C-2 K/S C-3

Figure 25

Effect of dyeing time on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf)

4.2.3.3 Effect of dye concentration The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with different concentrations (2-6% owf) of C.I. Reactive Orange 13 in the absence of salt and alkali at a temperature of 80 oC for 30 minutes. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 29.

105 Table 29 % Reflectance (at max. 500 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with different conc. of C.I. Reactive Orange 13 at 80 oC for 30 minutes
Dye conc. (% owf) 2 Cotton fabrica C C-1 C-2 C-3 3 C C-1 C-2 C-3 4 C C-1 C-2 C-3 5 C C-1 C-2 C-3 6 C C-1 C-2 C-3 % Reflectance at max. (% R) 53.58 42.87 26.10 16.03 51.27 38.32 25.99 15.92 50.26 37.81 25.55 15.62 49.96 35.12 20.89 13.87 49.70 33.07 17.97 12.57 Reflectance R = % R / 100 0.5358 0.4287 0.2610 0.1603 0.5127 0.3832 0.2599 0.1592 0.5026 0.3781 0.2555 0.1562 0.4996 0.3512 0.2089 0.1387 0.4970 0.3307 0.1797 0.1257 Colour strength K/S = (1 - R)2 / 2R 0.2010 0.3806 1.0462 2.1993 0.2315 0.4964 1.0537 2.2203 0.2461 0.5114 1.0846 2.2791 0.2506 0.5992 1.4979 2.6742 0.2545 0.6772 1.8722 3.0405

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

106

From Figure 26, it is clear that increase in the concentration of the dye resulted in an increase in the colour strength values of the untreated (C) and pretreated (C-1, C-2 and C-3) cotton fabrics. This may be due to the excess of dye anions in the dye solution at higher concentrations which interact with the fabric in addition to those having electrostatic interactions with the cationic dye sites of the pretreated fabrics.

3.5 3 2.5 K/S 2 1.5 1 0.5 0 0 1 2 3 4 5 6 7 K/S C K/S C-1 K/S C-2 K/S C-3

Dye conc. (% owf)

Figure 26

Effect of dye conc. on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13

4.2.3.4 Effect of cationic agent concentration The cotton fabrics pretreated with different concentrations of compound 30a (C-1), 30b (C-2) and 28c (C-3) were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt and alkali at a temperature of 80 oC for 30

107

minutes. The % Reflectance values (%R) of the dyeings were measured and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 30.

Table 30

% Reflectance (at max. 500 nm) and the colour strength (K/S) values of cotton fabrics pretreated with different conc. of cationic agents (C-1, C-2 and C-3) and dyed with C.I. Reactive Orange 13 (2% owf) at 80 oC for 30 minutes

Cationic agent conc. (% owf) 1

Cotton fabric C-1 C-2 C-3

a

% Reflectance at max. (% R) 49.23 34.88 24.86 42.87 26.10 16.03 43.57 26.88 17.40 43.88 27.12 18.84

Reflectance R = % R / 100 0.4923 0.3488 0.2486 0.4287 0.2610 0.1603 0.4357 0.2688 0.1740 0.4388 0.2712 0.1884

Colour strength K/S = (1 - R)2 / 2R 0.2617 0.6078 1.1355 0.3806 1.0462 2.1993 0.3654 0.9945 1.9605 0.3588 0.9792 1.7481

C-1 C-2 C-3

C-1 C-2 C-3

C-1 C-2 C-3

a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride]; C-2, Cotton pretreated C-3, with Cotton 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N28c N-Cyanoethyl-N-(2,3dimethylammonium chloride]; pretreated with

epoxypropyl)-N,N-dimethylammonium chloride

The effect of cationic agent concentration on the uptake of reactive dyes indicated that an increase in the concentration of cationic agent above 2% (owf)

108

causes a decrease in the colour strength of the pretreated dyeings (Figure 27). This may be due to the partial hydrolysis of the cationic agent that occurs at higher concentrations under alkaline conditions during the pretreatment step, resulting in a decrease in the cationic dye sites in the fibre which in turn decreased the colour strength of the dyeings.

2.5 2 1.5 K/S 1 0.5 0 0 1 2 3 4 5 Cationic agent conc. (% owf) K/S C-1 K/S C-2 K/S C-3

Figure 27

Effect of cationic agent concentration on the colour strength (K/S) of pretreated (C-1, C-2 and C-3) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf)

4.2.3.5 Effect of alkali (anhydrous Na2CO3) The effect of alkali on the reactive dyeing properties of pretreated fabrics was investigated. The pretreated cotton fabrics (C-1, C-2 and C-3; 2% owf) were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt but in the presence of alkali at a temperature of 80 oC for 30 minutes. The % Reflectance values (%R) of the dyeings were measured and from the

109

reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 31.

Table 31

% Reflectance (at max. 500 nm) and the colour strength (K/S) values of pretreated cotton fabrics (C-1, C-2 and C-3; 2% owf) dyed with C.I. Reactive Orange 13 (2% owf) at 80o C for 30 minutes using different amounts of alkali

Amount of alkali (g/L) NIL

Cotton fabric C-1 C-2 C-3

a

% Reflectance at max. (% R) 42.87 26.10 16.03 23.74 20.56 13.08 12.58 12.40 12.28

Reflectance R = % R / 100 0.4287 0.2610 0.1603 0.2374 0.2056 0.1308 0.1258 0.1240 0.1228

Colour strength K/S = (1 - R)2 / 2R 0.3806 1.0462 2.1993 1.2248 1.5347 2.8880 3.0374 3.0942 3.1330

10g/L

C-1 C-2 C-3

20g/L

C-1 C-2 C-3

a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride]; C-2, Cotton pretreated C-3, with Cotton 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N28c N-Cyanoethyl-N-(2,3dimethylammonium chloride]; pretreated with

epoxypropyl)-N,N-dimethylammonium chloride

The pretreated cotton fabrics (C-1, C-2 and C-3) have shown more pronounced results when the dyeing was carried out in the presence of alkali (Figure 28). The use of anhydrous sodium carbonate in the reactive dyeing of pretreated fabrics enhanced the colour strength of the dyeings even in the

110

absence of salt as a result of fixation of the dye with the fibre under alkaline conditions.

3.5 3 2.5 K/S 2 1.5 1 0.5 0 NIL 10g/L 20g/L K/S C-1 K/S C-2 K/S C-3

Amount of alkali (Na2CO3 anhydrous)

Figure 28

Effect of alkali (Na2CO3) on the colour strength (K/S) of pretreated (C -1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf)

As shown in Figure 28, colour strength values increase with the increase in the concentration of alkali. It is also clear that at higher alkali concentration, colour strength values of the pretreated fabrics (C-1, C-2 and C3) were independent of the cationic agent used. This indicates that the cationic agents used for the pretreatment of cotton fabrics have exhausted the dyes on to the fabric due to the interaction between cationic agents and anionic dye molecules and then fixation is brought about under alkaline conditions. Thus, the exhaustion of reactive dyes onto cotton fabrics can be obtained by the

111

pretreatment of cotton fabrics with cationic fixing agents instead of using high salt concentrations which is usually required for reactive dyeing. Using the above mentioned dyeing conditions, untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with three reactive dyes (2% owf) in the absence of salt and alkali (Table 32).

Table 32

Colour strength (K/S) and fastness properties of reactive dyes (2 % owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics in the absence of salt and alkali
Wash fastness ________________ Shade Staining Light fastness 5 4 3-4 3 5 3-4 3-4 3 5 4 4 3-4

Dye C.I. Reactive Orange 13

Cotton fabric C C-1 C-2 C-3

K/S 0.2010 0.3806 1.0462 2.1993 0.0820 0.1455 0.5602 0.7816 0.079 0.2838 0.7353 1.39

change on cotton 2-3 2 1 1 2 1-2 1 1 3 4 4-5 2-3 5 5 5 4-5 5 5 5 5 5 5 4-5 4-5

C.I. Reactive Red 45

C C-1 C-2 C-3

C.I. Reactive Blue 5

C C-1 C-2 C-3

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

112

Dyeing of pretreated fabrics (C-1, C-2 and C-3; 2% owf) was also carried out without salt but in the presence of alkali (anhydrous Na2CO3; 20g/L) at the same time. The colour strength and fastness properties of these dyeings are given in Table 33.

