A Literature On

STUDIES OF DYEING BEHAVIOUR OF POLYFUNCTIONAL REACTIVE DYES

Senthil Kumar.R.K Aniket Kulkarni Adesh Joshi Bajrang More

Department of Textile Chemistry DKTES Textile And Engineering Institute

Under The Guidance of Mr. Aravin Prince Periyasamy

1.1 INTRODUCTION: Reactive dyes are only textile colorants designed to have covalent bonding with the cellulose material. The reactive dyes are becoming significantly popular for dyeing cellulose fibre, because of their wide range, ease of application. The reactive dye is classified into mono, Bi and Poly functional reactive dyes. The mono functional reactive dyes have some disadvantage of less exhaustion, low fixation, hydrolyzed during dyeing and it causes to increase the TDS & etc. Poly functional reactive dyes are manufactured to overcome these disadvantages and these Polyfunctional reactive dyes provide a promising trend in the dye industry. The Polyfunctional Type Reactive Dyes shows many advantages namely better yield, Low salt content and posses higher exhaust value, improved leveling and excellent fastness properties1. These Dyes are also used in single color dyeing especially for pale, medium and dark shades, and it can be used to achieve the single bath dyeing in P/C. In this project we are going to study the dyeing behavior of Poly functional dyes under different conditions and this literature deals with the peculiar properties of these dyes and their environmental aspects as compared to conventional reactive dyes and uses of poly functional reactive dyes.

2.1 WHY POLY FUNCTIONAL REACTIVE DYES? Poly functional reactive dyes contain more than one reactive group in each molecule and offers a very high levels of fixation which leads to low colour usage to achieve a given depth of shade and a lower unfixed colour load in effluent. Innovative manufacturers have introduced dye ranges of this type over the last few years as pressure to reduce the colour load to waste water has increased particularly in Western Europe2. It should theoretically be possible to attain even greater fixation efficiency but encorporating additional reactive groups into the dye molecule. In practice this approach can be counterproductive owing to detrimental effect that additional groups can have on migration , leading to lower fixation, especially at heavier depths, and poor build up. However, several patent applications relating to reactive dyes with three reactive groups have appear. Also some commercially successful dyes of this type are now available, perhaps the more notable of these being the tri functional derivative Cibacron Red C-2G and Remazol Red BS. The formal possesses three reactive groups per single unit of chromophore. It thus represents an expensive route to high fixation. In the case of tri functional dye possessing only one chromophore unit the molecular weight contribution of the un coloured reactive groups can be comparable to that of chromophore3. Structures that incorporates three reactive groups disclosed by Bayer. These are claimed to display high reactivity and excellent fixation yields, which are very insensitive to minor variations in fixation temperature, even when dyeing at long liquor ratios3. These reactive dyestuffs are suitable for dyeing and printing natural and synthetic hydroxyl or amino containing materials such as silk, wool, synthetic polyamide fibres, cellulose containing fibrous materials such as linen, cellulose itself, regenerated cellulose and especially cotton, having improved fastness properties4. These reactive dyestuffs are distinguished by a high reactivity and excellent fixing capacity. Because of their poly functionality they give high fixing yields even from a long liquor. They are characterized by a tinctorial strength which is relatively independent of the dyeing temperature and can therefore be employed in the exhaustion process at low to moderate dyeing temperatures. In the pad-steam process they require only short steaming times. They produce dyeing of good depth of colour with good light and wet fastness properties5. They are suitable not only for the exhaust method but also for dyeing by the customary pad-dyeing method, whereby the material is impregenated with aqueous dyestuff
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solutions which, if desired, may also contain common salt and the dyestuff are fixed, after an alkali treatment or in the presence of alkali, if appropriate with the application of heat4.

2.1.1 HIGH EXHAUSION RATE: High exhaustion rate also means that a lower amount of color is required to achieve given depth of shade and hence salt loading can be reduced as this normally increases with increase in dyestuff concentration2.

2.1.2 HIGH FIXATION RATE: High fixation rate minimizes the amount of unfixed dye that must be removed at the end of the fixation stage to achieve the desired level of fastness performance. This means that shorter rinsing and soaping sequences are required which leads to considerable savings with water and energy consumption2.

