# US 10,479,860 B2 · Method for preparing highly transparent and highly heat-resistant polycarbonate ester

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- Number: US 10,479,860 B2
- Document ID: US10479860B2
- Status: Granted
- Kind: B2
- Application number: 15/540,052
- Filed: 2016-01-12
- Published: 2017-12-28
- Granted: 2019-11-19
- Earliest claimed: 2015-01-22
- Assignees: SK Chemicals Co., Ltd.
- Applicants: SK Chemicals Co., Ltd.
- Inventors: Kwang Sei Oh; Jong-In Lee
- Web page: https://patentgrep.com/patent/US10479860B2

## CPC

- C08G 63/64: Polyesters containing both carboxylic ester groups and carbonate groups
- C08G 63/66: Polyesters containing oxygen in the form of ether groups (C08G63/42, C08G63/58 take precedence)
- C08G 63/672: Dicarboxylic acids and dihydroxy compounds
- C08G 63/78: Preparation processes
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

A method for preparing a bio-based polycarbonate ester containing a repeating unit according to Formula 1 which comprises residue of Isosorbide and residue of CHDA (1,4-cyclohexanedicarboxylic acid). The method includes a nucleophilic reaction with phenol to prepare a 1,4-diphenyl-cyclohexanedicarboxylate, followed by a polycarbonate melt polycondensation reaction

## Claims

### Claim 1

A method for preparing a bio-based polycarbonate ester comprising a repeating unit of Formula 1, comprising the steps of:
(1) subjecting a reaction mixture comprising a compound of Formula 2 and a halogenation agent to convert the compound of Formula 2 into an intermediate reactant of Formula 2a and then subjecting the intermediate reactant of Formula 2a to a nucleophilic reaction with phenol to yield a diphenyl ester of Formula 3; and
(2) subjecting the diphenyl ester of Formula 3 prepared in step (1), a compound of Formula 4, and 1,4:3,6-dianhydrohexitol to a polycarbonate melt polycondensation reaction to yield the bio-based polycarbonate ester comprising the repeating unit of Formula 1:
wherein
R is methyl or hydrogen,
R1 and R2 are each independently a substituted or unsubstituted C1-C18 aliphatic group, or a substituted or unsubstituted C1-C18 aromatic group,
R3 is F, Cl, or Br, and
x is a real number of 0<x<1.

### Claim 2 (depends on 1)

The method of claim 1, wherein R3 is Cl.

### Claim 3 (depends on 1)

The method of claim 1, wherein the halogenation agent in step (1) is selected from the group consisting of phosgene, triphosgene, thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorous pentachloride, phosphorous pentabromide, and cyanuric fluoride.

### Claim 4 (depends on 1)

The method of claim 1, wherein the conversion of the compound of Formula 2 into the intermediate reactant of Formula 2a in step (1) is carried out at a reaction temperature of −30 to 150° C. under atmospheric pressure for a reaction time of 5 minutes to 48 hours.

### Claim 5 (depends on 1)

The method of claim 1, wherein the phenol is used in step (1) in an amount of 1 to 3 times the total moles of the compound of Formula 2.

### Claim 6 (depends on 1)

The method of claim 1, wherein the reaction mixture of step (1l further comprises with addition of at least one compound selected from the group consisting of tetrahydro-2,5-dimethyl-furandicarboxylate, 1,2-dimethyl-cyclohexanedicarboxylate, 1,3-dimethyl-cyclohexanedicarboxylate, decahydro-2,4-dimethyl-naphthalenedicarboxylate, decahydro-2,5-dimethyl-naphthalenedicarboxylate, decahydro-2,6-dimethyl-naphthalenedicarboxylate, decahydro-2,7-dimethyl-naphthalenedicarboxylate, tetrahydro-2,5-furandicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, decahydro-2,4-naphthalenedicarboxylic acid, decahydro-2,5-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, and decahydro-2,7-naphthalenedicarboxylic acid,
wherein the at least one compound is converted to a corresponding diphenyl ester thereof through step (1).

### Claim 7 (depends on 1)

The method of claim 1, wherein the compound of Formula 4 is dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, diphenyl carbonate, or ditolyl carbonate.

### Claim 8 (depends on 1)

The method of claim 1, wherein the melt polycondensation reaction in step (2) takes place in the presence of at least one additional diol compound selected from the group consisting of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecandimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2-bis(4-hydroxycyclohexyl)propane, and tetrahydro-2,5-furandimethanol derivable from a bio-based material.

### Claim 9 (depends on 8)

The method of claim 8, wherein the additional diol compound is used in an amount of less than 99 mol %, based on 100 mol % of 1,4:3,6-dianhydrohexitol.

### Claim 10 (depends on 1)

The method of claim 1, wherein the melt polycondensation reaction in step (2) comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is operated at a temperature of 130 to 250° C. under a reduced pressure of 5 to 700 Torr for 0.1 to 10 hours, and the second reaction zone is operated at a temperature of 210 to 290° C. under a reduced pressure of 20 Torr or lower for 0.1 to 10 hours.

### Claim 11 (depends on 1)

The method of claim 1, wherein a ratio of cis/trans cyclohexanedicarboxylate unit in the repeating unit of Formula 1 is in the range of 1%/99% to 99%/1%.