Table 33

Colour strength (K/S) and fastness properties of reactive dyes (2 % owf) on pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics in the presence of alkali (anhydrous Na2CO3; 20g/L)
Wash fastness ________________ Shade Staining Light fastness 5 5 4-5 4-5 4-5 4 4-5 4-5 4

Dye C.I. Reactive Orange 13

Cotton fabric C-1 C-2 C-3

K/S 3.23 3.09 3.13 1.09 1.16 1.14 3.82 4.71 5.25

change on cotton 2-3 3-4 4 2-3 4 2-3 3 4 4-5 5 5 5 5 5 5 5 5 5

C.I. Reactive Red 45

C-1 C-2 C-3

C.I. Reactive Blue 5

C-1 C-2 C-3

a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride]; C-2, Cotton pretreated C-3, with Cotton 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N28c N-Cyanoethyl-N-(2,3dimethylammonium chloride]; pretreated with

epoxypropyl)-N,N-dimethylammonium chloride

A comparative study of the reactive dyeing of pretreated cotton fabrics in the presence of alkali (Table 33) and untreated fabrics dyed by conventional

113

method (Table 34) revealed that cationic cotton showed lower colour strength but similar wash fastness results as compared to untreated fabrics dyed by conventional method.

Table 34

Colour strength (K/S) and fastness properties of reactive dyes (2 % owf) on untreated cotton fabrics dyed by conventional method
Wash fastness ________________ Shade Staining Light fastness 5 5 5

Dye

Cotton fabric

K/S 9.86 5.02 12.14

change on cotton 3-4 3-4 4-5 5 5 5

C. I. Reactive Orange 13 Untreated C. I. Reactive Red 45 C. I. Reactive Blue 5 Untreated Untreated

The overall results indicate that pretreated fabrics C-1, C-2 and C-3 could be dyed with reactive dyes in the absence of salt and alkali. Reactive dyeing of pretreated cotton fabrics without salt and alkali gave higher colour strength and comparable wash fastness properties relative to the corresponding untreated fabrics (Table 32). Although the use of alkali has further enhanced the colour strength values of pretreated dyeings (Table 33) yet the results were lower than the fabrics dyed by conventional method. On the contrary, the wash fastness results of the pretreated dyeings were similar to the untreated conventional dyeings. Thus, high electrolyte concentration can be avoided by the pretreatment of cotton fabrics with cationic fixing agents. The presence of some suitable groups in the cationic agents may further improve the results.

114

SHADES OF REACTIVE DYES ON UNTREATED (C) AND PRETREATED (C-1, C-2 and C-3; 2% owf) COTTON FABRICS

C.I. REACTIVE ORANGE 13 Untreated cotton (C)

(With salt and alkali) (Without salt and alkali)

Pretreated cotton
With alkali Without salt and alkali

C-1

C-2

C-3

115

C.I. REACTIVE RED 45 Untreated cotton (C)

(With salt and alkali) (Without salt and alkali)

Pretreated cotton
With alkali Without salt and alkali

C-1

C-2

C-3

116

C.I. REACTIVE BLUE 5 Untreated cotton (C)

(With salt and alkali) (Without salt and alkali)

Pretreated cotton
With alkali Without salt and alkali

C-1

C-2

C-3

117

4.2.4 DYEING OF UNTREATED AND PRETREATED COTTON FABRICS WITH ACID DYES Untreated cotton fabric (C) and cotton fabrics pretreated with compound 30a (C-1), 30b (C-2) and 28c (C-3) were dyed with acid dyes (1-4% owf) under neutral conditions (Figure 13). The effect of pretreatment on the dyeing properties of cotton fabrics with acid dyes was studied. This study was carried out with C.I. Acid Yellow 23 ( max. 400 nm). The % Reflectance values (%R) of the dyeings were measured using datacolor and from the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated using Kubelka-Munk equation (See Eqn.1 on page 72) and are given in Table 35.

118 Table 35 % Reflectance (at max. 400 nm) and the colour strength (K/S) values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with different concentrations of C.I. Acid Yellow 23 at 100 oC for 60 minutes
Dye conc. (% owf) 1 Cotton fabrica C C-1 C-2 C-3 2 C C-1 C-2 C-3 3 C C-1 C-2 C-3 4 C C-1 C-2 C-3 % Reflectance at max. (% R) 53.36 51.88 51.73 42.66 52.46 47.57 47.28 33.41 52.34 46.83 44.74 29.16 51.99 45.12 42.09 25.57 Reflectance R = % R / 100 0.5336 0.5188 0.5173 0.4266 0.5246 0.4757 0.4728 0.3341 0.5234 0.4683 0.4474 0.2916 0.5199 0.4512 0.4209 0.2557 Colour strength K/S = (1 - R)2 / 2R 0.2038 0.2231 0.2252 0.3853 0.2154 0.2889 0.2939 0.6636 0.2169 0.3018 0.3412 0.8604 0.2216 0.3337 0.3983 1.0832

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

From Figure 29, it can be observed that colour strength increased with increase in dye concentration applied to the cationised fabrics whereas in case of untreated fabric colour strength was very low because acid dyes have low

119

affinity for cellulose. It was also observed that colour strength (K/S) of the cotton fabric modified with compound 28c (C-3) was higher as compared to the other pretreated fabrics (C-1 and C-2) suggesting that additional group in compound 28c has also developed some interactions with the dye molecules.

1.2 1 0.8 K/S 0.6 0.4 0.2 0 0 1 2 3 4 5 Conc. of dye (% owf) K/S C K/S C-1 K/S C-2 K/S C-3

Figure 29

Effect of dye conc. on the colour strength (K/S) of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Acid Yellow 23

The colour strength and wash fastness results of acid dyeings (2% owf) (Table 36) revealed that cationic cotton could be dyed with acid dyes. Although the colour strength (K/S) values of cationic cotton were lower than that of wool dyed with the same acid dye however, the wash fastness results of acid dyes on cationic cotton were comparable to those on wool dyed with the same acid dye except the colour change of pretreated cotton fabrics dyed with

120

C.I. Acid Black 234. On the contrary, the colour change of untreated and pretreated cotton fabrics dyed with C.I. Acid Yellow 23 was better than that on wool dyed with the same acid dye. This difference of colour change during wash fastness testing indicated that C.I. Acid Yellow 23 was more firmly attached to the cationised cotton fibre as compared to C.I. Acid Black 234. This behaviour of acid dyes seems to be dependant on the structure of dyes.

Table 36

Colour strength (K/S) and wash fastness properties of acid dyes on wool, untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics
Wash fastness ___________________________ Staining Shade ____________ Cotton Wool 4 3-4 3-4 4 4-5 4-5 4 4 3-4 3 4-5 4-5 4-5 4-5 4-5 4-5 4 4 4 4 Light fastness 4-5 4 4 4 4 5 4 4-5 4-5 5

Dye C.I. Acid Yellow 23

Fabric C C-1 C-2 C-3 Wool

K/S 0.21 0.28 0.29 0.66 30.45 1.65 4.01 4.85 6.57 39.65

change 2 4 2 2 1 1 1 1 1 4-5

C.I. Acid Black 234

C C-1 C-2 C-3 Wool

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,Ndiethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3epoxypropyl)-N,N-dimethylammonium chloride

121

SHADES OF ACID DYES ON WOOL, UNTREATED (C) AND PRETREATED (C-1, C-2 and C-3; 2% owf) COTTON FABRICS

C.I. ACID YELLOW 23

Wool

Untreated cotton (C)

Pretreated cotton

C-1

C-2

C-3

C.I. ACID BLACK 234

Wool

Untreated cotton (C)

Pretreated cotton

C-1

C-2

C-3

122

4.2.5 AFTERTREATMENT

OF

DIRECT

DYES

WITH

BIS-

REACTIVE CATIONIC FIXING AGENT Cotton fabrics dyed with direct dyes (2% owf) were aftertreated with a bis-reactive cationic agent compound 30b under neutral and alkaline conditions. The % Reflectance (%R) values and the colour coordinates of the dyeings before and after wash fastness test were measured using datacolor. From the reflectance values at the max. of the dyeings (R), the colour strength (K/S) values of the dyed fabrics were calculated and are given in Table 37 and 39. 4.2.5.1 Effect of pH on the aftertreatment of direct dyeings Visual comparison of untreated and aftertreated dyeings have revealed a slight change in colour of the dyeings aftertreated with cationic fixing agent. This is usually encountered with such treatments [16]. The extent of this colour change imparted by aftertreatment at pH 7 varied only slightly than by aftertreatment at pH 11. This visual assessment was supported by colorimetric data obtained for untreated and aftertreated dyeings (Table 37). The results of Table 37 show a decrease in the colour strength (K/S) of the aftertreated dyeings indicating their low wet fastness due to the bleeding of some dye during warm (40 oC) aqueous aftertreatment process. However, this decrease in colour strength (K/S) was found to be dependant on the pH of the aftertreatment. Results indicated that colour strength (K/S) values of aftertreated dyeings were higher at pH 11 than at pH 7.