High fixation reactive dyes can applied on all types of dyeing machines but offer particular advantage on the most modern low liquor ratio dyeing machines fitted with polytasking controllers where additional advantages of reduced energy and water consumption can be exploited2. Thus, high fixation, polyfunctional reactive dyes have been in widespread use for many years in all European countries and world wise as well. Individual manufacturer provides comprehensive technical information for their high fixation dye ranges including detailed salt recommendations according to depth of shade, type of substrate, equipment in use etc. Thus recommendations should also have been design to ensure high level of reproducibility and maximize Right First Time performance2. Compared to conventional mono functional reactive dyestuff, poly functional reactive dyestuff are more expensive when considering price per kg only. However the high fixation efficiency, the savings on salt usage, and reduced water and energy consumption means that the total cost of processing can be significantly reduced2. The main driving force for the development of high fixation, poly functional reactive dyes have been the intro of legislation restricting the color of effluents discharged to sewer or river. Most European countries set color absorbance limits at various wavelengths which have to be complied with by discharger. This has meant an increase in charges for color removal treatments either on-site or at local municipal waste water treatment plants in some countries legislation also exist to limit to AOX level in effluent. An equally important factor
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has been the drive reduce the total cost of processing and high fixation dyes giving high levels of Right First Time can make a significant contribution in this respect2.

The fixation of a reactive dye with cellulose can be expressed either as a percentage of the total dye applied (fixation rate, sometimes also called absolute fixation) or as a percentage of the dye exhausted (exhaustion rate, sometimes also called fixation efficiency). In the case of monofunctional dyes, the fixation rate is approximately 60 % (with an exhaustion rate of about 70 %) so that 40 % of the dye is hydrolysed in water later it becomes waste and difficult to remove in ETP. In the case of bifunctional reactive dyes, 80 % fixation rate and over 90 % exhaustion rate is achieved. The immediate consequence is a significant reduction of unused dyestuff ending in the waste water stream (reduced colour and organic load)1. 2.1.3 ENVIRONMENTAL BENEFITS 2 Reduced color load Reduced salt consumption Reduced water and energy consumption Reduced AOX load

This is particularly advantageous when advanced oxidation techniques are applied to treat the dye in the effluent. It has to be noted, however, that a lower amount of dye in the effluent does not necessarily produce a reduction in visual colour. The tinctorial strength of new reactive dyes has significantly improved. This means that deeper and more intense shades are possible with less dye than necessary with other dyes or dye classes. Less dye is therefore left in the effluent, but visual colour may be still high1. A recent innovation from Dystar (Procion XL+ dyes) allows much shorter processing time on certain substrates by combining the pretreatment and dyeing steps using polyfunctional dyes that fix at 90 C. Savings of up to 40 % in water and energy consumption and more than 30 % of salt are claimed1. The main benefit achieved by the use of polyfunctional high fixation reactive dyes is the reduced color, COD load to effluent and less TDS. In the case of reactive dye containing

two or more reactive groups of similar reactivity, the potential for achieving a covalent linkage with the cellulose hydroxyl groups is significantly increased2. 2.2 PECULAR PROPERTIES OF POLYFUNCTIONAL REACTIVE DYES2: High reactivity Excellent fixation Low salt Less TDS

2.3 TYPES OF POLYFUNCTIONAL RECTIVE DYES: 2.3.1 TRIFUNCTIONAL REACTIVE DYES 6: Although relatively few products have been marketed with three reactive groups, increasingly this has been an area of patent interest. Ciba , Sumitomo , Hoechst and BASF have disclosed a number of different chromogenic types containing bis-VS/MCT and bisVS/MFT reactive groups, e.g.,

