Ionic liquids for solubilizing polymers
The present invention relates to a liquid composition which comprises at least one polymer and at least one ionic liquid, the cations of which are derived from polycyclic amidine bases, and a process for isolating cellulose from cellulose-containing sources using at least one such ionic liquid.
1. A process for obtaining at least one constituent of a lignocellulose material, wherein the constituent is solubilized selectively, or liberated selectively or solubilized and liberated selectively from a solubilized product of the lignocellulose material, and wherein at least one ionic liquid is employed for the solubilization and/or liberation, wherein the at least one ionic liquid is at least one ionic liquid represented by formula I
wherein
A together with the C—N group to which it is bonded, forms a 4- to 8-membered, saturated or unsaturated or aromatic ring, which is optionally substituted, which can optionally have further heteroatoms or heteroatom-containing groups, and which can have further fused-on saturated, unsaturated or aromatic carbocyclic rings or heterocyclic rings,
B together with the amidino group to which it is bonded, forms a 4- to 8-membered, mono- or polyunsaturated, non-aromatic ring, which is optionally substituted and can have further fused-on saturated, unsaturated or aromatic carbocyclic rings or heterocyclic rings,
R represents hydrogen or an organyl radical,
Y n− represents a mono-, di-, tri- or tetravalent anion, and
n represents one, two, three or four
and at least one polymer solubilized therein.
2. The process according to claim 1 , comprising obtaining a liquid phase enriched in lignin and a residue enriched in cellulose by treating the lignocellulose material with at least one ionic liquid of the general formula I.
3. The process according to claim 2 , comprising employing at least one ionic liquid of the general formula I for treating the lignocellulose material, wherein the anion is selected from the group consisting of tosylate, trifluoroacetate, saccharinate, lactate, hydrogensulfate, trifluoromethanesulfonate, di(ethylhexyl)phosphate and thiocyanate.
4. The process according to claim 1 , comprising obtaining a liquid phase enriched in lignin and in cellulose by treating the lignocellulose material with at least one ionic liquid of the general formula I, and separating the liquid phase into a fraction enriched in lignin and a fraction enriched in cellulose.
5. The process according to claim 4 , employing at least one ionic liquid of the general formula I for treating the lignocellulose material, wherein the anion is selected from the group consisting of chloride, methanesulfonate, formate, acetate and a di(C 1 -C 4 -alkyl)phosphate.
6. The process of claim 1 , wherein in the formula I the cations are selected from the group consisting of cations of formulae I.1 and I.2
wherein
R and A are defined according to claim 1 , and
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl, hetaryl, hydroxyl, SH, polyalkylene oxide, polyalkyleneimine, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, halogen, SO 3 H, sulfonate, NE 1 E 2 , nitro, alkoxycarbonyl, COOH, carboxylate, formyl, acyl or cyano, wherein E 1 and E 2 denote in each case identical or different radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl,
wherein the radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which represent alkyl radicals can have 1, 2, 3, 4 or 5 substituents selected from the group consisting of cycloalkyl, heterocycloalkyl, aryl, hetaryl, cycloalkoxy, cycloalkylthio, heterocycloalkoxy, heterocycloalkylthio, aryloxy, arylthio, hetaryloxy, hetarylthio, hydroxyl, SH, COOH, carboxylate, SO 3 H, sulfonate, NE 4 E 5 , (NE 4 E 5 E 6 ) + X − , halogen, nitro, formyl, acyl and cyano, wherein E 4 , E 5 and E 6 denote in each case identical or different radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl and X − represents an anion equivalent,
and wherein the radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which represent cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl and hetaryl radicals can have 1, 2, 3, 4 or 5 substituents which are selected from the group consisting of alkyl and the substituents for the alkyl radicals R 1 to R 6 , or
R 1 and R 3 , if present, R 4 and R 6 or a combination thereof, together with the ring carbons to which they are bonded, represent a 5- to 8-membered saturated, unsaturated or aromatic carbo- or heterocyclic radical, which is optionally and additionally fused with one, two or three cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the carbo- or heterocyclic radical and, if present, the fused-on groups independently of one another can each carry one, two, three or four substituents which are selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxyl, SH, halogen, COOH, carboxylate, SO 3 H, sulfonate, NE 7 E 8 , (NE 7 E 8 E 9 ) + X − , nitro, alkoxycarbonyl, formyl, acyl and cyano, wherein E 7 , E 8 and E 9 denote in each case identical or different radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl and X − represents an anion equivalent,
wherein in the formula I.1, R 1 and R 3 or R 3 and R 5 also together can represent the bond portion of a double bond between the ring atoms which carry these radicals.
7. The process of claim 1 , wherein in formula I, A, together with the C—N group to which it is bonded, represents a 5- to 8-membered ring which is optionally and additionally fused with one, two or three cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocyclic radical and, if present, the fused-on groups independently of one another can each carry one, two, three or four substituents which are selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl, hetaryl, hydroxyl, SH, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO 3 H, sulfonate, NE 10 E 11 , (NE 10 E 11 E 12 ) + X − , nitro, alkoxycarbonyl, formyl, acyl and cyano, wherein E 10 , E 11 and E 12 denote in each case identical or different radicals selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl and X − represents an anion equivalent.
8. The process of claim 1 , wherein in the formula I the cations are selected from the group consisting of cations of 1,5-diazabicyclo[4.3.0]non-5-ene and 1,8-diazabicyclo[5.4.0]undec-7-ene.
9. The process of claim 1 , wherein the polymer comprises at least one biopolymer.
10. The process of claim 1 , wherein the polymer is a polysaccharide or a modified polysaccharide.
11. The process of claim 1 , wherein the polymer is cellulose.
12. The process of claim 1 , wherein the polymer comprises at least one synthetic polymer.
13. The process of claim 1 , wherein the polymer is selected from the group consisting of a polyurethane, a polyurea, a polyamide, a polysulfone, a polyether sulfone, a homopolymer and a copolymer of cyclic ether, or mixtures thereof.
14. The process of claim 1 , wherein the polymer comprises cellulose and at least one synthetic polymer selected from the group consisting of a polyurethane, a polyurea, a polyamide, a polysulfone, a polyether sulfone, homopolymer and a copolymer of cyclic ether and mixtures thereof.
15. A liquid composition obtained by the process of claim 1 .