123 Table 37 Colorimetric data for untreated and aftertreated direct dyeings before wash fastness testing
Aftertreatment Dye C.I. Direct Orange 26 7 11 pH conc. (% owf) 0 2 4 2 4 C.I. Direct Red 31 7 11 0 2 4 2 4 C.I. Direct Black 22 7 11 0 2 4 2 4 L* 49.54 50.93 50.65 49.81 50.07 34.80 34.59 34.78 34.65 34.91 19.69 19.90 19.34 19.45 19.55 a* 60.40 59.69 60.11 61.39 61.09 46.97 45.34 45.69 45.86 46.12 -1.55 -0.67 -0.41 -1.05 -1.02 b* 51.78 52.82 52.88 51.97 51.56 0.73 1.04 1.01 1.42 1.43 -1.86 -2.28 -2.33 -2.04 -1.99 C* 79.55 79.70 80.06 80.43 79.94 46.98 45.35 45.71 45.89 46.14 2.42 2.38 2.36 2.30 2.23 ho K/S

40.61 23.04 41.51 21.53 41.34 22.15 40.25 22.70 40.16 21.84 0.89 16.31 1.31 15.30 1.27 15.46 1.77 15.79 1.78 15.62 230.17 18.77 253.74 17.39 260.06 18.09 242.87 18.54 242.84 18.31

The wash fastness results of untreated and aftertreated dyeings are shown in Table 38, from which it is apparent, that aftertreatment either under neutral or alkaline conditions improved the wash fastness of the dyeings. However, wash fastness imparted by aftertreatment at pH 11 was superior to that imparted by aftertreatment at pH 7. These findings are also supported by the colorimetric data of untreated and aftertreated dyeings after wash fastness testing (Table 39).

124 Table 38 Wash fastness data for untreated and aftertreated direct dyeings
Wash fastness ______________________________________ Staining Aftertreatment Shade Dye C.I. Direct Orange 26 7 11 pH conc. (% owf) 0 2 4 2 4 C.I. Direct Red 31 7 11 0 2 4 2 4 C.I. Direct Black 22 7 11 0 2 4 2 4 change 3-4 4 3 4-5 4-5 2 3 2-3 3 3 3-4 4 4-5 4-5 4-5 ________________________ Cotton 3 3-4 4 4 4 3 3-4 3 4 4 3-4 4 4 4-5 4 Viscose 3-4 4 4 4-5 4-5 3-4 4 3-4 4-5 4-5 4 4-5 4 4-5 4-5

125 Table 39 Colorimetric data for untreated and aftertreated direct dyeings after wash fastness testing
Aftertreatment Dye C.I. Direct Orange 26 7 11 pH conc. (% owf) 0 2 4 2 4 C.I. Direct Red 31 7 11 0 2 4 2 4 C.I. Direct Black 22 7 11 0 2 4 2 4 L* 51.79 50.73 50.33 50.61 50.49 39.83 36.69 38.25 37.33 37.69 21.99 20.79 20.57 19.18 19.86 a* 59.65 59.64 58.94 61.11 61.11 48.45 45.95 46.11 46.23 46.64 -2.31 -1.19 -1.17 -0.87 -0.86 b* 50.61 51.16 49.95 51.10 50.74 -2.17 -0.93 -1.59 -1.58 -1.58 -2.43 -2.43 -2.43 -2.18 -2.55 C* 78.23 78.58 77.26 79.66 79.43 48.50 45.96 46.14 46.26 46.67 3.35 2.71 2.70 2.35 2.69 ho K/S

40.31 18.85 40.62 20.56 40.28 19.93 39.90 20.84 39.71 20.75 357.43 11.45 358.83 12.26 358.02 11.71 358.04 12.49 358.06 12.42 226.50 16.13 243.89 16.68 244.24 16.99 248.13 18.39 251.36 17.88

A comparison of the colour strength (K/S) values of untreated and aftertreated dyeings after wash fastness testing clearly indicates that dyeings aftertreated under alkaline conditions have higher K/S values than the untreated and aftertreated dyeings under neutral conditions. This can be explained on the basis of reactive nature of cationic fixing agent being used as an aftertreatment. Under neutral conditions, cationic fixing agent interacts electrostatically with the anionic dye molecules forming a large complex of reduced aqueous solubility within the dyed substrate. While under alkaline conditions, cationic

126

fixing agent not only interacts electrostatically with the anionic dye molecules but also forms a covalent linkage with the hydroxy groups of cellulose as shown in Figure 7, explaining the observed higher wash fastness. 4.2.5.2 Effect of cationic agent concentration on the aftertreatment of direct dyeings The effect of cationic agent concentration on the aftertreated dyeings has also been investigated. Colorimetric data before wash fastness testing (Table 37) has shown that an increase in the concentration of cationic agent increases the colour strength of the aftertreated dyeings under neutral conditions. However under alkaline conditions, an increase in the concentration of cationic agent causes a decrease in the colour strength of the aftertreated dyeings. This is believed to be due to the partial hydrolysis of the cationic fixing agent that occurs at higher concentrations prior to its reaction with cellulose.

127

SHADE CHANGE OF DIRECT DYEINGS BY AFTERTREATMENT WITH A BIS-REACTIVE DERIVATIVE (30b)

C.I. Direct Orange 26

C.I. Direct Red 31

C.I. Direct Black 22

Untreated dyeings

Aftertreatment at pH 7

2%

4%

Aftertreatment at pH 11

2%

4%

CONCLUSIONS

129

Chapter 5 CONCLUSIONS

Eight mono-reactive and four bis-reactive 2,3-epoxy / 3-chloro-2hydroxy propyl derivatives of quaternary ammonium chloride were synthesised and evaluated as cationic fixing agents for improving the colour strength (K/S) and fastness properties of anionic dyes on cellulosic fabrics. The structures of the synthesised compounds were characterised using IR and
1

H-NMR

spectroscopy. Optimum conditions for the fixation of these cationic agents to the cotton fabrics were determined from the chlorine content of the fabric using compound 30b. It was found that pretreatment with cationic fixing agents (30a, 30b, 28c) has enabled the dyeing of cotton fabrics with anionic (direct, reactive and acid) dyes under neutral conditions in the absence of salt. Higher colour strength (K/S) and good wash fastness properties were obtained with the pretreated fabrics as compared to the untreated fabrics dyed with the same

130

direct and reactive dyes. The results showed that increase in the length of hydrocarbon chain attached to the quaternary nitrogen in bis-reactive derivatives decreased the colour strength of the dyeings but their wash fastness remained unaffected. It was interesting to note that colour strength of the dyeings pretreated with a mono-reactive derivative (28c) was comparable (in case of direct dyes) or superior (in case of reactive and acid dyes) to the fabrics pretreated with bis-reactive derivatives (30a and 30b). On the contrary, the wash fastness of the dyeings pretreated with a mono-reactive derivative (compound 28c) was comparable (in case of reactive dyes) or inferior (in case of direct dyes) to the dyeings pretreated with bis-reactive agents (compound 30a and 30b). These findings suggest that an additional group in the cationic agent may enhance the colour strength of the dyeings due to its interaction with the dye or the fibre but the wash fastness of the dyeings was related to its reactivity. Bis-reactive derivatives showed better wash fastness because of their greater fixation to the fabrics as compared to the mono-reactive derivatives. In comparison with conventional dyeings with direct and reactive dyes, pretreated fabrics required less dyeing time and showed similar wash fastness but slightly lower colour strength (K/S) values. Results also indicated that pretreated cotton fabrics could also be dyed with acid dyes which otherwise have little substantivity towards cotton. However, the colour strength and wash fastness comparable to acid-dyed wool was not obtained. It was also found that light fastness of the dyeings was lowered by pretreatment.

131

Aftertreatment of direct dyeings with a bis-reactive derivative (30b) improved the colour strength and wash fastness properties under neutral and alkaline conditions. However, aftertreatment under alkaline conditions produced dyeings with better wash fastness than by aftertreatment under neutral conditions. It could be concluded that pretreatment with cationic fixing agents has become an environmentally friendly and energy saving process for the direct and reactive dyeing of cotton fabrics by reducing the amount of salt & alkali and time taken for dyeing. Aftertreatment with cationic agents has slightly changed the colour of the direct dyeings but has beneficial effects on the wash fastness results.

