# US 2024/0199804 A1 · Method for producing thermoplastic resin, and compound therefor

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- Number: US 2024/0199804 A1
- Document ID: US20240199804A1
- Status: Published application
- Kind: A1
- Application number: 18/552,088
- Filed: 2022-03-15
- Published: 2024-06-20
- Earliest claimed: 2021-03-23
- Assignees: Mitsubishi Chemical Corporation; Agency for Science, Technology and Research
- Applicants: Mitsubishi Chemical Corporation; Agency For Science, Technology & Research
- Inventors: Shohei Tomita; Toshiki Monden; Mitsunobu Ito; Cun Wang; Martin Van Meurs; Boon Ying Tay
- Web page: https://patentgrep.com/patent/US20240199804A1

## CPC

- C08G 64/307: {and phenols}
- C08G 63/16: Dicarboxylic acids and dihydroxy compounds
- C08G 63/87: Non-metals or inter-compounds thereof (boron C08G63/84)
- C08L 67/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence)
- C08L 69/00: Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Provided is a method for producing at least one type of thermoplastic resin selected from polycarbonate, polyester and polyester carbonate. The method includes a step of subjecting a dihydroxy compound and diaryl carbonate and/or dicarboxylic acid ester to melt polycondensation in the presence of a transesterification catalyst selected from a compound represented by formula (1) and/or formula (2). In formula (1), R1 to R24 are each a hydrogen atom, an alkyl group having 1-10 carbon atoms or a cycloalkyl group. Some of the carbon atoms may be substituted by heteroatoms. Among R1 to R24, alkyl groups or the like substituted on the same N atom may bond to each other to form a ring. The values of a to d are each 0 or 1. X− is a monovalent anion. In formula (2), Ar1 to Ar12 are each a substituted or unsubstituted aryl group. M− is a monovalent anion.

## Claims

### Claim 1

A method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, polyester and polyester carbonate, comprising a process of melt polycondensation of a dihydroxy compound with a diaryl carbonate and/or a dicarboxylic acid ester in a presence of a transesterification catalyst selected from a compound represented by formula (1) below and/or a compound represented by formula (2) below.
in formula (1), R1˜R24 are each independently a hydrogen atom, an alkyl group having 1˜10 carbon atoms, or a cycloalkyl group, wherein some carbon atoms of the alkyl group and the cycloalkyl group may be replaced by heteroatoms, and among R1˜R24, alkyl groups substituted on a same N atom may be joined together to form a ring; R2 and R3, R4 and R5, R6 and R7, R8 and R1 may respectively be joined together to form a ring; R9 or R10, R1 or R2, and R11 or R12 may respectively be joined together to form a ring; R13 or R1, R3 or R4, and R15 or R16 may respectively be joined together to form a ring; R17 or R18, R5 or R6 and R19 or R20 may respectively be joined together to form a ring; R21 or R22, R7 or R8, and R23 or R24 may respectively be joined together to form a ring; R1 or R2, R3 or R4, and R5 or R6 may respectively be joined together to form a ring; R3 or R4, R5 or R6, and R8 or R7 may respectively be joined together to form a ring: R5 or R6, R8 or R7, and R1 or R2 may respectively be joined together to form a ring; and R7 or R8, R1 or R2, and R3 or R4 may respectively be joined together to form a ring; a˜d are independently 0 or 1; X− is a monovalent anion;
in formula (2), Ar1˜Ar12 each independently represent a substituted or unsubstituted aryl group; M− represents a monovalent anion.

### Claim 2 (depends on 1)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 1, wherein said dihydroxy compound is bisphenol A.

### Claim 3 (depends on 1)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 1, wherein said diaryl carbonate is diphenyl carbonate.

### Claim 4 (depends on 1)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 1, wherein said dicarboxylic acid ester is diphenyl terephthalate and/or diphenyl isophthalate.

### Claim 5 (depends on 1)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 1, comprising the process of melt polycondensation of an aromatic dihydroxy compound and a diaryl carbonate in the presence of said transesterification catalyst.

### Claim 6 (depends on 1)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 1, wherein said transesterification catalyst is a compound represented by said formula (1).

### Claim 7 (depends on 6)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 6, wherein said formula (1) is represented by the following formula (1b):
in formula (1B), R29˜R52 are each independently a hydrogen atom or an alkyl group having 1˜10 carbon atoms; among R29˜R52, alkyl groups substituted on a same N atom may be joined together to form a ring; R30 and R31, R32 and R33, R34 and R35, R36 and R29 may respectively be joined together to form a ring; i˜1 are independently 0 or 1, respectively; Y− is a monovalent anion.

### Claim 8 (depends on 6)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 6, wherein in said formula (1),
X− is at least one kind selected from a chloride ion, a bromide ion, a tetraphenylborate ion, a phenolate ion, a BPA monoanion represented by formula (3a) below, and a BPA monoanion BPA adduct represented by formula (3b) below.

