# US 11,299,594 B2 · Carbinol-functional silicone resin, and method for producing silicone-modified polyester

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- Number: US 11,299,594 B2
- Document ID: US11299594B2
- Status: Granted
- Kind: B2
- Application number: 17/048,167
- Filed: 2018-04-18
- Published: 2021-05-27
- Granted: 2022-04-12
- Earliest claimed: 2018-04-18
- Assignees: Dow Silicones Corporation
- Applicants: Dow Silicones Corporation
- Inventors: Guodong Shen; Wenjie Chen; Zhihua Liu
- Web page: https://patentgrep.com/patent/US11299594B2

## CPC

- C08G 77/445: containing polyester sequences
- C08G 63/6954: {derived from polxycarboxylic acids and polyhydroxy compounds}
- C08G 77/14: containing silicon bound to oxygen-containing groups
- C08G 77/18: to alkoxy or aryloxy groups
- C08G 77/38: Polysiloxanes modified by chemical after-treatment
- C08L 83/04: Polysiloxanes
- C09D 167/00: Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain (based on polyester-amides C09D177/12; based on polyester-imides C09D179/08); Coating compositions based on derivatives of such polymers
- C09D 167/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09D167/06 takes precedence)
- C08G 77/16: to hydroxy groups
- 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)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

Provided herein is a carbinol-functional silicone resin. The carbinol-functional silicone resin is prepared by reacting a raw silicone resin having at least 1 mass % of silicon atom-bonded hydroxyl groups, silicon atom-bonded alkoxy groups, or a combination thereof, and a dihydroxy-functional compound, in the presence of a condensation catalyst and a solvent. The carbinol-functional silicone resin can produce a solid silicone-modified polyester without gelation of the silicone resin.

## Claims

### Claim 1

A carbinol-functional silicone resin, wherein the carbinol-functional silicone resin is prepared by reacting a raw silicone resin having at least 1 mass % of silicon atom-bonded hydroxyl groups, silicon atom-bonded alkoxy groups, or a combination thereof, and a dihydroxy-functional compound, in the presence of a condensation catalyst and a solvent;
wherein the carbinol-functional silicone resin forms a silicone-modified polyester without gelation;
wherein the raw silicone resin is represented by the following compositional formula:
R1a(HO)b(R3O)cSiO(4-a-b-c)/2,
where R1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R3 is an alkyl group, and “a” is a number of from 0.8 to 1.8, provided that “b” and “c” are numbers such that at least 1 mass % of silicon atom-bonded hydroxyl groups, silicon atom-bonded alkoxy groups, or a combination thereof are present;
wherein the dihydroxy-functional compound is represented by the following general formula:
HO—(R2O)n—H,
where R2 is an alkylene group having 2 to 12 carbon atoms, and “n” is 1; and
with the provisos that:
when the raw silicone resin has i) only silicon atom-bonded hydroxyl groups or ii) only silicon atom-bonded alkoxy groups, the dihydroxy-functional compound is reacted with the raw silicone resin in an amount such that a mole ratio of hydroxyl groups in the dihydroxy-functional compound per silicon atom-bonded hydroxyl groups or silicon atom-bonded alkoxy groups in the raw silicone resin is in a range of from 0.5 to 2.0; and
when the raw silicone resin has iii) both silicon atom-bonded hydroxyl groups and silicon atom-bonded alkoxy groups, the dihydroxy-functional compound is reacted with the raw silicone resin in an amount such that a mole ratio of hydroxyl groups in the dihydroxy-functional compound per silicon atom-bonded hydroxyl groups and silicon atom-bonded alkoxy groups in the raw silicone resin is in a range of from 0.5 to 2.0.

### Claim 2 (depends on 1)

The carbinol-functional silicone resin according to claim 1, wherein the raw silicone resin is a silicone T resin.

### Claim 3 (depends on 1)

The carbinol-functional silicone resin according to claim 1, wherein the dihydroxy-functional compound is a compound selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and combinations thereof.

### Claim 4 (depends on 1)

The carbinol-functional silicone resin according to claim 1, wherein the condensation catalyst is a catalyst comprising metal ligand complexes.