. Ciba has also claimed dyes with a bis-VS/difluorochloropyrimidinyl , bis-MCT/VS or bis-MFT/VS combination. Hoechst has recently patented the interesting trifunctional combination of two (masked) vinyl sulphonyl groups attached to a single triazinyl ring .Reactive dyes with three halotriazinyl or triazinylpyridinium groups with VS/MCT plus a

difluorochloropyrimidinyl group or with a bis-VS/triazinylpyridinium combination have also been described. 2.3.2 TETRAFUNCTIONAL REACTIVE DYES 6: Ciba has filed patents covering a wide range of chromogens with two VS/MCT or VS/MFT reactive group combinations. Similarly Hoechst has shown interest in reactive dyes with four reactive groups and once again two pairs of VS/MCT or VS/MFT have been employed to this end. A typical example is the reddish-grey to black chromium complex .Other reactive group combinations have also been described e.g. two triazinylpyridinium reactive groups with has patented dyes with four monohalotriazinyl groups. -chloropropionamido groups . BASF

2.3.3 PENTAFUNCTIONAL REACTIVE DYES 6: An H-Acid red dye with five independent reactive groups has been described by Omura and coworkers

2.4 ADVANTAGES AND DISADVANTAGES OF POLYFUNCTIONAL REACTIVE DYES OVER OTHER REACTIVE DYES: Compared to conventional reactive dyes, Polyfunctional reactive dyestuffs are more expensive per kilogram, but the higher fixation efficiency, the savings on salt usage and the reduced water and energy consumption may equalize to the cost of the dye. Winch LR 20:1 Traditional reactive 1200 kg Jet LR 10:1 600 kg Low LR jet LR 5:1 300 kg

dyes(60 gpl salt) Low salt reactive 800 kg 400 kg 200 kg

dyes(40 gpl salt Table: Quantities of salt required to dye 100 kg fabric to a medium depth of shade Salt consumption for exhaust dyeing is reduced by about one third of the quantity needed for conventional reactive dyestuffs, with positive impact on effluent salinity and on smooth running of waste water treatment units. The significantly lower salt usage translates into reduced salt handling and dissolving time. An automation of salt and brine additions is facilitated by lower required salt quantity2. When reducing salt levels it is important to ensure that reproducibility levels are maintained as this can have major impact on water and energy consumption per unit of production. Under low liquor ratio dyeing conditions the substantivity of a dye stuff is increased due to increased mechanical pick up and exhaustion and fixation levels are also increased, but to lesser extent2. However migration and level dyeing behaviour are adversely affected unless there is an compensating reduction in salt concentration. It should also be mentioned that rinsing after dyeing needs efficient washing machinery because the norm fixed compounds of the high affinity type , low salt reactive dyestuffs are not as easy to wash out as low or medium affinity dyestuffs2.

Conventional reactive dyes: Advantages: Low cost High leveling properties Disadvantages: Polyfunctional reactive dyes: Advantages: High exhaustion High fixation Low hydrolyzed dye Less load to the effluent Disadvantages: High cost Low leveling property. Low exhaustion Low fixation High hydrolyzed dye High load to effluent

2.5 APPLICATION METHOD7: Polyfunctional reactive dyes, containing more reactive systems, offer very high levels of fixation in exhaust dyeing. Because of their more reactive groups, poly functional reactive dyes have increased probability of chemical reaction with cellulose fibres compared to other reactive dyes. If one of the reactive groups hydrolyses during the dyeing process, the other one can still chemically react with the hydroxyl groups of cellulose. Moreover, combining more reactive systems in the same dye delivers the advantages of the more individual groups (e.g. high degree of fixation with high fastness levels and wash-off). Polyfunctional reactive dyes can be applied in all types of dyeing machines, but offer particular advantage on the most modern low liquor ratio dyeing machines fitted with polytask controllers where additional advantages in terms of reduced energy and water consumption can be exploited. In particular, new reactive dyes with very good solubility can be applied at ultra-low liquor ratios. 2.6 P/C BLENDS WITH POLY FUNCTIONAL REACTIVE DYES: High affinity low salt reactive dyestuffs can also be favourably used for one bath dyeing polyester cellulose blends which saves time, water and energy. The lower salt concentration reduces the tendency of disperse dye stuffs to stain the cotton fibres of the
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blend (beneficial for fastness and reproducibility of shades). High affinity dyestuffs allow efficient colouration under conditions of longer liquor ratios with respect to cotton such as those that exists when dyeing P/C blends2. The technique is applicable both to existing and new dyeing machines. Low salt reactive dyestuffs can be applied on all conventional exhaust dyeing machines but offer particular advantage on the most modern low liquor ratio dyeing machines where additional advantages of reduced energy and water consumption can be exploited. Low salt reactive dyestuffs have been in use for the last five years in all European countries and throughout the world wide2. Individual manufacturer provide comprehensive technical information for their low salt dye stuff ranges including detailed salt recondemendation according to depth of shade, type of substrate, equipment in use etc. These recommendations should be also have been designed to ensure a high reproducibility and maximises Right First Time performance2. 2.7 FUTURE TRENDS IN REACTIVE DYES8: Research is being carried out for: Poly functional dye chemistry to improve reactivity, fixation levels and reproducibility. Increasing the robustness of individual dyes and dye combinations in trichromatic systems Enhancing reproducibility of trichromatic combinations used in most commonly applied dyeing processes. Reducing salt consumptions and/or unused dye in the effluent (Dyes with no salt, low alkali addition and 100% fixation.) Improving fastness properties (ex:light fastness, fastness to repeated laundering) Reactive dyes exclusively for printings, which are different from low molecular weight MCT dyes.