### Claim 9 (depends on 8)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 8, wherein in said (1), X− is at least one kind selected from a phenolate ion, a BPA monoanion represented by said formula (3a), and a BPA monoanion BPA adduct represented by said formula (3b).

### Claim 10 (depends on 6)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 6, wherein said formula (1) is represented by any of following formulas (1a)˜(1e):
in formulas (1a)˜(1e), Z1−˜Z3− each independently represent a monovalent anion; Me represents a methyl group.

### Claim 11 (depends on 1)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 1, wherein said transesterification catalyst is a compound represented by said formula (2).

### Claim 12 (depends on 11)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 11, wherein in said formula (2), Ar1−˜Ar12− are phenyl groups.

### Claim 13 (depends on 11)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 11, wherein, in said formula (2), M− is at least one kind selected from a chloride ion, a bromide ion, a tetraphenylborate ion, a phenolate ion, a BPA monoanion represented by formula (3a) below, and a BPA monoanion BPA adduct represented by formulas (3b), (3c) below.

### Claim 14 (depends on 13)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 13, wherein, in said formula (2), M− is at least one kind selected from a phenolate ion, a BPA monoanion represented by said formula (3a), and a BPA monoanion BPA adduct represented by said formulas (3b), (3c).

### Claim 15 (depends on 1)

The method for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate according to claim 1, wherein one or more of the following apply:
(a) said melt polycondensation is performed in the presence of 0.01˜1000 μmol of said transesterification catalyst per 1 mol of said dihydroxy compound;
(b) a temperature during said melt polycondensation reaction is 200˜350° C.; and
(c) a viscosity average molecular weight (Mv) of said at least one thermoplastic resin selected from a group consisting of a polycarbonate. a polyester. and a polyester carbonate produced is from 5,000 to 40,000.

### Claim 16

(canceled)

### Claim 17

(canceled)

### Claim 18

A transesterification catalyst for producing at least one thermoplastic resin selected from a group consisting of a polycarbonate, a polyester, and a polyester carbonate by melt polycondensation of a dihydroxy compound with a diaryl carbonate and/or a dicarboxylic acid ester, said catalyst being selected from any one of a group of compounds represented by formula (1) below and formula (2) below:
in formula (1), R1˜R24 are each independently a hydrogen atom, an alkyl group having 1˜10 carbon atoms, or a cycloalkyl group, wherein some carbon atoms of the alkyl group or the cycloalkyl group may be replaced by heteroatoms, and among R1˜R24, alkyl groups substituted on a same N atom may be joined together to form a ring; R2 and R3, R4 and R5, R6 and R7, R8 and R1 may respectively be joined together to form a ring; R9 or R10, R1 or R2, and R11 or R12 may respectively be joined together to form a ring; R13 or R14, R3 or R4, and R15 or R16 may respectively be joined together to form a ring; R17 or R18, R5 or R6 and R19 or R20 may respectively be joined together to form a ring; R21 or R22, R7 or R8, and R23 or R24 may respectively be joined together to form a ring; R1 or R2, R3 or R4, and R5 or R6 may respectively be joined together to form a ring; R3 or R4, R5 or R6, and R8 or R7 may respectively be joined together to form a ring; R3 or R6, R8 or R7, and R1 or R2 may respectively be joined together to form a ring; and R7 or R8, R1 or R2, and R3 or R4 may respectively be joined together to form a ring; a˜d are independently 0 or 1; X− is a monovalent anion.
in formula (2), Ar1˜Ar12 each independently represent a substituted or unsubstituted aryl group; M− represents a monovalent anion.

### Claim 19

A compound represented by any of following formulas (1a′)˜(1e′):
in formulas (1a′) and (1b′), L1− and L2− are at least one kind selected from a phenolate ion, a BPA monoanion represented by formula (3a) below, and a BPA monoanion BPA adduct represented by formula (3b) below; in said formulas (1c′)˜(1e′), L3−˜L5− represent a monovalent anion; Me represents a methyl group;

### Claim 20

A compound represented by the following formula (2):
in formula (2), Ar1˜Ar12 each independently represent a substituted or unsubstituted aryl group; M− represents a monovalent anion.

### Claim 21 (depends on 1)

The polycarbonate produced by the method for producing a thermoplastic resin according to claim 1,
wherein a viscosity average molecular weight of said polycarbonate is 14,000 or more and 30,000 or less, and
a total amount of compounds represented by following formulas (A)˜(E) measured in a hydrolysate of the polycarbonate is 300 wt. ppm or more and 550 wt. ppm or less with respect to the polycarbonate resin:
in formulas (A)˜(D), Ra˜Rf each independently represent a hydrogen atom or a methyl group;
in benzene rings in formulas (A)˜(E), one or more hydrogen atoms bonded to benzene rings may be substituted by a substituent.

### Claim 22 (depends on 21)

The polycarbonate of claim 21, wherein a terminal hydroxyl group concentration of said polycarbonate is 400 wt. ppm or more and 1000 wt. ppm or less.