### Claim 5 (depends on 1)

The carbinol-functional silicone resin according to claim 1, wherein the reaction is carried out at a temperature of not more than 150° C.

### Claim 6

A method for producing a silicone-modified polyester without gelation, the method comprising the following steps:
1) reacting a raw silicone resin having at least 1 mass % of silicon atom-bonded hydroxyl groups, silicon atom-bonded alkoxy groups, or a combination thereof, and a dihydroxy-functional compound, in the presence of a condensation catalyst and a solvent to produce a carbinol-functional silicone resin; and
2) esterifying the carbinol-functional silicone resin, a polyhydroxy-functional compound and a polycarboxyl-functional compound or derivative thereof, without using a solvent, to form the silicone-modified polyester without gelation;
wherein the raw silicone resin is represented by the following compositional formula:
R1a(HO)b(R3O)cSiO(4-a-b-c)/2,
where R1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R3 is an alkyl group with 1 to 6 carbon atoms, and “a” is a number of from 0.8 to 1.8, provided that “b” and “c” are numbers such that at least 1 mass % of silicon atom-bonded hydroxyl groups, silicon atom-bonded alkoxy groups, or a combination thereof are present; and
wherein the dihydroxy-functional compound is represented by the following general formula:
HO—(R2O)n—H,
where R2 is an alkylene group having 2 to 12 carbon atoms, and “n” is 1.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the raw silicone resin is a silicone T resin.

### Claim 8 (depends on 6)

The method according to claim 6, wherein the dihydroxy-functional compound is a compound selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and combinations thereof.

### Claim 9 (depends on 6)

The method according to claim 6, with the provisos that:
when the raw silicone resin has i) only silicon atom-bonded hydroxyl groups or ii) only silicon atom-bonded alkoxy groups, the dihydroxy-functional compound is reacted with the raw silicone resin in an amount such that a mole ratio of hydroxyl groups in the dihydroxy-functional compound per silicon atom-bonded hydroxyl groups or silicon atom-bonded alkoxy groups in the raw silicone resin is in a range of from 0.5 to 2.0; and
when the raw silicone resin has iii) both silicon atom-bonded hydroxyl groups and silicon atom-bonded alkoxy groups, the dihydroxy-functional compound is reacted with the raw silicone resin in an amount such that a mole ratio of hydroxyl groups in the dihydroxy-functional compound per silicon atom-bonded hydroxyl groups and silicon atom-bonded alkoxy groups in the raw silicone resin is in a range of from 0.5 to 2.0.

### Claim 10 (depends on 6)

The method according to claim 6, wherein the condensation catalyst is a catalyst comprising metal ligand complexes.

### Claim 11 (depends on 6)

The method according to claim 6, wherein step 1) is carried out at a temperature of not more than 150° C.

### Claim 12 (depends on 6)

The method according to claim 6, wherein the polyhydroxy-functional compound is a compound selected from the group consisting of glycerin, trimethylolpropane, trimethylolethane, trishydroxyethylisocyanurate, pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-, 1,2-, and 1,4-butanediols, heptanediol, hexanediol, octanediol, 2,2′-bis (4-cyclohexanol)propane, neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol, 1,4-dimethylolcyclohexane, 2,2,4-trimethylpentane diol, and combinations thereof.

### Claim 13 (depends on 6)

The method according to claim 6, wherein the polycarboxyl-functional compound is a compound selected from the group consisting of phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, benzophenone dicarboxylic acid, diphenic acid, 4,4-dicarboxydiphenyl ether, 2,5-pyridine dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4-hydroxybenzoic acid, trimellitic acid, trimellitic anhydride, and combinations thereof.

### Claim 14 (depends on 6)

The method according to claim 6, wherein step 2) is carried out at a temperature of not less than 150° C.

### Claim 15 (depends on 1)

The carbinol-functional silicone resin according to claim 1, wherein the raw silicone resin has 1 to 50 mass % of silicon atom-bonded hydroxyl groups, silicon atom-bonded alkoxy groups, or a combination thereof.

### Claim 16 (depends on 6)

The method according to claim 6, wherein the raw silicone resin has 1 to 50 mass % of silicon atom-bonded hydroxyl groups, silicon atom-bonded alkoxy groups, or a combination thereof.