# US 11,299,614 B2 · Sustainable, energy-curable polyester polyols and coatings or rigid foams therefrom

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- Number: US 11,299,614 B2
- Document ID: US11299614B2
- Status: Granted
- Kind: B2
- Application number: 16/548,296
- Filed: 2019-08-22
- Published: 2020-01-02
- Granted: 2022-04-12
- Earliest claimed: 2017-03-03
- Assignees: Carlisle Construction Materials, LLC
- Applicants: Carlisle Construction Materials, LLC
- Inventors: Matthew Thomas Brown; Michelle Samson; Gary Spilman; Rick Tabor; Kevin Anthony Rogers
- Web page: https://patentgrep.com/patent/US11299614B2

## CPC

- C08L 33/10: Homopolymers or copolymers of methacrylic acid esters
- C09D 167/06: Unsaturated polyesters having carbon-to-carbon unsaturation
- C08G 18/0823: {containing carboxylate salt groups or groups forming them}
- C08G 18/1808: {having alkylene polyamine groups}
- C08G 18/1816: {having carbocyclic groups}
- C08G 18/227: {of antimony, bismuth or arsenic}
- C08G 18/246: {containing also tin-carbon bonds}
- C08G 18/6229: {Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols}
- C08G 18/68: Unsaturated polyesters
- 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 18/7657: {containing two or more aromatic rings}
- C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates}
- C08G 63/54: the acids or hydroxy compounds containing carbocyclic rings
- C08G 63/676: in which at least one of the two components contains aliphatic unsaturation
- C08G 63/918: {Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation}
- C08L 33/066: {containing -OH groups}
- C08L 33/08: Homopolymers or copolymers of acrylic acid esters
- C08L 75/14: Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D 133/08: Homopolymers or copolymers of acrylic acid esters
- C09D 133/10: Homopolymers or copolymers of methacrylic acid esters
- C09D 175/14: Polyurethanes having carbon-to-carbon unsaturated bonds
- C08G 2110/0025: rigid
- C08L 2201/54: Aqueous solutions or dispersions
- C08L 2203/14: used for foams
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Maleate polyester polyols and coatings made from the polyols are disclosed. The polyester polyols comprise recurring units of (a) a digested thermoplastic polyester or an aromatic dicarboxylate source; (b) a diol; (c) 5 to 95 mole % of an α,β-unsaturated monomer; and (d) 5 to 95 mole % of adipic acid, succinic acid, or a mixture thereof, where the mole % ranges for (c) and (d) are based on the combined molar amounts of (c) and (d). The polyols have hydroxyl numbers within the range of 25 to 450 mg KOH/g, an average of 0.5 to 2.5 reactive unsaturation sites per molecule, and a viscosity less than 1500 cP at 75° C. The polyols are thermally curable or energy-curable. Coatings made from the maleate polyester polyols are also described. Traditional coatings based on polyisocyanates and/or (meth)acrylates can be made, in some cases with improved properties and reduced reliance on the acrylate or isocyanate-based components. Surprisingly, the maleate polyester polyols can also be cured directly using UV to produce coatings under ambient conditions without the need for either acrylic or isocyanate functionality, and this allows coating formulators to reduce cost and more easily achieve regulatory compliance without sacrificing important coating properties. Rigid polyisocyanurate and polyurethane foams produced from the maleate polyester polyols have improved fire retardance.

## Claims

### Claim 1

A polyester polyol comprising recurring units of:
(a) a digested thermoplastic polyester;
(b) a diol;
(c) 5 to 95 mole % of an α,β-unsaturated monomer; and
(d) 5 to 95 mole % of adipic acid, succinic acid, or a mixture thereof;
wherein the mole % ranges for (c) and (d) are based on the combined molar amounts of (c) and (d);
wherein the polyol has a hydroxyl number within the range of 25 to 450 mg KOH/g, an average of 0.5 to 2.5 reactive unsaturation sites per molecule, and a viscosity less than 1500 cP at 75° C.; and
wherein the polyol is thermally curable or energy-curable.

### Claim 2 (depends on 1)

The polyol 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 acid derivatives; polyhydroxyalkanoates; polyethylene furanoate; dihydroferulic acid polymers; and mixtures thereof.

### Claim 3 (depends on 1)

The polyol of claim 1 wherein the thermoplastic polyester is selected from the group consisting of virgin PET, recycled PET, virgin PETG, recycled PETG, and mixtures thereof.

