Polymer dissolution and blend formation in ionic liquids

• US 20050288484A1
• Filed: 03/24/2005
• Published: 12/29/2005
• Est. Priority Date: 03/26/2004
• Status: Active Grant

• Current Assignee: University of Alabama (University of Alabama System)
• Original Assignee: University of Alabama (University of Alabama System)
• Inventors: Chen, Ji, Rogers, Robin D., Swatloski, Richard P., Daly, Dan, Holbrey, John
• Granted Patent: US 7,888,412 B2
• Time in Patent Office: Days
• US Class Current: 528/480
• 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 3/005 Processes for mixing polymers
• CPC Class Codes: C08J 3/09 in organic liquids
• CPC Class Codes: C08J 3/091 characterised by the chemical constitution of the organic liquid
• CPC Class Codes: C08L 1/02 Cellulose; Modified cellulose
• CPC Class Codes: C08L 2205/03 containing three or more polymers in a blend
• CPC Class Codes: C08L 2205/035 containing four or more polymers in a blend
• CPC Class Codes: C08L 25/12 with unsaturated nitriles
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/20 Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
• CPC Class Codes: C08L 2666/26 Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
• CPC Class Codes: C08L 29/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: C08L 3/02 Starch; Degradation products thereof, e.g. dextrin
• CPC Class Codes: C08L 33/20 Homopolymers or copolymers of acrylonitrile C08L55/02 takes precedence
• CPC Class Codes: C08L 5/14 Hemicellulose; Derivatives thereof
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C08L 79/02 Polyamines

Abstract

The present invention relates to processes utilizing ionic liquids for the dissolution of various polymers and/or copolymers, the formation of resins and blends, and the reconstitution of polymer and/or copolymer solutions, and the dissolution and blending of “functional additives” and/or various polymers and/or copolymers to form advanced composite materials.

Claims

1. :

A process for forming a resin or blend, comprising;

mixing at least one ionic liquid, which is a liquid salt complex that exists in the liquid phase between about −

70 to about 300°

C., with at least two differing polymeric materials to form a mixture, and adding a non-solvent to the mixture to remove the ionic liquid from the resin or blend.

2. :

The process of claim 1, wherein the mixture is heated to about 100°

C.

3. :

The process of claim 1, wherein the number of polymeric materials is two.

4. :

The process of claim 1, wherein the number of polymeric materials is three.

5. :

The process of claim 1, wherein the number of polymeric materials is four.

6. :

The process of claim 1, wherein at least one of the polymeric materials is a member selected from the group consisting of cellulose, hemicellulose, starch, poly-2-hydroxymethylmethacrylate, polyamides, polyesters, polyimideamides, polybenzoimide, aramides, polyimides, polyvinyl alcohol, polyaniline, polyethylene glycol, polyacrylonitrile, polyethylene oxide with terminal amine groups, linear polyethyleneimine, and branched polyethyleneimine.

7. :

The process of claim 1, wherein the mixture is heated by a microwave.

8. :

The process of claim 1, wherein the at least one ionic liquid comprises at least one organic cation wherein the organic portion is a member selected from the group consisting of imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles, furans, thiophens, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles, isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophens, dibenzothiophens, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, annolines, phthalazines, quinazolines and quinoxalines, and combinations thereof; and

at least one anionic group selected from the group consisting of halogens, BX₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, NO₂⁻

, NO₃⁻

, SO₄²⁻

, BR₄⁻

, substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates, phosphites, polyoxometallates, substituted or unsubstituted carboxylates, triflates and noncoordinating anions; and

wherein R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.

9. :

The process of claim 1, wherein the non-solvent is water.

10. :

A process for forming a polymeric resin or blend comprising mixing a blend of cations and anions of one or more ionic liquids, wherein the blend is selected to optimize solubility of the polymeric resin or blend, with at least two differing polymeric materials, and adding a non-solvent to the mixture to remove the ionic liquid(s) from the resin or blend.

11. :

The process of claim 10, wherein the mixture is heated to about 100°

C.

12. :

The process of claim 10, wherein the number of polymeric materials is two.

13. :

The process of claim 10, wherein the number of polymeric materials is three.

14. :

The process of claim 10, wherein the number of polymeric materials is four.

15. :

The process of claim 10, wherein at least one of the polymeric materials is a member selected from the group consisting of cellulose, hemicellulose, starch, poly-2-hydroxymethylmethacrylate, polyamides, polyesters, polyimideamides, polybenzoimide, aramides, polyimides, polyvinyl alcohol, polyaniline, polyethylene glycol, polyacrylonitrile, polyethylene oxide with terminal amine groups, linear polyethyleneimine, and branched polyethyleneimine.

16. :

The process of claim 10, wherein the mixture is heated by a microwave.

17. :

The process of claim 10, wherein the one or more ionic liquids comprise at least one organic cation wherein the organic portion is a member selected from the group consisting of imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles, furans, thiophens, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles, isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophens, dibenzothiophens, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, annolines, phthalazines, quinazolines and quinoxalines, and combinations thereof; and

at least one anionic group selected from the group consisting of halogens, BX₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, NO₂⁻

, NO₃⁻

, SO₄²⁻

, BR₄⁻

, substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates, phosphites, polyoxometallates, substituted or unsubstituted carboxylates, triflates and noncoordinating anions; and

wherein R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.