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133

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Draper, S. L.; Beck, K. R.; Smith, C. B. Characterisation of the dyeing behaviour of cationic cotton with acid dyes, AATCC Review 2003, 3 (8), 51-55. Kanik, M.; Hauser, P. J. Printing of cationised cotton with reactive dyes, Color. Technol. 2002, 118 (6), 300-306. Kanik, M.; Hauser, P. J. Printing cationised cotton with direct dyes, Text. Res. J. 2004, 74 (1), 43-50. Hauser, P. J.; Kanik, M. Printing of cationised cotton with acid dyes, AATCC Review 2003, 3 (3), 25-28. Kanik, M.; Hauser, P. J.; Parrillo-Chapman, L. Effect of cationisation on inkjet printing properties of cotton fabrics, AATCC Review, 2004, 4 (6), 22-25. Kanik, M.; Hauser, P. J. Ink-jet printing of cationised cotton using reactive inks, Color. Technol. 2003, 119 (4), 230-234. Hauser, P. J. Finishing cationised cotton, Magic world of textiles, Book of the proceedings of the international textile, clothing and design conference, 2002, 274-277; Chem. Abs., 2003, 139, 118643d. Morris, H.; Hauser, P. J. The effects of a cationic reagent on typical finishes, AATCC Review 2003, 3(11), 17-19. Clipson, J. A.; Roberts, G. A. F. Differential dyeing cotton.1 Preparation and evaluation of differential dyeing cotton yarn, J.S.D.C. 1989, 105, 158-162. Clipson, J. A.; Roberts, G. A. F. Differential dyeing cotton. Par 2stoichiometry of interaction with acid and direct dyes, J.S.D.C. 1994, 110, 69-73. El-Shishtawy, R. M.; Youssef, Y. A.; Ahmed, N. S. E.; Mousa, A. A. Acid dyeing isotherms of cotton fabrics pretreated with mixtures of reactive cationic agents, Color. Technol. 2004, 120 (4), 195-200. Stead, C. V.; Evans, G. E.; Shore, J. Triazine dye fixing agents, G.B. Patent 2,119,367, 1983. Virkler, H. E.; Lewis, D. M.; Broadbent, P. J. Salt free dyeing of cellulosic fibres with anionic dyes, U.S. Patent 6,350,872, 2002.

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Clarke, H. T.; Gillespie, H. B.; Weisshaus, S. Z. The action of formaldehyde on amines and amino acids, J. Am. Chem. Soc. 1933, 55, 4579. Bue, S. R.; Ford, J. H.; Wise, E. C. An improved synthesis of alanine, J. Am. Chem. Soc. 1945, 67, 92-94. Galat, A. A new synthesis of alanine, J. Am. Chem. Soc. 1945, 67, 1414-1415. Encyclopedia of Industrial Chemical Analysis, Snell, F. D.; Ettre, L. S. Eds. Vol. 12, Interscience Publishers: New York, 1968, pp 196. Feigl, F. Spot Tests in Organic Analysis, Elsevier Publishing Company: Amsterdam, 1966, pp 251. Kortland, C.; Dammers, H. F. Qualitative and quantitative analysis of mixtures of surface-active agents with special reference to synthetic detergents, J.A.O.C.S. 1955, 32, 58-64. The dyeing of synthetic polymer and acetate fibres, Nunn, D. M. Ed. Dyers Company Publications Trust, 1979, pp 53. Standard Methods for the Determination of the Colour Fastness of Textiles and Leather, Society of Dyers and Colourists, Bradford: UK, 5th edition, 1990. AATCC Technical Manual, Vol. 79, American Association of Textile Chemists and Colorists, USA, 2004. Bluhm, L. H.; Li, T. Chromatographic purification of quaternary ammonium and pyridinium compounds on normal phase silica gel, Tetrahedron Lett. 1998, 39, 3623-3626.

123. 124. 125.

126. 127.

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VITA
Saima Sharif was born on January 02, 1975 in Lahore, Pakistan. She received Bachelor of Science degree from the University of Punjab in 1994. In 1996, she joined the Department of Chemistry, Government College Lahore and received Master of Science degree in 1997. In March 1999, she was appointed as a Lecturer in Chemistry at Govt. Islamia Degree College for Women, Hafizabad. Since then she has been working as a Lecturer. She enrolled in the University of Education, Lahore in 2003 and started her studies towards the Doctor of Philosophy degree under the supervision of Dr. Saeed Ahmad/ Chairman, Department of Chemistry, University of Science and Technology, Bannu-NWFP, Pakistan.

Publications
Role of quaternary ammonium salts in improving the fastness properties of anionic dyes on cellulose fibres, Saima Sharif, Saeed Ahmad and Mian Muhammad Izhar-ul-Haq, Coloration Technology, 2007, 123(1), 8-17. (U.K) (Review article) Synthesis and spectroscopic characterisation of epoxy / halohydroxy propyl derivatives of quaternary ammonium salts, Saima Sharif,

145

Saeed Ahmad and Mian Muhammad Izhar-ul-Haq, Chinese Journal of Chemistry. (Accepted) Aftertreatment of direct dyes on cotton with a bis-reactive cationic fixing agent, Saima Sharif, Saeed Ahmad, Mian Muhammad Izhar-ulHaq, Muhammad Naeem Khan and Muhammad Fauz-ul-Azeem, (Submitted) Effect of cationic fixing agents on the direct dyeing properties of cotton fabrics. (Submitted)

146

Appendix A COLOUR STRENGTH (K/S) CURVES OF UNTREATED (C) AND PRETREATED (C-1, C-2 and C-3) COTTON FABRICS DYED WITH DIRECT DYES (Table 25)

C / C.I. Direct Orange 26

C-1 / C.I. Direct Orange 26

147

C-2 / C.I. Direct Orange 26

C-3 / C.I. Direct Orange 26

C / C.I. Direct Red 31

148

C-1 / C.I. Direct Red 31

C-2 / C.I. Direct Red 31

C-3 / C.I. Direct Red 31

149

C / C.I. Direct Black 22

C-3 / C.I. Direct Black 22

150

Appendix B COLOUR STRENGTH (K/S) CURVES OF UNTREATED COTTON FABRICS DYED WITH DIRECT DYES BY CONVENTIONAL METHOD (Table 26)

C.I. Direct Orange 26

C.I. Direct Red 31

151

C.I. Direct Black 22

152

Appendix C COLOUR STRENGTH (K/S) CURVES OF UNTREATED (C) AND PRETREATED (C-1, C-2 and C-3) COTTON FABRICS DYED WITH REACTIVE DYES IN THE ABSENCE OF SALT AND ALKALI (Table 32)

C / C.I. Reactive Orange 13

C-1 / C.I. Reactive Orange 13

153

C-2 / C.I. Reactive Orange 13

C-3 / C.I. Reactive Orange 13

C / C.I. Reactive Red 45

154

C-1 / C.I. Reactive Red 45

C-2 / C.I. Reactive Red 45

C-3 / C.I. Reactive Red 45

155

C / C.I. Reactive Blue 5

C-1 / C.I. Reactive Blue 5

C-2 / C.I. Reactive Blue 5

156

C-3 / C.I. Reactive Blue 5

157

Appendix D COLOUR STRENGTH (K/S) CURVES OF UNTREATED (C) AND PRETREATED (C-1, C-2 and C-3) COTTON FABRICS DYED WITH REACTIVE DYES IN THE PRESENCE OF ALKALI (Table 33)

C-1 / C.I. Reactive Orange 13

C-2 / C.I. Reactive Orange 13

158

C-3 / C.I. Reactive Orange 13

C-1 / C.I. Reactive Red 45

C-2 / C.I. Reactive Red 45

159

C-3 / C.I. Reactive Red 45

C-1 / C.I. Reactive Black 5

C-2 / C.I. Reactive Black 5

160

C-3 / C.I. Reactive Black 5

161

Appendix E COLOUR STRENGTH (K/S) CURVES OF UNTREATED COTTON FABRICS DYED WITH REACTIVE DYES BY CONVENTIONAL METHOD (Table 34)

C.I. Reactive Orange 13

C.I. Reactive Red 45

162

C.I. Reactive Black 5

163

Appendix F COLOUR STRENGTH (K/S) CURVES OF WOOL, UNTREATED (C) AND PRETREATED (C-1, C-2 and C-3) COTTON FABRICS DYED WITH ACID DYES

C / C.I. Acid Black 234

C-1 / C.I. Acid Black 234

164

C-2 / C.I. Acid Black 234

C-3 / C.I. Acid Black 234

Wool / C.I. Acid Black 234

doi: 10.1111/j.1478-4408.2006.00053.x

Role of quaternary ammonium salts in improving the fastness properties of anionic dyes on cellulose bres
Saima Sharif,a,b Saeed Ahmadb,* and Mian Muhammad Izhar-ul-Haqa
a

Division of Science and Technology, University of Education, Township Campus, College Road, Township, Lahore-54770, Pakistan

Applied Chemistry Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore-54600, Pakistan Email: malikdrsaeed@yahoo.com

The object of this study was to review the developments taking place during 19902005 regarding the use of quaternary ammonium salts as dye xing agents for improving the fastness properties of anionic dyes on cellulose bres. As far as fastness properties are concerned, this review is restricted only to fastness to light, washing and water treatments.

