Ionic Liquids as Reaction Media for Cellulose

Homogeneous chemical modification of cellulose provides several advantages over heterogeneous reactions such as: increased reactivity, uniform product composi­tion, and efficient control over the overall degree of substitution (DS) as well as the distribution of functional groups within the anhydroglucose unit (AGU) and along the polymer chain. A variety of specific polysaccharide solvents that can be used not only for dissolution but also for the derivatization of cellulose have been reported in scientific literature [9]. They could be applied for preparing a broad variety of polysaccharide derivatives with potential applications from multi-kiloton food — and construction material industry to highly engineered materials for medical and biotechnological use. Nevertheless, none of the many cellulose solvents that could be utilized in lab-scale synthesis was found to be suitable for commercially attractive synthesis of cellulose derivatives up to now. Production of cellulose derivatives in technical scales is performed exclusively under heterogeneous con­ditions. In this context, ILs received a lot of interest because these versatile novel solvents might overcome the limitations of classical cellulose solvents; such as low dissolution power, inefficient solvent recycling, and incompatibility with derivati — zation reagents. In particular the broad structural diversity of ILs and the possibil­ities to create task-specific solvents by subtle manipulation of the molecular structure bear huge potential. Moreover, ILs have been employed with high effi­ciency in low-molecular chemistry as solvents for a vast number of advanced organic reactions that are still waiting to be transferred to cellulose derivatization [10]. Many cellulose derivatives could be prepared already by using ILs as reaction media for cellulose (Table 5.1). A comprehensive overview of the chemical deriv- atization of cellulose in ILs is provided in the following passages. Most of the synthesis described focused mainly on three particular imidazolium based ILs (Fig. 5.1) or slightly modified analogues. However, some reports on novel IL based reaction media were included as well.

Table 5.1 Overview of cellulose derivatives prepared in ionic liquids

Cellulose derivative

Reaction conditions

Entry

Type

DS rangea

ILb

Comments

Refs.

Cellulose esters

1

Acetate

0.9-2.8

AMIMCl

[11,12]

1.9-3.0

BMIMCl,

[13, 14]

EMIMCl,

BDMIMCl,

ADMIMBr

0.7-3.0

BMIMCl

Bacterial

[15]

cellulose

2.0-2.7

ABMIMCl

[16]

1.5-2.8

ABMIMCl

Microwave

[17]

used

2

Propionate

0.5-2.9

AMIMCl

Catalyst used

[18]

1.5-2.3

ABMIMCl

Microwave

[17]

used

3

Butyrate

0.5-2.8

AMIMCl

Catalyst used

[18]

2.4-2.8

ABMIMCl

Microwave

[17]

used

4

Pentanoate

2.9

ABMIMCl

Microwave

[17]

used

5

Hexanoate

2.7-2.9

ABMIMCl

Microwave

[17]

used

6

Laurate

0.3-1.5

BMIMCl

Phase

[14]

separation

7

Stearate

2.2-2.6

BMIMCl

[19]

8

Benzoate

1.0-3.0

AMIMCl

[20]

9

Fuorate

0.5-3.0

BMIMCl

CDI activation

[21]

10

Oxy-carboxylic

0.1-3.0

AMIMCl,

CDI activation,

[22]

acid ester

BMIMCl,

bacterial

EMIMCl

cellulose

11

2-halo-carboxylate

0.6-1.0

AMIMCl

Co-solvent used

[23, 24]

0.7

AMIMCl

Co-solvent used

[25]

0.3-1.9

BMIMCl

[26]

12

Succinate

0.2-2.3

BMIMCl

Co-solvent

[27-29]

used, cata­lyst used

13

Phthalate

0.1-2.5

BMIMCl

Catalyst used

[30,31]

14

Glutarate

0.3-1.2

BMIMCl

Ultrasound

[32]

used

15

Sulfate

0.1-1.5

AMIMCl,

Co-solvent used

[33]

BMIMCl,

EMIMCl

1.3-1.7

BMIMCl

Co-solvent used

[34]

16

Sulfonate (tosylate)

0.1-1.1

BMIMCl,

Co-solvent used

[35]

AMIMCl

0.8

AMIMCl

[36]

(continued)

Table 5.1 (continued)

Cellulose derivative

Reaction conditions

Entry

Type

DS rangea

ILb

Comments

Refs.

Cellulose ethers

17

Carboxymethyl

0.5

BMIMCl

Heterogeneous

[13]

18

Hydroxyalkyl

0.1-2.2

BMIMCl,

Co-solvent used

[37, 38]

BDMIMCl,

BDTAC,

EMIMAc

19

Triphenylmethyl

0.8, 1.8

AMIMCl

Co-solvent used

[39]

(trityl)

0.8-1.4

BMIMCl

Co-solvent used

[40]

20

Trimethylsilyl

0.4-2.9

BMIMCl,

Co-solvent used

[41]

EMIMAc

0.2-3.0

BMIMCl,

Heterogeneous

[42]

BMIMAc,

BMIMBz,

BMIMPr,

EMIMAc,

EMIMDEP

Miscellaneous derivatives

21

Phenyl carbamate

0.5-3.0

BMIMCl

[14]

0.5-3.0

BMIMCl

Bacterial

[15]

cellulose

22

graft-poly

0.8-1.0

AMIMCl

Catalyst used

[43]

(L-lactide)

(1.5—1.7)c

0.7-2.7

AMIMCl

Catalyst used

[44]

(1.4—4.5)c

0.5-2.0

BMIMCl

Catalyst used

[45]

(1.7-2.4)c

23

Mixed acetate/

0.4-2.5;

AMIMCl

Catalyst used

[46]

graft-poly

0.2-1.9

(L-lactide)

(3.5-9.3)c

24

graft-poly

0.1-2.4

BMIMCl

Catalyst used

[47]

(g-caprolactone)

(2.3—3.1)c

25

graft-poly

n. a.

BMIMCl

[48]

(N-iospropyl-

acrylamide)

26

graft-poly(acrylic

n. a.

BMIMCl

Cross linking

[49]

acid)

aDS: degree of substitution

bIonic liquids: cations: ADMIM+: 1-allyl-2,3-dimethylimidazolium, AMIM+: 1-allyl-3- methylimidazolium, BDMIM+: 1-butyl-2,3-dimethylimidazolium, BMIM+: 1-butyl-3-methylimi — dazolium, EMIM+: 1-ethyl-3-methylimidazolium, anions: Ac-: acetate, Bz-: benzoate, Cl-: chloride, DEP-:diethylposphate, Pr-: propionate

cValues in braces represent degree of polymerization of the grafted chain

image105

Fig. 5.1 Molecular structures of ionic liquids most frequently applied as homogeneous reaction media for derivatization of cellulose