# US 4,393,186 A · Thermoplastic polyurethanes prepared by reacting polyisocyanate, polyester polyol, cycloaliphatic diol and a monofunctional chain-terminating compound > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,393,186 A - Document ID: US4393186A - Status: Granted - Kind: A - Application number: 06/296,629 - Filed: 1981-08-27 - Granted: 1983-07-12 - Earliest claimed: 1979-06-19 - Assignees: Lord Corporation - Inventors: Dennis J. Damico; Vincent J. Pascarella - Web page: https://patentgrep.com/patent/US4393186A ## CPC - C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step - C08G 18/4205: {containing cyclic groups} - C08G 18/4277: {Caprolactone and/or substituted caprolactone} - C09J 175/06: from polyesters - C08L 2666/02: Organic macromolecular compounds, natural resins, waxes or and bituminous materials - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Novel polyurethanes especially suited for applications requiring initial heat resistance in a non-alcohol, non-exotic solvent system such as methyl ethyl ketone and having peel strengths of at least 5 pounds per linear inch (pli) uncrosslinked at about 180.degree. to about 200.degree. F., optionally containing crosslinkers, and which are typically used in the automobile industry, are described. The new polyurethanes are substantially free of reactive isocyanate and hydroxyl groups and comprise the reaction product of (a) at least one polyisocyanate having at least two reactive isocyanate groups; (b) at least one polyester polyol having at least two hydroxyl groups; (c) at least one cycloaliphatic diol chain-extending agent; and (d) at least one monofunctional isocyanate-reactive chain-terminating compound; said polyisocyanate being present in an excess amount with respect to said polyester polyol and said cycloaliphatic diol; said monofunctional isocyanate-reactive compund being present in an amount sufficient to ensure reaction of excess isocyanate groups; said polyester polyol comprising the reaction product of (i) at least one saturated acyclic, cyclic or aromatic monomeric or polymeric polyol having at least two hydroxy groups; (ii) from 30 to 100 mole percent terephthalic acid; and (iii) from 70 to 0 mole percent of at least one saturated or unsaturated acyclic, cyclic or aromatic carboxylic acid, other than terephthalic acid, having at least two carboxyl groups; said polyurethane having a molecular weight of at least 20,000. ## Claims ### Claim 1 A heat-resistant, thermoplastic polyurethane substantially free of reactive isocyanate and hydroxyl groups comprising the reaction product of (a) at least one polyisocyanate having at least two reactive isocyanate groups; (b) at least one polyester polyol having at least two hydroxyl groups; (c) at least one cycloaliphatic diol chain-extending agent; and (d) at least one monofunctional isocyanate-reactive chain-terminating compound; said polyisocyanate being present in an excess amount with respect to said polyester polyol and said cycloaliphatic, diol; said monofunctional isocyanate-reactive compound being present in an amount sufficient to ensure reaction of excess isocyanate groups; said polyester polyol having been prepared from the reaction of (i) at least one saturated acyclic, cyclic or aromatic monomeric or polymeric polyol having at least two hydroxyl groups; (ii) from 30 to 100 mole present terephthalic acid; and (iii) from 70 to 0 mole percent of at least one saturated or unsaturated acyclic, cyclic or aromatic carboxylic acid, other than terephthalic acid, having at least two carboxyl groups; said polyurethane having a molecular weight of at least 20,000. ### Claim 2 (depends on 1) A polyurethane according to claim 1 wherein said cycloaliphatic diol comprises dimethylolcyclohexane. ### Claim 3 (depends on 1) A polyurethane according to claim 1 wherein said polyester polyol is prepared from a polycarboxylic component comprising 30 mole percent terephtalic acid and 70 mole percent adipic acid. ### Claim 4 (depends on 3) A polyurethane according to claim 3 wherein said cycloaliphatic diol comprises dimethylolcyclohexane. ### Claim 5 (depends on 1) A polyurethane according to claim 1 wherein said polyester diol is prepared from 1,6-hexane diol, 50 mole percent terephthalic acid, 40 mole percent adipic acid and dimethylolcyclohexane, and said polyurethane has a molecular weight in the range from 60,000 to 300,000. ### Claim 6 (depends on 5) A polyurethane according to claim 5 wherein said polyisocyanate comprises a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. ### Claim 7 A heat-resistant, thermoplastic polyurethane substantially free of reactive isocyanate and hydroxyl groups comprising the reaction product of (a) at least one aromatic polyisocyanate having at least two reactive isocyanate groups; (b) at least one polycaprolactone having at least two hydroxyl groups; (c) at least one cycloaliphatic diol chain-extending agent; and (d) at least one monofunctional isocyanate-reactive chain-terminating compound; said polyisocyanate being present in an excess amount with respect to said polycaprolactone and said cycloaliphatic diol; said monofunctional isocyanate-reactive compound being present in an amount sufficient to ensure reaction of excess isocyanate groups; said polyurethane having a molecular weight of at least 20,000. ### Claim 8 (depends on 7) A polyurethane according to claim 7 wherein said cycloaliphatic diol comprises dimethylolcyclohexane. ### Claim 9 (depends on 7) A polyurethane according to claim 7 wherein said polyisocyanate comprises a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. ### Claim 10 (depends on 9) A polyurethane according to claim 9 wherein said cycloaliphatic diol comprises dimethylolcyclohexane and said polyurethane has a molecular weight in the range from 60,000 to 300,000.