Cellulose: chemical modification

CHEM-E2140
Eero Kontturi

3rd November 2015

Outline
(1) Chemical modification of cellulose motivation
(2) Background: terminology, challenges
(3) Esterification of cellulose
Inorganic esters:
- xanthogenate
- carbamate
Organic esters:
- formate
- acetate
(4) Etherification of cellulose:

- alkyl ethers
- hydroxyalkyl ethers
- carboxymethyl cellulose

(5) Regioselectivity in chemical modification of cellulose

Motivation for cellulose modification

Preparation of substances that have different properties from cellulose,
yet they are of renewable origin and biodegradable
- One of the most important properties is that most cellulose esters
and ethers are thermoplastic (cellulose is not)
Modified cellulose, i.e., cellulose derivatives often possess properties that
are not easily achieved with totally synthetic polymers
(With nanocellulose) modify the surface of nanocelluose to achieve better
compatibility with its environment (composites etc.)

Basic concepts
The idea of chemical modification of cellulose is to introduce
functional groups in the cellulose backbone

OH

OR
O

O
O

HO
OH

RO
OR

Usually achieved by substituting the protons in the hydroxyl groups

of cellulose to a varying extent

Basic concepts
Degree of substitution (DS)
Quality which measures the average amount of substituted hydroxyl
groups in an anhydroglucose unit

n/2

Cellulose acetate with DS=2

Carboxymethyl cellulose
with DS=0.5

Basic concepts
Regioselectivity: which OH group/groups are modified

Basic concepts
(1) Homogeneous modification
Cellulose is dissolved and individualized cellulose chains are modified
in a homogeneous solution
Uniform, homogeneous modification
(2) Heterogeneous modification
Fibres, microfibrils, nanocrystals etc. are modified in a heterogeneous
suspension
Usually results in surface modification (not necessarily)

Challenges
The fundamental challenge in chemical modification of cellulose is that
cellulose is relatively inert and does not automatically obey the common
rules of organic chemistry
(For example, cellulose hydroxyl groups are alcohols but they do not form
esters with carboxylic acids under normal conditions)
Regioselectivity is often difficult to achieve

Esterification of cellulose

Commercial cellulose esters

Klemm et al. Angew. Chem. Int. Ed. 2005, 44, 3358.

Esterification of cellulose
Inorganic esters:
- cellulose xanthogenate
- cellulose carbamate
- cellulose sulphate
- cellulose nitrate

Cellulose xanthogenate
Cell-OH Cell-OCell-O- + CS2 Cell-O-CSS- Na+
Half ester, achieved by a reaction between cellulose alkoxy ion (Cell-O-)
and carbon disulfide (CS2) in alkaline medium
Cellulose xanthogenate is water-soluble because of the polyelectrolyte
(charged) nature it introduces to the cellulose chain
The reaction is important in practice because of its use in viscose process
- cellulose xanthogenate is produced from native cellulose
- cellulose xanthogenate is dissolved
- the dissolved xanthogenate is regenerated in acid solution,
enabling controlled regenaration of cellulose into fibres and films

Cellulose xanthogenate
Cell-OH Cell-OCell-O- + CS2 Cell-O-CSS- Na+
Chemistry of xanthogenation is relatively complex:
ca. 70% of CS2 input is converted into cellulose xanthogenate
the rest is consumed by mainly formation of inorganic sulfidic
products

Cellulose xanthogenate
Cell-OH Cell-OCell-O- + CS2 Cell-O-CSS- Na+
Xanthogenated cellulose material

DS at C-2/C-3

DS at C-6

Fiber xanthogenate
(DS 0.61)

0.38

0.17

Viscose, non-ripened (DS 0.58)

0.34

0.24

Viscose, moderately ripened (DS 0.49)

0.16

0.32

Viscose, extensively ripened (DS 0.28)

0.32

Ripening: phase of the viscose process where the DS of xanthogenate is reduced to

the level that is desired for the fibre spinning process.

