# US 9,751,978 B2 · High recycle content polyols from thermoplastic polyesters and lignin or tannin

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- Number: US 9,751,978 B2
- Document ID: US9751978B2
- Status: Granted
- Kind: B2
- Application number: 15/266,247
- Filed: 2016-09-15
- Published: 2017-01-05
- Granted: 2017-09-05
- Earliest claimed: 2015-01-21
- Assignees: Resinate Materials Group, Inc.
- Applicants: Resinate Materials Group, Inc.
- Inventors: Shakti Mukerjee; Kevin Anthony Rogers; Matthew James Beatty; Gary E. Spilman
- Web page: https://patentgrep.com/patent/US9751978B2

## CPC

- C08G 63/916: {Dicarboxylic acids and dihydroxy compounds}
- C08G 18/3206: {aliphatic}
- C08G 18/4225: {derived from residues obtained from the manufacture of dimethylterephthalate and from polyhydroxy compounds}
- C08G 18/6492: {Lignin containing materials; Wood resins; Wood tars; Derivatives thereof}
- C08G 18/664: {with compounds of group C08G18/3203}
- C08G 18/73: acyclic
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 63/133: Hydroxy compounds containing aromatic rings
- C08G 63/668: derived from polycarboxylic acids and polyhydroxy compounds
- C08G 63/676: in which at least one of the two components contains aliphatic unsaturation
- C08G 63/914: {derived from polycarboxylic acids and polyhydroxy compounds}
- C08J 11/24: containing hydroxyl groups
- C09D 167/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09D167/06 takes precedence)
- C09D 167/03: the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings
- C09D 175/06: from polyesters
- C08J 2367/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence)
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- Y02W 30/62: Plastics recycling; Rubber recycling
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- 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)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

Polyester polyols, processes for making them, and applications for the polyols are disclosed. In some aspects, the polyols comprise recurring units from a thermoplastic polyester or an aromatic polyacid source, a glycol, and a lignin, tannin, or mixture thereof. Optionally, the polyols incorporate recurring units of a hydrophobe. The polyols are made in one or multiple steps; in some aspects, the thermoplastic polyester or aromatic polyacid source and the glycol are reacted first, followed by reaction with the lignin, tannin, or mixture thereof. High-recycle-content polyols having desirable properties and attributes for formulating polyurethane products, including two-component polyurethane coatings, can be made. The polyols provide a sustainable alternative to bio- or petrochemical-based polyols.

## Claims

### Claim 1

A polyurethane or polyurethane/polyisocyanurate made from a polyester polyol comprising recurring units from:
(a) a digested thermoplastic polyester;
(b) a glycol; and
(c) a lignin, a tannin, or a mixture thereof;
wherein the molar ratio of glycol to thermoplastic polyester recurring units is at least 0.8, the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 0.1 to 35 wt. %, and the polyol has a hydroxyl number within the range of 25 to 800 mg KOH/g.

### Claim 2 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the thermoplastic polyester is selected from the group consisting of polyethylene terephthalate; polybutylene terephthalate; polytrimethylene terephthalate; glycol-modified polyethylene terephthalate; copolymers of terephthalic acid and 1,4-cyclohexanedimethanol; isophthalic acid-modified copolymers of terephthalic acid and 1,4-cyclohexanedimethanol; copolymers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol with isophthalic acid, terephthalic acid or orthophthalic derivatives; polyhydroxyalkanoates; polyethylene furanoate; dihydroferulic acid polymers; and mixtures thereof.

### Claim 3 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the thermoplastic polyester is selected from the group consisting of virgin PET, recycled PET, and mixtures thereof.

### Claim 4 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the glycol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, pentaerythritol, sorbitol, neopentyl glycol, glycerol, trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, bisphenol A ethoxylates, diethylene glycol, tetraethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycols having a number average molecular weight up to about 400 g/mol, block or random copolymers of ethylene oxide and propylene oxide, and mixtures thereof.

### Claim 5 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the molar ratio of glycol to thermoplastic polyester is within the range of 1.5 to 4.5.