### Claim 4 (depends on 1)

The polyol of claim 1 wherein the diol 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, 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 polyol of claim 1 wherein the molar ratio of diol to thermoplastic polyester is within the range of 1.5 to 4.5.

### Claim 6 (depends on 1)

The polyol of claim 1 comprising 25 to 95 mole % of the α,β-unsaturated monomer and 5 to 75 mole % of adipic acid, succinic acid, or a mixture thereof.

### Claim 7 (depends on 1)

The polyol of claim 1 wherein the α,β-unsaturated monomer is selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, itaconic acid, itaconic anhydride, alkyl esters thereof, substituted derivatives thereof, and mixtures thereof.

### Claim 8 (depends on 1)

The polyol of claim 1 wherein the α,β-unsaturated monomer is selected from the group consisting of acrylic acid, methacrylic acid, sorbic acid, methylene malonic acid, muconic acid, anhydrides thereof, alkyl esters thereof, substituted derivatives thereof, and mixtures thereof.

### Claim 9 (depends on 1)

The polyol of claim 1 wherein the polyol comprises 5 to 35 wt. % of digested thermoplastic polyester recurring units based on the amount of polyester polyol.

### Claim 10 (depends on 1)

The polyol of claim 1 having a hydroxyl number within the range of 25 to 350 mg KOH/g.

### Claim 11 (depends on 1)

The polyol of claim 1 wherein the polyol is energy-curable essentially in the absence of a photoinitiator.

### Claim 12

A polyester polyol comprising recurring units of:
(a) an aromatic dicarboxylate source;
(b) a diol;
(c) 5 to 95 mole % of an α,β-unsaturated monomer; and
(d) 5 to 95 mole % of adipic acid, succinic acid, or a mixture thereof;
wherein the mole % ranges for (c) and (d) are based on the combined molar amounts of (c) and (d);
wherein the polyol has a hydroxyl number within the range of 25 to 450 mg KOH/g, an average of 0.5 to 2.5 reactive unsaturation sites per molecule, and a viscosity less than 1500 cP at 75° C.; and
wherein the polyol is thermally curable or energy-curable.

### Claim 13 (depends on 1)

An acrylate-free, isocyanate-free coating made by energy-curing the polyol of claim 1, optionally in the presence of a photoinitiator.

### Claim 14 (depends on 1)

An acrylate-free polyurethane or polyisocyanurate coating made by reacting the polyol of claim 1 with a polyisocyanate, a polyisocyanate dimer, or a polyisocyanate trimer under thermal conditions, energy-curing conditions, or both.

### Claim 15 (depends on 1)

A coating made by reacting a blend comprising a urethane-(meth)acrylate resin and the polyol of claim 1 under thermal conditions, energy-curing conditions, or both, optionally in the presence of a polyisocyanate, a polyisocyanate dimer, or a polyisocyanate trimer.

### Claim 16 (depends on 1)

A urethane-(meth)acrylate resin made by:
(a) reacting the polyol of claim 1 with a polyisocyanate, a polyisocyanate dimer, or a polyisocyanate trimer to give an intermediate; and
(b) reacting the intermediate with a hydroxyalkyl (meth)acrylate monomer to give the resin.

### Claim 17 (depends on 16)

A coating made from the resin of claim 16.

### Claim 18 (depends on 1)

An aqueous polyurethane dispersion made from the polyol of claim 1.

### Claim 19 (depends on 18)

A coating made from the polyurethane dispersion of claim 18.

### Claim 20 (depends on 1)

A blend comprising a mono- or poly(meth)acrylate with the polyol of claim 1.

### Claim 21 (depends on 20)

A coating made from the blend of claim 20.

### Claim 22 (depends on 1)

A non-isocyanate polyurethane made from the polyol of claim 1.

### Claim 23 (depends on 1)

A rigid polyisocyanurate foam or a rigid polyurethane foam made from the polyol of claim 1.

### Claim 24 (depends on 1)

A rigid polyisocyanurate foam or a rigid polyurethane foam prepared from a polyol blend comprising:
(a) the polyol of claim 1; and
(b) at least one other polyol;
wherein the fire retardance of the rigid polyisocyanurate foam or rigid polyurethane foam as measured by CA TB-117 is improved versus a rigid polyisocyanurate foam or rigid polyurethane foam prepared from a polyol or polyol blend without the use of the polyol in (a).

### Claim 25 (depends on 1)

A method for improving the fire retardance as measured by CA TB-117 of a rigid polyisocyanurate foam or a rigid polyurethane foam, the method comprising formulating the foam to include as a polyol component the polyol of claim 1.