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Cellulose carbamate

High temperature reaction (~140): processed above the melting point of

urea
Catalyzed by metal salts, particularly zinc sulphate is used
Urea forms isocyanic acid which is the actual reagent with cellulose:
O

140C
NH
H2N

NH2

O + NH3

Cellulose carbamate

Cellulose carbamate with DS 0.2-0.3 can be dissolved in aqueous NaOH

Basis for the CarbaCell process:
Aimed at substituting the environmentally hazardous viscose process
Enabled by the effortless conversion of carbamate into cellulose in
alkali
No commercial applications as of yet

Cellulose sulphate

Can be prepared in a large variety of systems, usually containing either

SO3 or sulphuric acid
Water soluble at above DS 0.2-0.3
Preparation is generally accompanied by severe chain degradation due
to acid hydrolysis
No commercial applications as of yet

Cellulose nitrate
Traditionally produced in a ternary system: HNO3/H2SO4/H2O
Nitrogen contents of commercial cellulose nitrates range from 10.5-13.6%

Nitrogen content vs. DS

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Cellulose nitrate
The chemistry of traditional nitration is relatively complex:

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Cellulose nitrate
Nitrogen content vs. reaction time on nitration of spruce sulphite pulp

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Cellulose nitrate
Celluloid (combs, hair ornaments, ping pong balls)
Explosives (nitrogen content above 12.6%)
Filters, membranes
Component in lacquers

Esterification of cellulose
Organic esters:
- Cellulose formate
- Cellulose acetate

Cellulose formate
O
OH

HCOOH

O
HO

OH

H2O

Among the only organic esterifications that proceed spontaneously with

the free acid itself
Cellulose formate is unstable: cellulose formate with DS 2.0-2.5 is
decomposed to cellulose and formic acid in 10 h in boiling water

Cellulose formate
Effect of catalyst on the formylation of cellulose

Very high DS values of cellulose formate can be achieved

Philipp et al. Cellulose Chem. Technol. 1990, 24, 667.

Cellulose acetate

Cellulose acetylation proceeds with acetic anhydride and a suitable

catalyst in water-free conditions

Cellulose acetate preparation

Heterogeneous acetylation (2 different methods):
(1) Fibrous acetylation: native cellulosic fibre is acetylated and no clear
changes in gross morphology of the fibres are observed
(2) Solution process: native cellulosic fibre is acetylated and as the
acetylation proceeds, the acetylated cellulose chains on the surface are
solubilized into the solution
NOTE: The solution process (2) is occasionally called homogeneous
acetylation, but in reality it is a heterogeneous process that may eventually
lead into a homogeneous product (cellulose acetate solution).
NOTE: All industrial procedures are initially heterogeneous processes.

Cellulose acetate preparation

Schematic view on the
solution process: acetylated
cellulose chains are
released to the solution from
the cellulose microfibril
surface.

Cellulose acetate preparation

Acetylation

Cross sectional views of

Valonia microfibrils upon
heterogeneous solution
acetylation. Electron
microscopy and schematic
images.

Sassi and Chanzy Cellulose 1995, 2, 111.

Cellulose acetate

First, cellulose triacetate (CTA) is

formed after which it is
deacetylated in homogeneous
conditions.

Cellulose acetate deacetylation

Medium: DMSO/Water/aliphatic diamine

Hexamethylenediamine

Dimethylamine

Aliphatic
amines are
selective
towards C-2
/C-3 in
deacetylation.

Regioselectivity of deacetylation depends on the

reaction medium
Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,
Wiley-VCH, 1998.

Cellulose acetate solubility

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Cellulose acetate applications

Cellulose ethers
- methyl cellulose
- carboxymethyl cellulose
- hydroxyethyl cellulose
- hydroxypropyl cellulose

Commercial cellulose ethers

Methyl cellulose preparation

Conventional preparation by Williamson reaction with gaseous or liquid

chloroform (SN2 type nucleophilic substitution)
40% NaOH used in the industrial procedure (heterogeneous reaction)
DS 1.5-2.0 are produced commercially

Methyl cellulose preparation

Heterogeneous methylation of alkali cellulose with excess CH3Cl
90C
80C

90C
80C

70C

70C

Fast initial stage in methylation

Levelling off at just below DS 2

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Methyl cellulose solubility

DS dependence of solubility of methyl cellulose (and ethyl cellulose)

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Methyl cellulose solubility

At DS 1.7-2.3 the solubility of methyl cellulose is temperature sensitive at
ca. 50-60C: it forms gels above a critical temperature and the gelation
is reversible along the hysteresis loop.