Introduction
The practice of dyeing has recently led to increased requirements in terms of quality of dyeings and protability of the dyeing process. There is still a need for novel dyeing processes that improve properties, in respect of application and fastness properties of the dyeings. Cellulose bres can be dyed with direct and reactive dyes. The afnity of direct dyes for cotton is due to the linear and planar structure of the dye molecules, which enables close alignment with chains of cellulose molecules resulting in signicant hydrogen bonding. Generally, the dyed cellulosic bres have a fastness to washing that does not meet the requirements of todays consumers. This is particularly the case not only for many direct dyes but to a lesser extent for reactive dyes also [1]. Although direct dyes possess inadequate wet fastness properties they are still widely used for their ease of application, comparatively low cost and wide range of shades [2]. Acid dyes, which are primarily used for the dyeing of nitrogenous bres such as wool, silk and nylon, are also anionic in nature. The relatively nonlinear structure of these acid dyes does not facilitate close alignment with the molecular chains in cellulose, which in turn prevents hydrogen bonding. Therefore, these dyes are not substantive to cellulosic bres. However, cationised cellulosic bres can be dyed with acid dyes of both the non-metallised and premetallised types. This increase in substantivity is due to the interaction of anionic sulphonic groups in the dye molecules with the cationic groups in the modied cellulose [3]. Notable improvements in the wet fastness properties of anionic dyes can be brought about by pretreatment or aftertreatment of textile bres. The use of pretreatments or aftertreatments to improve the fastness properties of dyeings has a long and prolic history. Various pretreatment and aftertreatment systems have been developed but at the moment most widely used are cationic xing agents. These chemicals function by

forming a complex of high molecular weight and low aqueous solubility and therefore high wet fastness [4]. Amines [5], quaternary ammonium [6], phosphonium [7] and tertiary sulphonium compounds [8] can be used as dye xing agents. By far the most important type of cationic xing agents used in textile processing is quaternary ammonium salt. Different quaternary ammonium salts [9,10] have been applied to the bres either as pretreatment or aftertreatment to improve the fastness properties of anionic dyes. There has been signicant new developments in this area with respect to developing commercially feasible xing agents in the last one and half decade. These new developments during the period from 1990 to 2005 form the subject matter of this review article. As far as the fastness properties are concerned, this review is restricted only to fastness to light, washing and water treatments.

General development
Most early dyeing processes used naturally occurring coloured compounds, e.g. dye woods [11], which had no signicant afnity for cotton and silk. These processes required a metal salt mordant before dyeing and after dyeing, xation with tannin. The major growth and establishment of the synthetic dye industry was initiated with the discovery of Congo Red, the rst direct dye for cotton, in 1884 [12]. Although some early direct dyeings were claimed to be fast to soaping [13] it was soon appreciated that fastness to light and wet treatments left much to be desired. From 1930 onwards, complexing of direct dyes, present on the bre, with aqueous solutions of cationic xing agents began to be fully exploited. The importance and use of these agents was greatly extended by the development of products rising from the condensation of cyanamide (1) or similar compounds with formaldehyde. These resin xatives [14] of which Fibrox (2) was a

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Sharif et al. Role of quaternary ammonium salts

classical example [15], could be applied by a simple, nishing technique to cellulosic bres dyed or printed with direct dyes. This resin xative class was rapidly extended to provide a large number of agents based on the condensation products of formaldehyde with cyanamide derivatives [16], which were suitable for aftertreatment of direct dyes on cellulose bres. Later on, the reaction products of cyanamide or cyanamide derivatives with monofunctional or polyfunctional amines and the condensates of these amines with formaldehyde or N-methylol derivatives were used as an aftertreatment to improve the wet fastness properties of anionic dyes on cellulose bres [17,18]. Other relevant developments in this area have already been reviewed in detail [19].
H2N C N 1

NH2 HN N N C NH 2 n Xn

Extensive research work has shown that formaldehydebased resin nished products release formaldehyde into the atmosphere directly or during processing, handling, garment manufacturing and subsequent wearing of textiles due to the hydrolysis of unreacted or partially crosslinked N-methylol derivatives present on the bre. Direct release of formaldehyde into the working environment causes severe irritation to eyes, nasal passages and respiratory tract while an unreacted or partially crosslinked resin causes an allergenic response of the skin upon continuous handling of textiles [20]. For reasons of these health problems associated with formaldehyde, there was an increasing demand for non-formaldehyde xing agents. It has also been reported that formaldehyde containing xing agents for direct dyeing could be substituted by nitrogen containing non-formaldehyde xatives without sacricing the performance properties of the nished goods. Selection of suitable non-formaldehyde xatives could actually produce better products than using the formaldehyde xative [21]. Nitrogenous-based dye xing agents have also been reported to improve overall fastness properties, without affecting the tone and depth of shades of reactive dyes on cotton substrates. The results indicated that commercial non-formaldehyde and formaldehyde-based dye-xing agents could be replaced by laboratory developed nitrogenous-based dye xing agents [22]. After the discovery of reactive dyes, dyeing with reactive dyes became the most versatile method for the coloration of cellulosic fabrics. These dyes were used instead of aftertreated direct dyes. However, the fundamental problem of reactive dyeing is that the reaction of reactive dye with water (hydrolysis) competes with the formation of the desired covalent bond between the dye and textile substrates (xation reaction). As the hydrolysed dye cannot react with the bre it should be washed off thoroughly in order to achieve the desired superior wet fastness of the

reactive dyeing. This involves expensive washing off procedures and the treatment of the efuent. Thus, reactive dyes have both economic and environmental drawbacks because of high salt usage and insufcient xation caused by hydrolysis leading to pollution of the efuent [23]. However, if an aftertreatment is given prior to the rinsing stage, hydrolysed dye also gets xed showing improved wet fastness. Therefore, aftertreatment still remained an extremely useful way of improving the wet fastness properties of a deep dyeing that failed to meet the necessary standards. Developments taking place during the recent decade have enabled direct dyes to compete with reactive dyes in the eld of severe wet fastness requirements. The production, in the 1960s, of polyfunctional crosslinking xing agents [24,25] capable of reacting with both dye and bre was a signicant development. These agents were used to after-treat dyes on cellulosic, polyamide and wool bres. During 1980s there was a great revival of interest in the techniques for enhancing the dyeability of cellulosic bres with reactive or direct dyes by pretreatment with a great variety of cationic products usually based on nitrogen. This modication of cellulosic bres with cationic agents resulted in increased substantivity of anionic dyes for cellulosic bres by introducing new cationic sites. Lewis and Lei reviewed numerous chemicals that can be used to provide cationic charges to cotton bres [26]. Pretreatment of cellulosic bres with cationic agents has been reported to enhance the uptake of anionic dyes and facilitate the xation of reactive dyes in the absence of either salt or alkali [27,28]. The cationised bre not only has improved substantivity for direct and reactive dyes, but could also be dyed with acid dyes [3]. The use of anionic dyes (acid, direct and reactive dyes) and cationic xing agents is widespread in dyeing processes. Many studies have been devoted to improve the fastness properties of anionic dyes by pretreating or aftertreating the bres with amines or reactive cationic agents. Most of these studies have used monomeric or polymeric quaternary ammonium salts having different reactive groups. These include dialkyl azetidinium chloride, epoxypropyl/halo-hydroxypropyl trialkyl derivatives of ammonium chloride, mono- and bis-reactive haloheterocyclic compounds and poly-epichlorohydrin dimethylamine derivatives. The mechanisms of dyeing cotton textiles pretreated with quaternary compounds of epoxypropyl type and mono- and bis-reactive chlorotriazine type were studied. The high reactivity and better thermal stability of chlorotriazine type agents than epoxypropyl type agents made them suitable for padbatch or exhaust applications rather than the more costly padbake process and gave effective enhancement of reactive dye uptake [29]. Later on, it was found that the pretreatment of cotton fabric with bis-reactive cationic agent promoted higher extents of dye exhaustion and xation than that with mono-reactive cationic agent [30]. The presence of heterocyclic ring and imino groups in the chloroazine type agents contributes towards the higher substantivity of these agents for cellulose substrates than the epoxypropyl type agents. The low substantivity and poor thermal stability of
9

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Sharif et al. Role of quaternary ammonium salts

epoxypropyl agents made them unsuitable for exhaust application and was also responsible for the poor dye penetration due to signicant migration of agent during the thermal reaction step of padbake process leading to nonuniform distribution of cationic dye sites on the bre [29]. The reactivity of cotton with such types of compounds has been studied under a variety of conditions [9,31,32] but no best procedure has yet been established. Recent work has shown that cotton cationised through a padbatch process gave excellent dye penetration indicating the uniform distribution of cationic dye sites through this process. Thus, a padbatch process seems to be good for achieving high yields of cationically modied cotton with uniform distribution of dye sites [33]. The padbatch dyeing technique has now become an important dyeing method for its simplicity, low consumption of energy and water, and excellent reproducibility [34].

