# US 2013/0158142 A1 · Hybrid phd/pmpo polyols for polyurethane foam applications > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2013/0158142 A1 - Document ID: US20130158142A1 - Status: Published application - Kind: A1 - Application number: 13/327,879 - Filed: 2011-12-16 - Published: 2013-06-20 - Earliest claimed: 2011-12-16 - Assignees: Bayer MaterialScience AG - Inventors: Rick L. Adkins; Brian L. Neal - Web page: https://patentgrep.com/patent/US20130158142A1 ## CPC - C08G 18/4072: {Mixtures of compounds of group C08G18/63 with other macromolecular compounds} - C08F 283/006: {on to polymers provided for in C08G18/00 (C08F283/004 takes precedence)} - C08G 18/0876: {the dispersing or dispersed phase being a polyol} - C08G 18/3231: {Hydrazine or derivatives thereof} - C08G 18/632: {onto polyethers} - C08G 18/636: {characterised by the presence of a dispersion-stabiliser} - C08G 18/7621: {being toluene diisocyanate including isomer mixtures} - C08G 2110/0008: flexible - C08G 2110/0083: prepared using water as the sole blowing agent - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract This invention relates to hybrid polymer polyols. These hybrid polymer polyols comprise the free-radical polymerization product of (A) a base polyol comprising (1) a polymer modified polyol selected from (a) dispersions of polyureas and/or polyhydrazodicarbonamides in a hydroxyl group containing compound and (b) polyisocyanate polyaddition polyols, and (2) optionally, a polyol having a functionality of 2 to 6 and an OH number of from 20 to 500; (B) optionally, a preformed stabilizer; and (C) one or more ethylenically unsaturated monomers, in the presence of (D) a free-radical polymerization initiator, and (E) optionally, a polymer control agent. The present invention also relates to a process for the preparation of these hybrid polymer polyols, foams prepared from these hybrid polymer polyols and to a process for the preparation of these foams. ## Claims ### Claim 1 A stable, low-viscosity hybrid polymer polyol comprising the free-radical polymerization product of: (A) a base polyol component comprising: (1) from 1 to 100% by weight of a polymer modified polyol selected from the group consisting of: (a) one or more dispersions of a polyurea and/or polyhydrazodicarbonamide in a hydroxyl group containing compound, and (b) one or more polyisocyanate polyaddition polyols; and (2) from 0 to 99% by weight of a polyol having a functionality of from 2 to 6, and an OH number of from 20 to 500; wherein the sum of the %'s by weight of (A)(1) and (A)(2) totals 100% by weight of component (A); (B) optionally, a preformed stabilizer; and (C) one or more ethylenically unsaturated monomers; in the presence of: (D) a free-radical polymerization initiator; and (E) optionally, a polymer control agent; wherein the solids content of the hybrid polymer polyol ranges from 20 to 70% by weight, and comprises (i) from 1% to 60% by weight of polyureas and/or polyhydrazodicarbonamides or polyisocyanate polyaddition products, and (ii) from 40% to 99% by weight of graft copolymers comprising the ethylenically unsaturated monomers, with the sum of the %'s by weight of (i) and (ii) totaling 100% by weight of the solids in the hybrid polymer polyol. ### Claim 2 (depends on 1) The stable, low-viscosity hybrid polymer polyol of claim 1, wherein (A) said base polyol component comprises: (1) from 2 to 80% by weight of a polymer modified polyol selected from the group consisting of: (a) one or more dispersions of a polyurea and/or polyhydrazodicarbonamide in a hydroxyl group containing compound, and (b) one or more polyisocyanate polyaddition polyols; and (2) from 20 to 98% by weight of a polyol having a functionality of from 2 to 4 and an OH number of from 25 to 300; wherein the sum of the %'s by weight of (A)(1) and (A)(2) totals 100% by weight of component (A). ### Claim 3 (depends on 1) The stable, low-viscosity hybrid polymer polyol of claim 1, wherein (A)(1)(a) said one or more dispersions of a polyurea and/or polyhydrazodicarbonamide is the reaction product of (i) at least one organic polyisocyanate, with (ii) one or more amine functional compounds selected from the group consisting of primary and/or second amino-group containing di- and/or polyamines, hydrazines, hydrazides and mixtures thereof, in (iii) a hydroxyl group containing compound. ### Claim 4 (depends on 3) The stable, low-viscosity hybrid polymer polyol of claim 3, in which (i) said organic polyisocyanate is toluene diisocyanate, (ii) said amine functional compound is hydrazine hydrate, and (iii) said hydroxyl group containing compound is a polyether polyol having a functionality of about 3 and an OH number of about 35, wherein the resultant polyhydrazodicarbonamide polyol has a functionality of about 3 and an OH number of about 28. ### Claim 5 (depends on 1) The stable, low-viscosity hybrid polymer polyol of claim 1, wherein (C) said one or more ethylenically unsaturated monomers comprise styrene, acrylonitrile or mixtures thereof. ### Claim 6 (depends on 5) The stable, low-viscosity hybrid polymer polyol of claim 5, wherein C) said ethylenically unsaturated monomers comprise