18. :

The process of claim 10, wherein the non-solvent is water.

19. :

A process for forming a resin or polymer blend with targeted rheological properties, comprising mixing at least one ionic liquid, which is a liquid salt complex that exists in the liquid phase between about −

70 to about 300°

C., with at least two differing polymeric materials, in a ratio to give a polymer blend with predicted properties, to form a mixture, and adding a non-solvent to the mixture to remove the ionic liquid from the resin or blend.

20. :

The process of claim 19, wherein the mixture is heated to about 100°

C.

21. :

The process of claim 19, wherein the number of polymeric materials is two.

22. :

The process of claim 19, wherein the number of polymeric materials is three.

23. :

The process of claim 19, wherein the number of polymeric materials is four.

24. :

The process of claim 19, wherein at least one of the polymeric materials is a member selected from the group consisting of cellulose, hemicellulose, starch, poly-2-hydroxymethylmethacrylate, polyamides, polyesters, polyimideamides, polybenzoimide, aramides, polyimides, polyvinyl alcohol, polyaniline, polyethylene glycol, polyacrylonitrile, polyethylene oxide with terminal amine groups, linear polyethyleneimine, and branched polyethyleneimine.

25. :

The process of claim 19, wherein the mixture is heated by a microwave.

26. :

The process of claim 19, wherein the at least one ionic liquid comprises at least one organic cation wherein the organic portion is a member selected from the group consisting of imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles, furans, thiophens, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles, isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophens, dibenzothiophens, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, annolines, phthalazines, quinazolines and quinoxalines, and combinations thereof; and

at least one anionic group selected from the group consisting of halogens, BX₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, NO₂⁻

, NO₃⁻

, SO₄²⁻

, BR₄⁻

, substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates, phosphites, polyoxometallates, substituted or unsubstituted carboxylates, triflates and noncoordinating anions; and

wherein R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.

27. :

The process of claim 19, wherein the non-solvent is water.

28. :

A resin or blend, comprising at least two differing polymeric materials isolated from one or more ionic liquids.

29. :

The process of claim 28, wherein the mixture is heated to about 100°

C.

30. :

The process of claim 28, wherein the number of polymeric materials is two.

31. :

The process of claim 28, wherein the number of polymeric materials is three.

32. :

The process of claim 28, wherein the number of polymeric materials is four.

33. :

The process of claim 28, wherein at least one of the polymeric materials is a member selected from the group consisting of cellulose, hemicellulose, starch, poly-2-hydroxymethylmethacrylate, polyamides, polyesters, polyimideamides, polybenzoimide, aramides, polyimides, polyvinyl alcohol, polyaniline, polyethylene glycol, polyacrylonitrile, polyethylene oxide with terminal amine groups, linear polyethyleneimine, and branched polyethyleneimine.

34. :

The process of claim 28, wherein the mixture is heated by a microwave.

35. :

The process of claim 28, wherein the at least one ionic liquid comprises at least one organic cation wherein the organic group is a member selected from the group consisting of imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles, furans, thiophens, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles, isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophens, dibenzothiophens, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, annolines, phthalazines, quinazolines and quinoxalines, and combinations thereof; and

at least one anionic group selected from the group consisting of halogens, BX₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, NO₂⁻

, NO₃⁻

, SO₄²⁻

, BR₄⁻

, substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates, phosphites, polyoxometallates, substituted or unsubstituted carboxylates, triflates and noncoordinating anions; and

wherein R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.

36. :

The process of claim 28, wherein the amounts of the at least two differing polymeric materials are adjusted to produce a targeted property.

37. :

The process of claim 28, wherein the amounts of the at least two differing polymeric materials are adjusted to produce a targeted rheological property.

38. :

A mixture comprising at least two differing polymeric materials and one or more ionic liquids.

39. :

The process of claim 38, wherein the mixture is heated to about 100°

C.

40. :

The process of claim 38, wherein the number of polymeric materials is two.

41. :

The process of claim 38, wherein the number of polymeric materials is three.

42. :

The process of claim 38, wherein the number of polymeric materials is four.

43. :

The process of claim 38, wherein at least one of the polymeric materials is a member selected from the group consisting of cellulose, hemicellulose, starch, poly-2-hydroxymethylmethacrylate, polyamides, polyesters, polyimideamides, polybenzoimide, aramides, polyimides, polyvinyl alcohol, polyaniline, polyethylene glycol, polyacrylonitrile, polyethylene oxide with terminal amine groups, linear polyethyleneimine, and branched polyethyleneimine.

44. :

The process of claim 38, wherein the mixture is heated by a microwave.

45. :

The process of claim 38, wherein the at least one ionic liquid comprises at least one organic cation wherein the organic group is a member selected from the group consisting of imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles, furans, thiophens, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles, isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophens, dibenzothiophens, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, annolines, phthalazines, quinazolines and quinoxalines, and combinations thereof; and

at least one anionic group selected from the group consisting of halogens, BX₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, NO₂⁻

, NO₃⁻

, SO₄²⁻

, BR₄⁻

, substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates, phosphites, polyoxometallates, substituted or unsubstituted carboxylates, triflates and noncoordinating anions; and

wherein R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.