# US 11,078,325 B2 · Method of preparing polyurethanes from oligomeric polyol compositions and polyisocyanates

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- Number: US 11,078,325 B2
- Document ID: US11078325B2
- Status: Granted
- Kind: B2
- Application number: 16/105,161
- Filed: 2018-08-20
- Published: 2019-08-08
- Granted: 2021-08-03
- Earliest claimed: 2017-04-13
- Assignees: Presidium USA, Inc.
- Applicants: Presidium USA, Inc
- Inventors: James Henry Blumsom; Andrew John Tennant; James A. Cella; David Goldwasser; Daniel J. Brunelle; Stephen Burks; Richard Heggs
- Web page: https://patentgrep.com/patent/US11078325B2

## CPC

- C08G 59/62: Alcohols or phenols
- C08G 18/02: of isocyanates or isothiocyanates only
- C08G 18/3206: {aliphatic}
- C08G 18/3215: {containing aromatic groups or benzoquinone groups}
- C08G 18/3284: {containing four hydroxy groups}
- C08G 18/40: High-molecular-weight compounds {(C08G18/2805 takes precedence)}
- C08G 18/4222: {derived from aromatic polyhydroxy compounds and polycarboxylic acids}
- C08G 18/4244: {containing oxygen in the form of ether groups}
- C08G 18/44: Polycarbonates
- C08G 18/46: having heteroatoms other than oxygen
- C08G 18/4615: {containing nitrogen}
- C08G 18/48: Polyethers
- C08G 18/4829: {Polyethers containing at least three hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/5021: {having nitrogen}
- C08G 18/7664: {containing alkylene polyphenyl groups}
- C08G 64/42: Chemical after-treatment
- C08L 75/04: Polyurethanes
- C08G 2310/00: Agricultural use or equipment
- C08J 2375/04: Polyurethanes
- 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)
- 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)

## Abstract

There is provided an oligomeric polyol composition having (a) an oligomeric network containing residues of at least one polyhydroxylated aromatic compound and residues of at least one polyol having at least three hydroxyl groups; and (b) a plurality of peripheral groups having one or more pendant hydroxyl groups bound to the oligomeric network by a plurality of linking units. The residues of the polyol may optionally contain one or more oxygen ether groups, one or more amino ether groups, or both of one or more oxygen ether groups and one or more amino ether groups. Reaction of the oligomeric polyols with isocyanate monomers affords a new class of polyurethanes having superior heat and water resistance. The new polyurethanes exhibit lower peak exotherms, typically less than 250° F. during in-mold polymerization. Articles prepared from polyurethanes incorporating such oligomeric polyol compositions exhibit flexural strengths and moduli in excess of 10,000 psi and 400,000 psi respectively, and outstanding green strength.

## Claims

### Claim 1

A method comprising:
(a) mixing a first reactant comprising one or more polyisocyanates or latent polyisocyanates with a second reactant comprising an oligomeric polyol composition to form a reactive mixture, the oligomeric polyol composition comprising:
(i) at least one oligomeric polyol component;
(ii) one or more monomeric polyols; and
(iii) one or more polyhydroxylated aromatic compounds;
wherein the at least one oligomeric polyol component comprises residues of either or both of the one or more monomeric polyol and the one or more polyhydroxylated aromatic compound linked by one or more carbonate groups and optionally one or more, oxygen ether groups; and
wherein the at least one monomeric polyol comprises more than three secondary hydroxyl groups; and
(b) curing the reactive mixture to afford a cured polyurethane product;
wherein during step (b) at least a portion of the hydroxyl groups of the at least one oligomeric polyol component and at least a portion of the hydroxyl groups of the one or more monomeric polyols react with one or more isocyanate groups or latent isocyanate groups of the polyisocyanates or latent polyisocyanates; wherein the cured polyurethane product exhibits at least one of the following physical characteristics: a heat distortion temperature in excess of 110 degrees centigrade; a peak exotherm less than 250 degrees Fahrenheit during in-mold curing/polymerization; a flexural strength in excess of 10,000 psi; a flexural modulus in excess of 400,000 psi; and a Young's modulus below 50,000 psi.