Sandene 8425 (aliphatic polyamine derivative; Clariant) showed improved dye absorption and rmness of colour in the absence of salt in a neutral medium [37,38]. The above-modied bre also enhanced the exhaustion and xation of acid (Table 1) [3] and reactive dyes [39] on cotton in the absence of salt in a neutral medium. The effect of alkali pretreatment followed by 1,1-dimethyl-3hydroxyazetidinium chloride (DMAC) treatment on the dyeability of cotton yarn with reactive dyes has been reported to produce a much stronger colour yield than by DMAC treatment without alkali pretreatment [40].
Cl Me N Me 4 Cl Et N 5 OH Et OH

Monomeric quaternary ammonium salts

The use of cationic agents in the form of primary, secondary, tertiary and quaternary amino residues has been known since 1926 [5,6]. To investigate systematically the effect of attaching a variety of amines to the cellulose bre, cotton was modied by pretreatment with Nmethylolacrylamide (3; Allied Colloids) to introduce a pendant-activated double bond (Scheme 1). By introducing amino residues at these new sites good colour yield and high xation values of reactive dyes were achieved at pH 57 in the absence of electrolyte but light fastness was lowered. Cellulose modied with only N-methylolacrylamide also gave high colour yields with dyes containing pendant aliphatic amino residues in the presence of electrolyte under alkaline conditions [27].
O HO N H CH2 3

Recently, a new bre-reactive quaternary compound containing an acrylamide residue was synthesised and applied to cotton fabrics using a padbake process. It was found that the treated bre could be dyed with reactive dyes without the addition of salt or alkali. The reactive dyes were almost completely exhausted and showed a high degree of covalent bonding with the pretreated cellulose [35]. Cationic starch had also been used for the modication of cotton fabrics. Dyeing of this modied bre with reactive dyes using a continuous dyeing method gave improved dye xation and level dyeing without the presence of salt compared with untreated cotton. The dyeings also showed good wash and rub fastness [36]. Azetidinium chloride An investigation of the direct dyeing of cotton cationised with 1,1-dimethyl-3-hydroxy azetidinium chloride (4), 1,1-diethyl-3-hydroxy azetidinium chloride (5) or
O Cell OH HO N H

Epoxy and halohydroxy propyl derivatives Several patents have covered the preparation of epoxy and halohydroxy propyl derivatives of ammonium chloride [4145]. Many attempts have been made to x epoxy and halohydroxy propyl derivatives to cellulose via an ether linkage. Epoxypropyl derivatives of ammonium chloride react with cellulose under alkaline conditions to form ethers (Scheme 2). However, when halohydroxypropyl derivatives have been used for the cationisation of cellulosic fabrics under alkaline conditions, an epoxide ring is rst formed in the cationising agent by the action of alkali and it then reacts with the hydroxyl group of cellulose under alkaline conditions (Scheme 3). Alkali is required both for the formation of epoxide ring and for its reaction with cellulose. Thus, both epoxy and halohydroxy propyl derivatives have the same reactive group. The rst product of this type was Glytac A (Protex; 6), which reacted with cellulose via the glycidyl group at alkaline pH [46]. 3-Chloro-2-hydroxypropyltrialkyl derivatives of ammonium chloride (7) were synthesised through the reaction of various trialkylamines with epichlorohydrin and were used for the cationisation of cellulosic bres under alkaline conditions. Cationised bres showed slightly better light fastness than those on nylon or wool dyed with the same acid dye (Ciba) but their wash fastness decreased with increasing length of hydrocarbon chain (Table 2) [47]. The use of 2,3-epoxypropyltrimethyl ammonium chloride (6) as pretreatment, a simultaneous treatment or an aftertreatment increased the xation and fastness properties (except rubbing fastness) of direct dyes on cotton textiles. It has been observed that a pretreatment generally produced better results than an aftertreatment. An increase in the number of solubilising groups on the
O

CH2 ZnCl2 / 150 C

Cell

N H

CH2

H2O

Scheme 1 10 2007 The Authors. Journal compilation 2007 Society of Dyers and Colourists, Color. Technol., 123, 817

Sharif et al. Role of quaternary ammonium salts

Table 1 Properties of acid dyes with cationic cotton using no salt at pH 7 K/S Fastness properties Washinga Dye CI Acid Red 73 Treatmentb I II III I II III I II III I II III I II III I II III After wash 3.62 9.34 1.04 2.51 6.18 1.05 1.23 3.25 0.64 3.87 7.14 1.95 2.72 12.14 2.51 4.63 12.51 3.25 After DMFc 0.95 4.02 0.39 0.50 0.98 0.35 0.35 0.37 0.21 2.03 4.76 0.41 2.66 5.88 0.43 3.20 7.55 0.68 A 4 23 23 23 2 2 2 2 3 2 4 2 34 4 3 2 34 2 C 4 2 4 2 23 45 34 4 34 34 4 4 23 45 45 4 34 2 W 34 2 34 23 23 45 2 3 45 2 3 3 23 4 45 23 34 3 Light 4 6 56 23 6 3 5 45 4 5 5 6 6 6 6 6 6 6

CI Acid Orange 7

CI Acid Yellow 36

CI Acid Green 12

CI Acid Red 183

CI Acid Red 214

a A, change in colour; C, staining on cotton; W, staining on wool b I, Sandene 8425; II, 1,1-dimethyl-3-hydroxy azetidinium chloride (DMA-AC); III, 1,1-diethyl-3-hydroxy azetidinium chloride (DEA-AC) c DMF, dimethyl formamide

R1 Cl R2 N R3 O Cell OH

OH

R1 R2

Cl N R3 OH O Cell

Table 2 Fastness properties of acid dye on cotton cationised with different quaternary salts Wash fastness Cationic agenta CMAC CEAC CPAC CP5AC CDTAC Change in colour 45 4 3 3 12 45 45 Light fastness 45 45 45 45 45 4 4

Scheme 2

R1 R2 R1 N Cl

Cl N R3 OH Cl OH R1 R2 N

Cl R3 Cl N R3 OH O Cell O

Dye CI Acid Red 127

Substrate Cotton

Staining 3 3 23 23 2 23 23

OH R3 O Cell OH

R1 R2

R2

Nylon Wool

Scheme 3

Me N O Me 6 Cl Me

a CMAC, 3-chloro-2-hydroxypropyltrimethyl ammonium chloride; CEAC, 3-chloro-2-hydroxypropyltriethyl ammonium chloride; CPAC, 3-chloro-2-hydroxypropyltripropyl ammonium chloride; CP5AC, 3-chloro-2-hydroxypropyltripentyl ammonium chloride; CDTAC, 3-chloro-2-hydroxypropyldimethyltetradecyl ammonium chloride

Cl Cl OH 7 N R3

R1 R2

R1 = R2 = R3 = CH3 C2H5 C 3H 7 C5H11

direct dye molecules generally resulted in a deterioration of the rubbing fastness of pretreated fabrics and an improvement in the case of aftertreated fabrics [48]. This treatment has also been reported to increase the xation

of various reactive dyes on cotton but reduced the fastness properties of dyed fabrics [49]. A comparative study of the reactive dyeing of unmodied cotton and cotton cationised with compound 6 with dyes having four different reactive groups showed that cationic cotton gave the same colour fastness as the unmodied cotton, but usually with higher colour yields [50]. Cotton modied with this agent through a cold padbatch process has been reported to show excellent colour yields and fastness properties for a number of direct (Crompton & Knowles), reactive and acid dyes (Dystar), without the use of electrolytes or multiple rinses, which are normally employed in cotton dyeing (Table 3) [32,33].
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Sharif et al. Role of quaternary ammonium salts