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Methyl cellulose applications

Some applications of methyl cellulose

Carboxymethyl cellulose

The most important ionic cellulose derivative

Generally produced by a substitution reaction of monochloroacetic acid to
alkoxy cellulose

Carboxymethyl cellulose - preparation

Requires 20-30% NaOH concentration

1 mol NaOH consumed per 1 mol CMC substitution (main reaction)
2 mol NaOH consumed per 1 mol sodium glycolate (side reaction)
Temperature 50-70C
Exothermic process
Heterogeneous process in water/isopropanol (or water/t-butanol)

Carboxymethyl cellulose - preparation

Commercial grades possess DS values 0.4-0.8

CMC is water-soluble when DS>0.4

Carboxymethyl cellulose - solubility

Aqueous CMC solution does not usually represent a complete dissolution
down to the molecular level
Considerable part of the solution could be separated from the solution by
centrifugation, indicating poorly dissolved aggregates etc.

Higher DS
generally less
insoluble fragments
However, depends on
starting material and
preparation process

Klemm et al. Comprehensive Cellulose Chemistry Vol. 2,

Wiley-VCH, 1998.

Carboxymethyl cellulose applications

99.5 %

Information from CPKelco

Hydroxyethyl cellulose
Hydroxyethyl cellulose (HEC)

A range of reactions occurs when HEC is prepared with ethylene oxide in

water
The hydroxyalkyl side chain can grow further from the first substitution

Hydroxyethyl cellulose

Quantification of substitution:
DS: as usual, i.e., number of substituted hydroxyl groups in cellulose per
anhydroglucose unit
MS: molecular substitution, denoting the average number of alkylene oxide
molecules added per anhydroglucose unit

Hydroxyethyl cellulose

MS/DS ratio represents the average length of the HEC side chains
With high substitutions, MS/DS reaches a plateau

Arisz et al. Cellulose 1996, 3, 45.

Hydroxyethyl cellulose preparation

Heterogeneous system
NaOH/cellulose between 0.3:1 to 1:1
H2O/cellulose between 1.2:1 to 3.5:1
Temperature: 30-80C
MS (DS) determined by ethylene oxide input

Hydroxyethyl cellulose
Not thermoplastic: decomposes below 100C
Soluble in water above MS 1
Major applications:

Hydroxypropyl cellulose

Thermoplastic (can be extruded at 160)

Soluble in cold water at MS 4
Gelling in water at 40C, precipitation at 45C

Regioselective cellulose modification

Background
Generally, cellulose hydroxyl groups react in the order O6>O2>O3
Reactivity of different hydroxyl groups can be tuned by reaction conditions
but they are rarely exclusive
Regioselective synthesis applies various pathways to achieve nearly
complete regioselectivity of certain OH group / groups
Regioselectively prepared cellulose derivatives yield information on the
structure-property relationship of polysaccharides and the function of the
different hydroxyls on cellulose

Background
Terminology

Pathways to regioselectivity
Regioselective reactions with cellulose nearly always require
homogeneous reaction conditions where cellulose is completely dissolved
Solvents applied: dimethylacetamide/LiCl, tert-butyl ammonium fluoride /
dimethylsulfoxide (TBAF/DMSO)

Pathways to regioselectivity

Koschella et al. Macromol. Symp. 2006, 244, 59.

Protecting group: trityl

One of the most popular protective groups for regioselective modification is
triphenylmethyl (trityl):

6-mono-O-methyl cellulose

Two different
protecting groups:
trityl and
1-propenyl

Kondo et al. Carbohydr. Res. 1993, 238, 231.

Protecting group: TDMS

= Thexyldimethylsilyl

Highly swollen yet heterogeneous medium exclusive for C-6

Homogeneous 2,6 selective

Koschella et al. Macromol. Symp. 2006, 244, 59.

Fox et al. Biomacromolecules 2011, 12, 1956.

3-mono-O-ethyl cellulose

Soluble in water and DMSO

Koschella et al. Polym. Bull. 2006, 57, 33.

Summary
Important cellulose esters: cellulose xanthogenate, cellulose nitrate,
cellulose acetate
Important cellulose ethers: methyl cellulose, carboxymethyl cellulose,
hydroxyethyl cellulose
Regioselective cellulose modification is a modern trend; it is an important
scientific advance in cellulose modification