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3. PLAN OF WORK: 3.1 OBJECTIVE: In this project an attempt has been made to assure the optimum conditions for dyeing of poly functional reactive dyes. In this project we are checking the fixation rate, exhaustion rate, percentage hydrolysis, color strength of the polyfunctional dye at different different concentrations of salt and alkali and by changing the fixation time and temperature. As in poly functional reactive dye salt required is about one-third of the conventional reactive dye we also trying to reduce the effluent load. 3.2 MATERIALS REQUIRED: Fabric-100% cotton Desized, Scoured and Bleached fabric Weave-plain Warp count-60s Weft count-60s

3.3 CHEMICALS REQUIRED: Polyfunctional Reactive Dyes (from Clariant/Bayer/ Huntsman) Common Salt Sodium Carbonate Sodium Silicate Soap And Detergent

3.4 MACHINES REQUIRED: Low Liquor Dyeing Machine(Mathis Labomat) Padding Mangle Steamer Baker Dryer Crock Meter Launderometer Fabric Strength Tester Computer Colour Marching
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3.5 METHOD: 3.5.1 Exhaustion Method: HE Method and Migration Method Salt Content: Depending On the Dye and Shade Temperature Range: 95C,85C,60C, Room Temperaure Fig1- Room Temperature

Fig 2-At 60C

Fig 3-At 85C

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Fig 4-At 95C

Time: 30 Mins,45 Mins,60 Mins,75 Mins,90 Mins Alkali Content: Depending On The Dye And Shade 3.5.2 Dyeing By: Pad Batch: Cold Batch And Hot Batch Pad Steam, Pad Dry Bake, Pad Dry Steam, Pad Dry Pad Steam. 3.6 TESTING: 3.6.1 Measurement of concentration and exhaustion of reactive dyes9: The measured extinction coefficients were used to calculate the concentration of those dyes used in the lab dyeing. To do this, twelve lab dyeing tubes were used. Four tubes were used for each dye of the proposed dye recipe (i.e. four tubes for dye 1; four tubes for
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dye 2; and four tubes for dye 3. The laboratory dyeing protocol normally used by the dye house was followed; the only exception being that the dyes were not mixed. 5ml sample was taken from tubes containing dye 1, dye 2 and dye 3. These three samples were diluted to a suitable concentration so that they can be analysed using the spectrophotometer to determine the absorbance. A suitable concentration is one where 5ml of sample is diluted to 250ml solution. Lab dyeing was conducted according to the dyeing profile. After 20 minutes another three samples of 5 ml were taken from each of the three dyes and analysed using the spectrophotometer to determine the absorbance. The same procedure is repeated after the addition of soda ash, 20 minutes after the addition of soda ash and at the end of the dyeing.