Table 3 Fastness properties of direct reactive, and acid dyes with nylon, conventional cotton and cationised cotton Colour fastness Dye Cotton fabric K/S Change in colour Staininga Light fastnessb

Conventional cotton and cationised cotton CI Direct Blue 78 Untreated Cationic CI Direct Blue 86 Untreated Cationic CI Direct Red 80 Untreated Cationic CI Direct Yellow 106 Untreated Cationic CI Reactive Blue 21 Untreated Cationic CI Reactive Blue 203 Untreated Cationic CI Reactive Red 239 Untreated Cationic CI Reactive Orange 107 Untreated Cationic Nylon and cationised cotton CI Acid Black 172 Nylon Cationic cotton CI Acid Blue 221 Nylon Cationic cotton CI Acid Red 260 Nylon Cationic cotton CI Acid Yellow 79 Nylon Cationic cotton

8.67 13.99 8.76 44.74 14.16 20.11 10.29 14.46 15.08 53.34 16.37 24.24 8.24 12.40 6.91 18.24

2 45 1 5 2 45 3 5 45 4 45 45 5 5 45 4 45 25 45 35 5 35 45 45

25 4 25 45 2 5 35 5 5 5 45 45 45 45 5 5 45 45 45 45 45 35 45 45

5 5 5 5 35 45 5 5 5 45 5 45 45 45 5 45 5 5 5 45 5 5 5 5

a Staining of nylon fabric during laundering, and staining on cotton b 20 h

The dyeing behaviour of cotton, cationised with 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (8; Fisher Scientic), with direct dyes was investigated. Findings revealed that cationised cotton could be dyed without salt and required less rinsing to remove unxed dye than cotton dyed by conventional methods [51]. Dyeing of this cationised cotton with bre-reactive dyes showed deeper shades. Moreover, nonlinear colour behaviour occurred with cationised cotton at lower concentrations than with unmodied cotton, suggesting that predicting shades on cationised cotton requires caution [52]. Signicant differences in dyeing rates and dye uptake of acid dyes on this cationic cotton were observed over untreated cotton. Fastness to laundering and light was greatly improved for cationic cotton over untreated cotton, but remained somewhat lower than the values for nylon [53].

Cl Me Me N Me OH 8 Cl

[54] and direct dyes [55]. Printing on cationic cotton with acid dyes could be carried out at neutral pH because of the presence of cationic charges on the bres at all pH values, avoiding the need for a pH regulator in the print paste and for neutralisation during washing. This technique did not need an intensive washing procedure, and thus appeared to be a more environmentally friendly printing process [56]. The effect of cationisation on the quality of ink-jet printing on cotton fabrics was also investigated. Ink-jet printing with reactive dyes or reactive inks on cationised cotton was found to have good potential as a cost-effective and more environmentally friendly printing method using less dye, less thickener and less alkali without relinquishing outline sharpness [57,58]. Epoxy and halohydroxy propyl derivatives of diallylamine (9 and 10) have also been reported in this regard. Cotton pretreated with these agents showed improved fastness properties for a number of direct dyes (Table 4) [59].

CH3 X N O CH2 9 X = OSO3CH3 CH2

X Cl OH

CH3 N CH2 CH2 10

The printing properties of cationised cotton that had been pretreated with compound 6 were found to be very effective in reducing xation (steaming) times and washing off processes, and in increasing colour yield and wet fastness properties for a number of reactive
12

OSO3C2H5

SO3C6H4CH3

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Sharif et al. Role of quaternary ammonium salts

Table 4 Fastness properties of direct dyes on untreated and treated cotton fabrics

Cl N N N 13 N H Et N I Et Et

ISO C2S wash fastness Cationic agenta I I I I Cotton fabric Without With Without With Without With Without With Change in colour 4 5 4 5 45 5 45 5 Staining on cotton

N H

Dye CI Direct Red 80 CI Direct Blue 71 CI Direct Violet 66 CI Direct Green 26

HN
2 34 2 5 4 5 34 5

NH N N N Cl 14 H N Et I N Et Et

H N I Et N Et Et

N N N Cl

a I, N-(3-chloro-2-hydroxypropyl)-N-methyl-N,N-diallyl ammonium p-toluenesulphonate

Table 5 Fastness properties of direct dyes on untreated (C) and pretreated cotton fabrics with mono- (C-1) and bis-reactive (C-2) cationic agents Wash fastnessa

Mono- and bis-reactive haloheterocyclic derivatives Mono- and bis-reactive haloheterocyclic compounds having monochlorotriazine as the reactive group have also been used for the cationisation of cellulose. Although these treatments enhanced the uptake of dye, there are practical drawbacks to all these treatments, including hue changes, poor penetration into the bre [29] and light fastness limitations [26]. Monofunctional cationic agents of monochlorotriazine type (11) were evaluated on cotton yarn in the production of differential dyeing effects. Yarn pretreated with these cationic agents show better uptake of acid and direct dyes than does untreated yarn [60]. The stoichiometry of interaction of both acid and direct dyes with cotton modied with a reactive cationic agent (12) was examined. The results showed that the presence of the cationic sites enhanced the amount of dye taken up by diffuse adsorption [61]. Recent developments revealed that cotton fabrics pretreated with mono- and bis-reactive cationic agents (13 and 14) showed fairly high degrees of exhaustion and xation of direct dyes under neutral conditions in the absence of salt. Improved fastness was also achieved for this modied bre when compared with untreated samples. Results also indicated that cotton pretreated with the bis-reactive cationic agent showed higher degrees of dye exhaustion and xation relative to cotton pretreated with mono-reactive agent (Table 5) [30].
Cl N N H N 11 Cl N N H N N N H 12 Et N Et Cl N N H Et N X R Et

Dye CI Direct Yellow 50 CI Direct Orange 61 CI Direct Blue 71 CI Direct Green 26

Cotton fabricb C C-1 C-2 C C-1 C-2 C C-1 C-2 C C-1 C-2

F (%)

Change in colour 34 4 45 34 4 45 3 4 4 34 45 45

SC 34 4 45 3 4 45 2 4 4 3 45 45

SW 3 4 45 34 4 45 12 34 4 3 45 45

Light fastness 45 5 45 45 45 45 4 4 2 4 34 2

32 75 3 45 83 1 28 68 2 29 58

a SC, staining on cotton; SW, staining on wool b C-1, cotton cationised with monochlorotriazine mono-reactive cationic agent; C-2, cotton cationised with bischlorotriazine bis-reactive cationic agent

HN H N N N N Cl CI Me N Me Me 15

NH N N N Cl CI N Me Me Me H N

Reactive cationic agents, phenylmonochlorotriazinyl and epoxypropyl, were used for cotton pretreatment using a paddrycuring technique. The dyeability of cationised cotton fabrics using CI Acid Red 1 was found to be dependent on the cationic agent concentration and the appropriate mixture used [62]. More complex multifunctional structures (15) have also been evaluated by exhaust applications and these gave effective enhancement of dye uptake [63].

Polymeric quaternary ammonium salts

Many cationic polymers have been applied to cellulose with a view to enhance the uptake of anionic dyes and it is considerably more difcult in these instances
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Sharif et al. Role of quaternary ammonium salts

to interpret the precise mechanism of the interactions involved, apart from the obvious participation of electrostatic forces between the dye anions and the basic groups (often quaternary nitrogen atoms) in the polymer. Polyamide-epichlorohydrin resin (Hercosett 125; Hercules Powder Corpn), having azetidinium cation (16) as the reactive group, was applied to cotton with a view to producing a modied bre suitable for the absorption and xation of reactive dyes at neutral pH in the absence of salt. Selected highly reactive dyes gave good colour yield and xation but lower xation values were obtained when dyes of low reactivity were applied to the pretreated cotton [64]. It was thought that better xation of both high and low reactivity dyes might be achieved by introducing more highly nucleophilic sites into the cotton. Incorporation of thiourea and ethylenediamine into the polymer during the application process has benecial effects on the results obtained. Thiourea addition inhibits the crosslinking of the resin, leaving more nucleophilic NH groups as sites for dye reaction [65]. Ethylenediamine promotes crosslinking of the resin but itself provides extra NH groups as dye reactive sites [66]. Derivatives of poly-epichlorohydrin, instead of epichlorohydrin were prepared and used as new cationic agents. Poly-epichlorohydrin dimethylamine derivative (17) was applied to cotton under alkaline conditions by the exhaustion method. Pretreatment of cotton with this agent not only reduced the amount of salt needed, but also increased the exhaustion efciency and perspiration fastness of direct dyes (BAY; Table 6) [2].
CI N 16 OH