### Claim 6 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the lignin is an organosolv lignin, an alkali lignin, or a mixture thereof.

### Claim 7 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 2 to 25 wt. %.

### Claim 8 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the polyol has a hydroxyl number within the range of 35 to 500 mg KOH/g.

### Claim 9 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the polyol has a combined recycle and bio-renewable content as defined herein greater than 80 wt. %.

### Claim 10 (depends on 1)

The polyurethane or polyurethane/polyisocyanurate of claim 1 wherein the polyol has an average hydroxyl functionality within the range of 1.8 to 2.2.

### Claim 11

An aqueous polyurethane dispersion made from a polyester polyol comprising recurring units from:
(a) a digested thermoplastic polyester;
(b) a glycol; and
(c) a lignin, a tannin, or a mixture thereof;
wherein the molar ratio of glycol to thermoplastic polyester recurring units is at least 0.8, the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 0.1 to 35 wt. %, and the polyol has a hydroxyl number within the range of 25 to 800 mg KOH/g.

### Claim 12 (depends on 11)

A coating made from the polyurethane dispersion of claim 11.

### Claim 13 (depends on 11)

The aqueous polyurethane dispersion of claim 11 wherein the thermoplastic polyester is selected from the group consisting of virgin PET, recycled PET, and mixtures thereof.

### Claim 14 (depends on 11)

The aqueous polyurethane dispersion of claim 11 wherein the lignin is an organosolv lignin, an alkali lignin, or a mixture thereof.

### Claim 15 (depends on 11)

The aqueous polyurethane dispersion of claim 11 wherein the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 2 to 25 wt. %.

### Claim 16 (depends on 11)

The aqueous polyurethane dispersion of claim 11 wherein the polyol has a combined recycle and bio-renewable content as defined herein greater than 80 wt. %.

### Claim 17

A two-component polyurethane coating made from a polyester polyol comprising recurring units from:
(a) a digested thermoplastic polyester;
(b) a glycol; and
(c) a lignin, a tannin, or a mixture thereof;
wherein the molar ratio of glycol to thermoplastic polyester recurring units is at least 0.8, the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 0.1 to 35 wt. %, and the polyol has a hydroxyl number within the range of 25 to 800 mg KOH/g.

### Claim 18 (depends on 17)

The coating of claim 17 wherein the thermoplastic polyester is selected from the group consisting of virgin PET, recycled PET, and mixtures thereof.

### Claim 19 (depends on 17)

The coating of claim 17 wherein the lignin is an organosolv lignin, an alkali lignin, or a mixture thereof.

### Claim 20 (depends on 17)

The coating of claim 17 wherein the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 2 to 25 wt. %.

### Claim 21 (depends on 17)

The coating of claim 17 wherein the polyol has a combined recycle and bio-renewable content as defined herein greater than 80 wt. %.

### Claim 22

A curable resin comprising a reaction product of an acrylate or methacrylate source and a polyester polyol comprising recurring units from:
(a) a digested thermoplastic polyester;
(b) a glycol; and
(c) a lignin, a tannin, or a mixture thereof;
wherein the molar ratio of glycol to thermoplastic polyester recurring units is at least 0.8, the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 0.1 to 35 wt. %, and the polyol has a hydroxyl number within the range of 25 to 800 mg KOH/g.

### Claim 23 (depends on 22)

A UV-cured coating made from the resin of claim 22.

### Claim 24 (depends on 22)

The curable resin of claim 22 wherein the thermoplastic polyester is selected from the group consisting of virgin PET, recycled PET, and mixtures thereof.

### Claim 25 (depends on 22)

The curable resin of claim 22 wherein the lignin is an organosolv lignin, an alkali lignin, or a mixture thereof.

### Claim 26 (depends on 22)

The curable resin of claim 22 wherein the amount of lignin, tannin, or mixture thereof incorporated into the polyol is within the range of 2 to 25 wt. %.

### Claim 27 (depends on 22)

The curable resin of claim 22 wherein the polyol has a combined recycle and bio-renewable content as defined herein greater than 80 wt. %.