Cellulose Solutions in Ionic Liquids

• US 20080190321A1
• Filed: 04/07/2006
• Published: 08/14/2008
• Est. Priority Date: 04/15/2005
• Status: Active Grant

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Maase, Matthias, Stegmann, Veit
• Granted Patent: US 7,749,318 B2
• Time in Patent Office: Days
• US Class Current: 106/200.2
• CPC Class Codes: C08B 1/003 Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids solutions used in the manufacture of monocomponent artificial filaments or cellulose or derivatives thereof D01F2/02
• CPC Class Codes: C08J 2301/02 Cellulose; Modified cellulose
• CPC Class Codes: C08J 3/091 characterised by the chemical constitution of the organic liquid
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids
• CPC Class Codes: Y10T 428/2989 Microcapsule with solid core [includes liposome]

Abstract

The present invention relates to a solution comprising cellulose and an ionic liquid comprising anions and cations as solvent, wherein the cations comprise at least one atom selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus which is present in protonated form, its preparation and use for physical and chemical treatment.

Claims

1. A solution comprising cellulose and an ionic liquid comprising anions and cations as solvent, wherein the cations comprise at least one atom selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus which is present in protonated form.

2. The solution according to claim 1, wherein the cations comprise at least one nitrogen atom which is present in protonated form as an ammonium cation.

3. The solution according to claim 1, wherein said solution comprises more than 1% by weight of cellulose, based on the total weight of the solution.

4. The solution according to claim 1, wherein said anions and cations form a salt of general formula (I)

[A]_n⁺ [Y]ⁿ⁻

 

 

(I),

where n is 1, 2, 3 or 4, [A]⁺ is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation and [Y]ⁿ⁻

is a monovalent, divalent, trivalent or tetravalent anion;

or

mixed salts of general formulae (II)

[A¹]⁺[A²]⁺[Y]ⁿ⁻

 

 

(IIa), where n=2;

[A¹]⁺[A²]⁺[A³]⁺[Y]ⁿ⁻

 

 

(IIb), where n=3;

[A¹]⁺[A²]⁺[A³]⁺[A⁴]⁺[Y]ⁿ⁻

 

 

(IIc), where n=4, and

where [A¹]⁺, [A²]⁺, [A³]⁺ and [A⁴]⁺ are selected independently from among the groups mentioned for [A]⁺, and [Y]ⁿ⁻

is as defined under (A);

or

mixed salts of general formulae (III)

[A¹]⁺[A²]⁺[A³]⁺[M¹]⁺[Y]ⁿ⁻

 

 

(IIIa), where n=4;

[A¹]⁺[A²]⁺[M¹]⁺[M²]⁺[Y]ⁿ⁻

 

 

(IIIb), where n=4;

[A¹]⁺[M¹]⁺[M²]⁺[M³]⁺[Y]ⁿ⁻

 

 

(IIIc), where n=4;

[A¹]⁺[A²]⁺[M¹]⁺[Y]ⁿ⁻

 

 

(IIId), where n=3;

[A¹]⁺[M¹]⁺[M²]⁺[Y]ⁿ⁻

 

 

(IIIe), where n=3;

[A¹]⁺[M¹]⁺[Y]ⁿ⁻

 

 

(IIIf), where n=2;

[A¹]⁺[A²]⁺[M⁴]²⁺[Y]ⁿ⁻

 

 

(IIIg), where n=4;

[A¹]⁺[M¹]⁺[M⁴]²⁺[Y]ⁿ⁻

 

 

(IIIh), where n=4;

[A¹]⁺[M⁵]³⁺[Y]ⁿ⁻

 

 

(IIIi), where n=4;

or

[A¹]⁺[M⁴]²⁺[Y]ⁿ⁻

 

 

(IIIj), where n=3, and

where [A¹]⁺, [A²]⁺ and [A³]⁺ are selected independently from among the groups mentioned for [A]⁺, [Y]ⁿ⁻

is as defined under (A) and [M¹]⁺, [M²]⁺, [M³]⁺ are monovalent metal cations, [M⁴]²⁺ is a divalent metal cation and [M⁵]³⁺ is a trivalent metal cation.