similar to their untreated counterparts [67]. Pretreated fabrics also gave improved printability with pigment and anionic dyes. The prints obtained on cationised cotton showed better overall fastness properties than prints obtained on untreated cotton [68]. Three commercial cationic xing agents, namely Matexil FC-PN (a phenol formaldehyde ammonium chloride condensate, ICI), Matexil FC-ER (poly diallyldimethyl ammonium chloride; 18, ICI) and Solx E (Ciba), originally marketed as aftertreating agents for direct dyes, were used as pretreatments for cotton modication. Pretreatment was found to increase the colour strength of the dyeings when dyeing had been carried out without electrolyte. However, when electrolyte was used, the pretreated samples exhibited generally lower colour strength than the standard dyeings. The wash fastness of the dyeings almost remained unaffected by pretreatment while light fastness was slightly lowered [69]. The study of the effect of different pretreatment agents on the uptake of 1:2 metal complex acid dyes by samples of cotton/polyamide fabrics showed excellent dye uptake by the pretreated samples compared with the untreated samples. The pretreatment using Matexil FC-ER (18, ICI) or a development cationic xing agent gave the most uniform results [70]. Homopolymer or copolymers of alkyl diallylamine with epichlorohydrin have also been reported to improve the wet fastness properties of anionic dyes on textile bres [1].

Me

N CI Me 18

O H N CI Me Me 17
n

CI N(CH3)2OH 19
n

A commercial cationic xing agent, Solx E (modied quaternary polyamine derivative; Ciba) was used to pretreat cotton prior to dyeing with six commercial direct dyes in the presence of electrolyte. Pretreatment enhanced the colour strength but wash fastness was
Table 6 Fastness properties of direct dyes on untreated and treated (poly-epichlorohydrin dimethylamine) cotton Wash fastness Cotton fabric Untreated Treated Untreated Treated Untreated Treated Change in colour 35 3 35 3 35 25 Staining on cotton 3 3 35 3 45 45 Light fastness 4 35 4 35 4 35

Dye CI Direct Blue 78 CI Direct Orange 39 CI Direct Blue 86

K/S 14.02 14.26 11.58 11.90 6.06 11.74

Aftertreatment of the dyeings produced on cellulosic bres, pretreated with xing agent 18 and Fixogene CXF (copolymer of dimethylamine and epichlorohydrin; 19, ICI), with cationic polymers enhanced the light and wash fastness of acid (Table 7) [71] and reactive dyes [72]. The subsequent application of syntan (synthetic tanning agent) to the aftertreated dyeings enhanced the effectiveness of commercial cationic xing agents 18 and Fixogene CXF, in improving the wash fastness of three commercial direct dyes (Ciba-Geigy) on cotton but the effect of syntan was both dye and xing agent specic (Table 8) [4]. It has also been examined that wash fastness was noticeably better when these xing agents were applied under alkaline conditions (Table 9) [73]. A new bre modication technique based on a cationic acrylic copolymer (polymer pL) has been established. Pretreatment of cotton with this polymer increased both the substantivity and reactivity of the bre towards reactive dyes, even under neutral or acidic conditions [74]. Recently, poly(vinylamine chloride) has been investigated

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Sharif et al. Role of quaternary ammonium salts

Table 7 Fastness properties of acid dyes on cotton Pretreatmenta Aftertreatmentb Wash fastness Staining Cotton sample Material % Material % Shade change C W N K/S Light fastness

CI Acid Green 106 1C 1.1 PT1 1.2 PT1 1.2 PT1 1.4 PT1 1.5 PT2 1.6 PT2 1.7 PT2 1.8 PT2 CI Acid Red 315 2C.1 2.1.1 PTI 2.1.2 PTI 2.1.3 PTI 2.1.4 PT2 2.1.5 PT2 2.1.6 PT2 CI Acid Yellow 235 2C.2 2.2.1 PT1 2.2.2 PT1 2.2.3 PT1 2.2.4 PT2 2.2.5 PT2 2.2.6 PT2

2 2 2 2 2 2 2 2

AT1 AT2 AT3 AT1 AT2 AT3

2 2 2 2 2 2

3 34 34 4 2 34 23 45

45 5 5 5 45 5 5 5

0.9 5.60 5.78 5.80 5.73 6.05 6.01 6.06 5.97 1.96 9.89

67

2 2 2 2 2 2

AT1 AT3 AT1 AT3

2 2 2 2

3 34 4 23 34 4

23 3 3 23 3 34

4 45 45 34 4 45

3 34 4 3 34 4

10.93

2 2 2 2 2 2

AT1 AT3 AT1 AT3

2 2 2 2

3 34 34 2 34 4

45 45 5 45 45 5

34 4 45 3 4 45

4 45 45 4 45 45

2.17 7.23

67

6.54

a PT1, Matexil FC-ER; PT2, Fixogene CXF b AT1, Matexil FC-ER; AT2, Fixogene CXF; AT3, copolymer of diallyldimethylammonium and diallyl-2-hydroxy-3-chloropropyl ammonium chloride

Table 8 Fastness properties of direct dyes on cotton aftertreated with cationic xing agents/syntan K/S Dye CI Direct Red 89 Aftertreatmentsb Nil 4% 4% 4% 4% Nil 4% 4% 4% 4% Nil 4% 4% 4% 4% Before wash 14.84 14.21 13.77 14.74 14.45 10.98 10.49 10.31 10.36 10.65 17.06 17.06 16.81 16.08 16.81 After wash 11.13 12.75 13.34 12.72 13.26 8.01 9.94 10.11 8.81 8.73 12.42 16.94 16.14 15.79 15.96 Wash fastnessa S 4 45 45 45 45 3 4 4 4 4 3 45 45 45 45 C 1 23 23 12 2 1 23 3 12 12 1 23 23 12 2 V 12 3 3 2 23 12 3 34 2 2 12 3 3 2 2

M FC-ER M FC-ER/2% F AXF F CXF F CXF/2% F AXF M FC-ER M FC-ER/2% F AXF F CXF F CXF/2% F AXF M FC-ER M FC-ER/2% F AXF F CXF F CXF/2% F AXF

CI Direct Yellow 106

CI Direct Blue 85

a S, change in shade; C, staining of adjacent cotton; V, staining of adjacent viscose b M, Matexil; F, Fixogene

as a pretreatment for the salt-free dyeing of cotton with reactive dyes. Dye xation was found to be much higher than by conventional dyeing without pretreatment, even in the presence of a large amount of salt. Dyed cotton pretreated with poly(vinylamine chloride) showed excellent wash fastness and good rub fastness [75].

Conclusion
Different quaternary ammonium salts have been applied to the cellulosic bres either as pretreatment or aftertreatment to improve the fastness properties of anionic dyes on cellulosic bres. These treatments

2007 The Authors. Journal compilation 2007 Society of Dyers and Colourists, Color. Technol., 123, 817

15

Sharif et al. Role of quaternary ammonium salts

Table 9 Fastness properties of direct dyeings aftertreated with Fixogene CXF and Matexil FC-ER under neutral and alkaline conditions Colour fastness Staininga Dye CI Direct Red 89 7 11 7 11 CI Direct Yellow 106 7 11 7 11 CI Direct Blue 85 7 11 7 11
a C, cotton; V, viscose

pH

Cationic agent Nil 4% 4% Nil 4% 4% Nil 4% 4% Nil 4% 4% Nil 4% 4% Nil 4% 4%

K/S 14.84 14.74 14.64 14.84 14.21 13.18 10.98 10.36 10.57 10.98 10.49 10.57 17.06 16.08 16.68 17.06 17.06 17.40

Shade change 4 45 45 4 45 45 3 4 4 3 4 4 3 45 45 3 45 45

C 1 12 2 1 23 3 1 12 23 1 23 34 1 12 2 1 23 3

V 12 2 23 12 3 3 12 2 3 12 3 4 12 2 3 12 3 4

Fixogene CXF Fixogene CXF Matexil FC-ER Matexil FC-ER Fixogene CXF Fixogene CXF Matexil FC-ER Matexil FC-ER Fixogene CXF Fixogene CXF Matexil FC-ER Matexil FC-ER

enhanced the exhaustion, xation and wet fastness properties of anionic dyes on cellulose bres.

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