# US 8,785,592 B2 · Preparation of poly(alkylene carbonate) containing cross-linked high molecular weight chains

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- Number: US 8,785,592 B2
- Document ID: US8785592B2
- Status: Granted
- Kind: B2
- Application number: 13/226,985
- Filed: 2011-09-07
- Published: 2012-03-15
- Granted: 2014-07-22
- Earliest claimed: 2010-09-09
- Assignees: SK Innovation Co., Ltd.
- Applicants: Ji Su Jeong; Sung Jae Na; Sujith Sudevan; Myung Ahn Ok; Yong Gyu Han; Kwang Jin Chung; Bun Yeoul Lee; Anish Cyriac
- Inventors: Ji Su Jeong; Sung Jae Na; Sujith Sudevan; Myung Ahn Ok; Yong Gyu Han; Kwang Jin Chung; Bun Yeoul Lee; Anish Cyriac
- Web page: https://patentgrep.com/patent/US8785592B2

## CPC

- C08G 64/34: and cyclic ethers
- C08G 64/0216: {containing a chain-terminating or -crosslinking agent}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Provided is preparation of poly(alkylene carbonate) through alternating copolymerization of carbon dioxide and epoxide. According to the disclosure, by introducing a diepoxide compound to alternating copolymerization of carbon dioxide and epoxide compound using a metal(III) prepared with salen-type ligands containing quaternary ammonium salt as a catalyst, some of the polymer chains may be cross-linked to thus increase an average molecular weight of the copolymer and extend a distribution of molecular weight. A resin prepared according to this method may have high mechanical strength and rheological advantages.

## Claims

### Claim 1

A method for preparation of poly(alkylene carbonate) comprising, carrying out alternating copolymerization of carbon dioxide and epoxide compound in the presence of a metal catalyst and a compound having at least two epoxide functional groups as a chain linker,
wherein the metal catalyst is a complex represented by Chemical Formula 1:
wherein
M represents trivalent cobalt or trivalent chromium;
A represents an oxygen or sulfur atom;
Q represents a diradical for linking two nitrogen atoms;
R1 through R10 independently represent hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; or a hydrocarbyl-substituted metalloid radical of a Group 14 metal;
two of the R1 through R10 may be linked to each other to form a ring;
at least one of the hydrogen contained in the R1 through R10 and Q is substituted with a cationic group selected from the group consisting of Chemical Formula a, Chemical Formula b and Chemical Formula c;
X− independently represents a halogen anion; HCO3−; BF4−; ClO4−; NO3−; PF6−; (C6-C20)aryloxy anion; (C6-C20)aryloxy anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20)alkylcarboxy anion; (C1-C20)alkylcarboxy anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20)arylcarboxy anion; (C6-C20)arylcarboxy anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20)alkoxy anion; (C1-C20)alkoxy anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20)alkylcarbonate anion; (C1-C20)alkylcarbonate anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20)arylcarbonate anion; (C6-C20)arylcarbonate anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20)alkylsulfonate anion; (C1-C20)alkylsulfonate anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20)alkylamido anion; (C1-C20)alkylamido anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20)arylamido anion; (C6-C20)arylamido anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20)alkylcarbamate anion; (C1-C20)alkylcarbamate anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20)arylcarbamate anion; or (C6-C20)arylcarbamate anion with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms;
Z represents a nitrogen or phosphorus atom;
R21, R22, R23, R31, R32, R33, R34 and R35 independently represent (C1-C20)alkyl; (C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a hydrocarbyl-substituted metalloid radical of a Group 14 metal; two of R21, R22 and R23, or two of R31, R32, R33, R34 and R35 may be linked to each other to form a ring;
R41, R42 and R43 independently represent hydrogen; (C1-C20)alkyl; (C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a hydrocarbyl-substituted metalloid radical of a Group 14 metal; two of R41, R42 and R43 may be linked to each other to form a ring;
X′ represents an oxygen atom, a sulfur atom or N—R (wherein R represents (C1-C20)alkyl);
n represents an integer of adding 1 to the total number of cationic groups contained in R1 through R10 and Q;
X− may be coordinated with M;
Nitrogen atom of imine may be de-coordinated from M.

### Claim 2 (depends on 1)

The method of claim 1, wherein the epoxide compound is at least one selected from the group consisting of (C2-C20)alkyleneoxide with or without halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyloxy substituent(s); (C4-C20)cycloalkyleneoxide with or without halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alkyloxy substituent(s); and (C8-C20)styreneoxide with or without halogen, (C1-C20)alkyloxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyloxy or (C1-C20)alkyl substituent(s).

### Claim 3 (depends on 1)

The method of claim 1, wherein,
M represents a trivalent cobalt;
A represents oxygen;
Q represents trans-1,2-cyclohexylene, phenylene or ethylene;
R1 and R2 are the same as or different from primary (C1-C20)alkyl;
R3 through R10 independently represent hydrogen or —[YR513-a{(CR52R53)bN+R54R55R56}a];
Y represents C or Si;
R51, R52, R53, R54, R55 and R56 independently represent hydrogen; halogen; (C1-C20)alkyl; (C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20)alkenyl; (C2-C20)alkenyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkyl(C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20)aryl(C1-C20)alkyl; (C6-C20)aryl(C1-C20)alkyl with at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20)alkoxy; (C6-C30)aryloxy; formyl; (C1-C20)alkylcarbonyl; (C6-C20)arylcarbonyl; or a hydrocarbyl-substituted metalloid radical of a Group 14 metal, two of R54, R55 and R56 may be linked to each other to form a ring;
a represents an integer of 1 to 3, and b represents an integer of 1 to 20;
n represents an integer of 4 or more as a value of adding 1 to a total number of quaternary ammonium salts contained in R3 through R10;
provided that when a represents 1, at least three of R3 through R10 represent —[YR512{(CR52R53)bN+R54R55R56}], when a represents 2, at least two of R3 through R10 represent —[YR51{(CR52R53)bN+R54R55R56}2], when a represents 3, at least one of R3 through R10 represent —[Y{(CR52R53)bN+R54R55R56}3].

### Claim 4 (depends on 3)

The method of claim 3, wherein a complex of Chemical Formula 3 below is used as the catalyst:
wherein
R61 and R62 independently represent methyl or ethyl; X− independently represents a nitrate or acetate anion; nitrogen of imine may be coordinated or de-coordinated with cobalt, and each X− may be coordinated with cobalt.