### Claim 2 (depends on 1)

The method of claim 1, wherein the one or more polyisocyanates or latent polyisocyanates comprises a monomeric polyisocyanate, a polyisocyanate prepolymer, a blocked polyisocyanate, a polymeric polyisocyanate, or a mixture of two or more of the foregoing.

### Claim 3 (depends on 1)

The method of claim 1, wherein the one or more polyisocyanates comprises a prepolymer which is a polymeric reaction product of a monomeric polyisocyanate and a polyether polyol.

### Claim 4 (depends on 3)

The method of claim 3, wherein the monomeric polyisocyanate comprises diphenylmethane diisocyanate and the polyether polyol comprises a polyoxypropylene diol.

### Claim 5 (depends on 1)

The method of claim 1, wherein either or both of the first reactant and the second reactant comprises a filler.

### Claim 6 (depends on 5)

The method of claim 5, wherein the filler comprises one or more clay fillers, glass flake fillers, glass fiber fillers, carbon black fillers, carbon fiber fillers, basalt fiber fillers, or mixtures thereof.

### Claim 7 (depends on 1)

The method of claim 1, in which steps (a) and (b) are conducted in the absence of an exogenous catalyst.

### Claim 8 (depends on 1)

The method of claim 1, wherein steps (a) and (b) are conducted in the absence of an exogenous mold release agent.

### Claim 9 (depends on 1)

The method of claim 1, further comprising adding one or more mold release agents to the second reactant prior to step (a).

### Claim 10 (depends on 1)

The method of claim 1, further comprising adding one or more diamine chain extenders to the second reactant prior to step (a).

### Claim 11 (depends on 1)

The method of claim 1, further comprising a step of transferring the reactive mixture into a heated mold prior to step (b), and wherein the cured polyurethane product is a molded article.

### Claim 12 (depends on 1)

The method of claim 1, wherein the at least one oligomeric polyol component comprises an oligomeric network comprising residues of the one or more polyhydroxylated aromatic compounds and residues of the one or more monomeric polyols; and
a plurality of peripheral groups each comprising one or more hydroxyl groups bound to the oligomeric network by a plurality of linking units, wherein at least a portion of the linking units are oxygen atoms of carbonate linkages and optionally hydrocarbyl ether linkages.

### Claim 13 (depends on 12)

The method of claim 12, wherein at least a portion of the linking units are carbonate linkages.

### Claim 14 (depends on 1)

The method of claim 1, wherein the oligomeric polyol component comprises carbonate species comprising one or more carbonate groups and two or more residues of the monomeric polyol.

### Claim 15 (depends on 1)

The method of claim 1, wherein the oligomeric polyol composition comprises the reaction product of one or more aromatic polycarbonates with one or more monomeric polyols having more than three secondary hydroxyl groups;
wherein the at least one oligomeric polyol component comprises residues of at least one polyhydroxylated aromatic compound derived from the one or more aromatic polycarbonates and residues of the one or more monomeric polyols; and
wherein at least a portion of the residues of the one or more polyhydroxylated aromatic compounds derived from the one or more aromatic polycarbonates and the residues of the one or more monomeric polyols are linked by carbonate groups.

### Claim 16 (depends on 15)

The method of claim 15, wherein the one or more aromatic polycarbonates comprises bisphenol A polycarbonate.

### Claim 17 (depends on 15)

The method of claim 15, wherein the one or more monomeric polyols comprises a monomeric polyol having four or more secondary hydroxyl groups.

### Claim 18 (depends on 15)

The method of claim 15, wherein the oligomeric polyol component further comprises residues of one or more monomeric polyols comprising four or more primary hydroxyl groups.

### Claim 19 (depends on 15)

The method of claim 15, wherein the oligomeric polyol composition is formed in the presence of a metal hydroxide catalyst comprising potassium hydroxide at a temperature of 120° C. or greater and 160° C. or less during a reaction time of 45 minutes or greater and 90 minutes or less, and the one or more aromatic polycarbonates and the one or more monomeric polyols are reacted in a molar ratio of repeat units of the one or more aromatic polycarbonates to the one or more monomeric polyols of 0.25 to 1 or greater, and 1 to 1 or less.

### Claim 20 (depends on 1)

The method of claim 1 wherein the one or more monomeric polyols contains one or more oxygen ether groups.