Glucomannan:

Content: 2 5% Composed of b-D-glucopyranose and b-D-mannopyranose Linked: (1 4) bonds

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Reactivity and Accessibility of Cellulose

HO CH2 O OH O OH H2C OH O OH O O OH

Reactivity: Etherification: Ionization of hydroxyl Acidity and dissociation tendency: HO-6 < HO-3 < HO-2 Esterification: Highest reactivity: HO-6
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Accessibility: Relative ease by which hydroxyl groups can be reached by the reactants. Sterical reason: HO-6 is the most reactive for bulky substituent. Accessibility Vs. Crystallinity
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Effect of crystallinity and hydrogen bonding on the acetylation of cotton fibers.

a. Original fibers b. Destruction of crystalline by ethylene amine treatment, followed by subsequent drying. c. As (b), but without subsequent drying.
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Degree of Substitution (DS)

Strongly swollen state cellulose: OH accessible to the reactants Homogeneous products obtained when DS = 3 Less than DS-3: 1. Unreacted glucose units 2. Monosubstituted units : 2-derivatives HO CH2 3-derivatives O 6-derivatives OH
O

OH O OH O O

3. Disubstituted units : 2,6-derivatives 3,6-derivatives

OH

H2C

OH

2,3-derivatives

4. Fully substituted units: 2,3,6-derivative

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Swelling and Dissolution of Cellulose:

Swelling extent: solvent and nature of cellulose sample Swelling type: intercrystalline swelling intracrystalline swelling Significant swelling in diameter and insignificant in length of cellulose fiber Water retention of cellulose fibers varies depending on: Equilibration of hysteresis Chemical composition Swell in electrolyte solution: hydrated ions require more space than water molecules Intracrystalline swelling: by concentrated solution of strong bases or acids and some salts: Limited : combined at certain stoichiometric proportion with cellulose ordered region, not destroying interfibrillar bonding Unlimited: bulky swelling agents form complexes with cellulose and break adjacent bonds. HHT341 Dr. Nyoman Wistara 6

Properties of Common Cellulose Solvents (Sjostrom 1993)

Abbreviation Schweizers solution (Cuoxam) CED (Cuen) Cadoxen

Formula [Cu(NH3)4](OH2)

Properties Dark blue. Extensive depolymerization of cellulose in the presence of oxygen. Dark blue. Depolymerization of cellulose in the presence of oxygen. Colorless, useful for optical measurements. Cellulose shows good stability in this solvent. Greenish. Cellulose shows good stability in this solvent.

[Cu(en)2](OH)2a [Cd(en)3](OH)2

EWNN
a b

[FeT3]Na6b

en is ethylenediamine T is tartrate

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ESTERS A. Ester of Inorganic Acids

Cellulose is esterified with certain inorganic acids:
Nitric acid Sulfuric acid Phosphoric acid Acid prerequisites:

Bring about strong swelling

Esterifification: typical equilibrium reaction: alcohol and acid ester + water The most important product: cellulose nitrate

(1) Cellulose Nitrate

HONO2 + 2H2SO4
NO2 + HO Cell
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NO2 + H3O + 2HSO4 .. (1)

NO2 OH Cell
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NO2 OH Cell + H (2)

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Commercial Grades of Cellulose Nitrate:

DS 1.9 2.0 1.9 2.3 2.0 2.3 2.4 2.8 Ethanol Esters, ethanol, ether-alcohol Esters Acetone Solvent Applications Plastics Lacquers Films, cements Explosives

(2) Cellulose Sulfate:

Prepared using a variety of reagent combinations. Active agents is SO3 Suitable reagents for preparing cellulose acetate: Sulfuric acid/ethanol, propanol, butanol Fuming sulfuric acid/sulfur trioxide Sulfur trioxide/sulfur dioxide, dimethylformamide, carbon disulfide Chlorosulfonic acid/sulfur dioxide, pyridine Water soluble, can be used as thickening agents.

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The Reaction Steps:

2 H2SO4

H3O + HSO4 + SO3

......... (1)

H Cell OH + SO3 Cell O SO3 Cell O SO3 + H ......... (2)

H Cell OH + H2SO4 Cell O H + HSO4 Cell O SO3 + H3O .....(3)

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B. Ester of Organic Acids

(1) Cellulose Acetate:
Replacing cellulose nitrate in many products

Acetylation of cellulose is a heterogeneous system:

Reagent diffusion controlling the reaction rate. Fiber need to be swollen Production via solution process:

Pulp treatment with AcOH + catalyst (H2SO4) swell and

increase fiber reactivity Acetylation: addition of acetic anhydride + H2SO4 (catalyst) in the presence of AcOH. After full acetylation, triacetate is dissolved. Fibrous acetylation: need suitable liquid (e.g. benzene) Other catalyst: perchloric acid, zinc chloride

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Commercial Grade of Cellulose Acetate:

DS 1.8 1.8 2.2 2.3 2.3 2.4 2.5 2.6 2.8 2.9 2.9 3.0

Solvents Water propanol chloroform Acetone Acetone Acetone Methylene chloride ethanol Methylene chloride

Applications Composite fabrics Lacquers, plastics Acetate rayon X ray and safety films Insulating foils Fabrics

Typical Specifications for Acetylation Grade Pulp:

A Cellulose (%) Pentosan (%) Intrinsic viscosity (dm3/kg) Ether extractable (%) Ash (%) Iron (mg/kg)

> 95.6 < 2.1 550 - 750 < 0.15 < 0.08 < 10

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Mechanism of acid-catalyzed acetylation:

OH CH3 O CH3 O +H OH CH3

O OH CH3 O
- CH3COOH -H

C O C CH3
+ Cell OH

C O C CH3

C O C CH3 HO Cell

C O C CH3

O CH3 C O Cell

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ETHERS
Prepared by treating alkali cellulose with alkyl, aryl halides (or sulfates), and unsaturated compound activated by electron-attracting groups. Most soluble in water Have similar properties and specific characteristic complete each other Water soluble at low DS With hydrophobic substituents and high DS soluble in organic solvent

Types of Commercial Cellulose Ethers :

Cellulose ether Methylcellulose Ethylcellulose Hydoxymethylcellulose Cyanoethylcellulose

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Reagent Methyl chloride, dimethyl sulfate Ethyl chloride Ethylene oxide Acrylonitrile
Dr. Nyoman Wistara

Solvent Water Organic solvents Water Water Organic solvents

DS 1.5 2.4 2.3 2.6 0.5 1.2 1.3 3.0 2.0

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Carboxymethylcellulose Sodium chloroacetate

(1) Alkyl Ethers : Alkylation by using alkyl chloride Used as additives: agricultural products, food products, ceramics, pharmaceutical, cements, textiles, paper products, and plywood. Mechanism bimolecular nucleophilic substitution (SN2):

Cell

OH

+ HO

Cell

+ H2O

Cell

+ R

Cl C2H5 )

Cell

OR + Cl

(R = CH3 or

By products: ethanol or methanol :

RCl + HO

ROH + Cl

Ethanol or methanol then react with alkyl chloride to form diethyl or dimethyl ether :

ROH + HO

RO + H2O ROR + Cl
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RO
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+ R

Cl

(2) Hydroxyalkyl Ethers :

Obtained from cellulose reaction with alkene oxides or their corresponding chlorohydrins. Reaction mechanism: base-catalyzed SN2 type substitution. Commercial productions : hydroxyethyl and hydroxypropylcellulose reagents: ethylene oxide and propylene oxide. Formation:

Cell

+ H2C O

CH2

Cell

CH2CH2O

Ethylene can also reacts with hydroxide ions to form ethylene glycol:

HO

+ H2C O

CH2

CH2OH

CH2O

Ethylene can further polymerize to polyethylene oxide terminal primary hydroxyl group of the substituent reacts with additional epoxide ethylene pendant chains:

Cell

CH2CH2OH + n H2C O

CH2

HO

Cell

(O CH2CH2)n+1OH

Polymerization DS of hydroxyalkyl cellulose lower than MS MS/DS relative length of side chains a half react w/ cellulose and a half for side chains Used for: thickener of latex paint, emulsion polymerization of PVA, paper sizing etc. HHT341 Dr. Nyoman Wistara 16

(3) Carboxymethylcellulose (CMC) :

Most widely used water-soluble cellulose derivative. Prepared from : cellulose and sodium chloroacetate. DS : 0.4 1.4; solubility increases with increasing DS. DS: 0.6 0.8 good water solubility; 0.05 0.25 soluble in alkali only. Used for: detergents, food, ice cream, paper coating, emulsion paints, drilling fluids, ceramics, pharmaceuticals, and cosmetics. Reaction mechanism:

Cell

O + CH2COO Cl

Cell

CH2COO + Cl

(4) Cyanoethylcellulose :
Cellulose react with a,b unsaturated compounds containing strongly electronattracting groups substituted ethyl ethers . Cyanoethylation acrylonitrile as reagent in strongly basic catalyst (NaOH). Used for: insulation paper Reaction mechanism:
Cell O + CH2 CH C N Cell OCH2CH2CN +H2O Cell O CH2 CH C N Cell O CH2 CH C N + HO

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CELLULOSE XANTHATE :
Cellulose xanthate (dithiocarbonate) Treatment of alkali cellulose with carbon disulfide Viscose rayon and cellophane proceed via the xanthate extremely important cellulose derivative Xanthation reaction:

S Cell
The process:
Alkali cellulose : Pressing 18% NaOH 15 30 oC Shredded and Ripening to DP: 200 400

O + C S

Cell

O C S

Xanthation : 25 30 oC 3 hours DS: 0.5

Dissolving In aqueous NaOH

Rayon fibers

Spinning (into acid bath)

Filtered

Viscose (orange-colored)

The rayon fiber:

Cell

C S

Cell

OH + CS2

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