5. The solution according to claim 1, wherein the ionic liquid comprises at least one cation selected from the group consisting of cations of formulae (IVa) to (IVy):

6. The solution according to claim 1, wherein the ionic liquid comprises at least one anion selected from the group consisting of

the group of halides and halogen compounds of the formulae:

F⁻

, Cl⁻

, Br⁻

, I⁻

, BF₄⁻

, PF₆⁻

, AlCl₄⁻

, Al₂Cl₇⁻

, Al₃Cl₁₀⁻

, AlBr₄⁻

, FeCl₄⁻

, BCl₄⁻

, SbF₆⁻

, AsF₆, ZnCl₃⁻

, SnCl₃⁻

, CuCl₂⁻

, CF₃SO₃⁻

, (CF₃SO₃)₂N⁻

, CF₃CO₂⁻

, CCl₃CO₂⁻

, CN⁻

, SCN⁻

, OCN⁻

the group of sulfates, sulfites and sulfonates of the general formulae;

SO₄²⁻

, HSO₄⁻

, SO₃²⁻

, HSO₃⁻

, R^aOSO₃⁻

, R^aSO₃⁻

the group of phosphates of the general formulae

PO₄³⁻

, HPO₄²⁻

, H₂PO₄⁻

, R^aPO₄²⁻

, HR^aPO₄⁻

, R^aR^bPO₄⁻

the group of phosphonates and phosphinates of the general formulae;

R^aHPO₃⁻

, R^aR^bPO₂⁻

, R^aR^bPO₃⁻

the group of phosphites of the general formulae;

PO₃³⁻

, HPO₃²⁻

, H₂PO₃⁻

, R^aPO₃²⁻

, R^aHPO₃⁻

, R^aR^bPO₃⁻

the group of phosphonites and phosphinites of the general formulae;

R^aR^bPO₂⁻

, R^aHPO₂⁻

, R^aR^bPO⁻

, R^aHPO⁻

the group of carboxylic acids of the general formula;

R^aCOO⁻

the group of borates of the general formulae;

BO₃³⁻

, HBO₃²⁻

, H₂BO₃⁻

, R^aR^bBO₃⁻

, R^aHBO₃⁻

, R^aBO₃²⁻

, B(OR^a)(OR^b)(OR^c)(OR^d)⁻

, B(HSO₄)⁻

, B(R^aSO4)⁻

the group of boronates of the general formulae;

R^aBO₂²⁻

, R^aR^bBO⁻

the group of carbonates and carbonic esters of the general formulae;

HCO₃⁻

, CO₃²⁻

, R^aCO₃⁻

the group of silicates and silicic esters of the general formulae;

SiO₄⁴⁻

, HSiO₄³⁻

, H₂SiO₄²⁻

, H₃SiO₄⁻

, R^aSiO₄³⁻

, R^aR^bSiO₄²⁻

, R^aR^bR^cSiO₄⁻

, HR^aSiO₄², H₂R^aSiO₄⁻

, HR^aR^bSiO₄⁻

the group of alkyl silane and aryl silane salts of the general formulae;

R^aSiO₃³⁻

, R^aR^bSiO₂²⁻

, R^aR^bR^cSiO⁻

, R^aR^bR^cSiO₃⁻

, R^aR^bR^cSiO₂⁻

, R^aR^bSiO₃²⁻

the group of carboximides, bis(sulfonyl)imides and sulfonylimides of the general formulae;

7. The solution according to claim 1 which has a temperature of not more than 180°

C.

8. A process for preparing a solution according to claim 1, which comprises the steps of

a) addition of adding cellulose to a solution comprising an ionic liquid comprising anions and cations as solvent, wherein the cations comprise at least one nitrogen atom which is present in protonated form as an ammonium cation, and

b) mixing of the solution until the cellulose is completely dissolved.

9. A method for the physical or chemical treatment of cellulose comprising the use of an ionic liquid comprising anions and cations as solvent, wherein the cations comprise at least one atom selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus which is present in protonated form.