3.6.2 CALCULATION Extinction coefficient 9 The data of concentration and absorbance at a particular wavelength are used to draw the calibration curve. The slope of the curve is the extinction coefficient for this dye. The extinction coefficients can be used to estimate the concentration of those dyes used in the lab dyeing. Concentration and Exhaustion 8 The following equation was used to calculate the concentration. A = cl (1) Where, A = absorbance, = extinction coefficient c = concentration of the dye and l = path length of the cell, which is normally 1cm.
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The concentrations of dye in the dye bath were used to calculate the exhaustion (%E) at each stage of dyeing for each dye. For example the exhaustion after stage one is given by, E1% = (C0 C1)*100/ C0, where, C0 = Concentration at the initial stage and C1 = Concentration after 20 minutes of dyeing. Similarly, the exhaustion after stage two is given by, E2% = (C0 C2)*100/ C0, where, C2 = Concentration after 40 minutes of dyeing. Thus, E3, E4, etc. i.e., the exhaustion at different stages of dyeing can be calculated to plot the exhaustion curve. Using the above method the exhaustion data of each dye against time was recorded and then the exhaustion curve characteristics of the three dyes of a particular shade was plotted. This was done three times in two different industries for two different groups of dyes. 3.6.3 Fixation measurement through Colour strength9 Fixation of the dye into the fibre was measured using computer colour matching system, which is commonly used in textile dyeing factories to match the shade of sample fabrics with test dyeing. It can also be used to calculate how efficient the dyeing recipe was for fixing the dye to the fabric and thereby giving an estimation of how much dye is being wasted. The colour matching software can measure the colour strength on the fabric and then the fixation can be calculated for any single dye. To determine the fixation, the dyed fabric was cut into two pieces at the end of dyeing and one piece was left in the open air. The other piece was treated in an aqueous solution containing 5g/l washing agent and 2.5 g/l Na2CO3, using 50:1 or 40:1 liquor ratio at 980C for 30 min. Washing treatment for another 30 minutes with fresh solution was carried out unless colour bleeding occurs. The sample was rinsed thoroughly in cold water and left to dry in the open air. Each fabric sample was folded so that there are four layers of material. The sample was placed in the colour matching equipment and four different reflectance measurements were made on one side of the fabric. These four reflectances are averaged to calculate the colour strength (K/S). Alternatively, K/S can be measured directly from some measuring equipment. The fixation can then be calculated as, F(%)=(K2/S2)/(K1/S1)*100 Where, K1/S1 and K2/S2 are respectively the colour strengths of the unwashed and washed dyed samples. These data only gave an approximate fixation value as there are hydrolysed as well as unfixed dyes present in the fabric which cannot be washed off. It can however be assumed that the real value will not be much different from this approximate value.

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3.6.4 Fastness: Color fastness to washing(ISO 2,ISO 3) Color fastness to rubbing Color fastness to light

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4. REFERENCES: 1. Dyeing of cellulosic fibres with poly functional reactive dyes by exhaust method 2. Reactive dyes for textile fibres by A Hunter M Renfrew 3. Poly functional azo reactive group dyestuffs containing a morpholinyl substituted fluorotriazine radical-United Patents: Patent No:5459244 4. Textile Dyeing and coloration By J. Richard Aspland 5. Shading process using poly functional reactive and non reactive dyestuffs bonded in fixing-United Patents/Patent No :4504272 6. Textile chemicals Environmental Data And Facts K.Lacasse and W.Baumann 7. http://www.ineris.fr/ippc/sites/default/interactive/bref_text/breftext/anglais/bref/B REF_tex_gb27.html 8. The Indian Textile Journal February 2010 Reactive dyes: Past and Future by RH Deshpande and Y M Indi Page No-38-41 9. Journal of mechanical engineering vol ME38 dec 2007 Comparitive testing of reactive dyes by Razia Sultana and M. Zulhash Uddin 10. Advances in colour chemistry theory vol-3 Synthesis and Structure A.T Peters and H.S Freemann 11. Asian Dyer March 2010: Chemical processing of textiles in India by M L Gulrajani Page No-39-45 12. Bi- and Poly functional reactive dyestuffs, their preparation and their use-United States Patent/Patent no:5597902 13. Recent developments in reactive dyes by John A Taylor-Rev.Prog.Coloration Volume 30 2000 Page no:93-107 14. A study on poly functional reactive dyes and their combinations by College of Materials Science and Chemical Engineering, Zhejiang University, Hangzhou 310027

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