a mixture of styrene and acrylonitrile in a weight ratio of about 80:20 to 20:80. ### Claim 7 (depends on 1) The stable, low-viscosity hybrid polymer polyol of claim 1, wherein the solids content of the hybrid polymer polyol ranges from 25 to 65% by weight, and comprises (i) from 3 to 55% by weight of polyureas and/or polyhydrazodicarbonamides or polyisocyanate polyaddition products, and (ii) from 45% to 97% by weight of graft copolymers comprising the ethylenically unsaturated monomers, with the sum of the %'s by weight of (i) and (ii) totaling 100% by weight of the solids in the hybrid polymer polyol. ### Claim 8 (depends on 1) The stable, low-viscosity hybrid polymer polyol of claim 1, which additionally comprises a chain transfer agent. ### Claim 9 A process for the preparation of a stable, low-viscosity hybrid polymer polyol comprising (I) free-radically polymerizing: (A) a base polyol component comprising: (1) from 1 to 100% by weight of a polymer modified polyol selected from the group consisting of: (a) one or more dispersions of a polyurea and/or polyhydrazodicarbonamide in a hydroxyl group containing compound and (b) one or more polyisocyanate polyaddition polyols; and (2) from 0 to 99% by weight of a polyol having a functionality of from 2 to 6, and an OH number of from 20 to 500; wherein the sum of the %'s by weight of (A)(1) and (A)(2) totals 100% by weight of component (A); (B) optionally, a preformed stabilizer; and (C) one or more ethylenically unsaturated monomers; in the presence of: (D) a free-radical polymerization initiator; and (E) optionally, a polymer control agent; wherein the resultant hybrid polymer polyol has a solids content of from 20 to 70% by weight, which comprises (i) from 1% to 60% by weight of polyureas and/or polyhydrazodicarbonamides or polyisocyanate polyaddition products, and (ii) from 40% to 99% by weight of graft copolymers comprising the ethylenically unsaturated monomers, with the sum of the %'s by weight of (i) and (ii) totaling 100% by weight of the solids in the hybrid polymer polyol ### Claim 10 (depends on 9) The process of claim 9, wherein (A) said base polyol component comprises: (1) from 2 to 80% by weight of a polymer modified polyol selected from the group consisting of: (a) one or more dispersions of a polyurea and/or polyhydrazodicarbonamide in a hydroxyl group containing compound, and (b) one or more polyisocyanate polyaddition polyols; and (2) from 20 to 98% by weight of a polyol having a functionality of from 2 to 4 and an OH number of from 25 to 300; wherein the sum of the %'s by weight of (A)(1) and (A)(2) totals 100% by weight of component (A). ### Claim 11 (depends on 9) The process of claim 9, wherein (A)(1)(a) said one or more dispersions of a polyurea and/or polyhydrazodicarbonamide is the reaction product of (i) at least one organic polyisocyanate, with (ii) one or more amine functional compounds selected from the group consisting of primary and/or second amino-group containing di- and/or polyamines, hydrazines, hydrazides and mixtures thereof, in (iii) a hydroxyl group containing compound. ### Claim 12 (depends on 11) The process of claim 11, in which (i) said organic polyisocyanate is toluene diisocyanate, (ii) said amine functional compound is hydrazine hydrate, and (iii) said hydroxyl group containing compound is a polyether polyol having a functionality of about 3 and an OH number of about 35, wherein the resultant polyhydrazodicarbonamide polyol has a functionality of about 3 and an OH number of about 28. ### Claim 13 (depends on 9) The process of claim 9, wherein (C) said one or more ethylenically unsaturated monomers comprise styrene, acrylonitrile or mixtures thereof. ### Claim 14 (depends on 13) The process of claim 13, wherein (C) said ethylenically unsaturated monomers comprise a mixture of styrene and acrylonitrile in a weight ratio of about 80:20 to 20:80. ### Claim 15 (depends on 9) The process of claim 9, wherein the solids content of the hybrid polymer polyol ranges from 25 to 65% by weight, and comprises (i) from 3 to 55% by weight of polyureas and/or polyhydrazodicarbonamides or polyisocyanate polyaddition products, and (ii) from 45% to 97% by weight of graft copolymers comprising the ethylenically unsaturated monomers, with the sum of the %'s by weight of (i) and (ii) totaling 100% by weight of the solids in the hybrid polymer polyol. ### Claim 16 (depends on 9) The process of claim 9, which additionally comprises a chain transfer agent. ### Claim 17 (depends on 1) A process for the preparation of a polyurethane foam, comprising reacting: (I) a polyisocyanate component, with (II) an isocyanate-reactive component comprising the stable, low viscosity hybrid polyol of claim 1: in the presence of (III) a blowing agent, and (IV) at least one catalyst ### Claim 18 (depends on 17) The process of claim 17, wherein (II) said isocyanate-reactive component comprises (1) from 5 to 100% by weight of the hybrid polymer polyol, and (2) from 0 to 95% by weight of one or more conventional isocyanate-reactive components selected from the group consisting of polyether polyols, polyester polyols, polyoxyalkylene polyols, crosslinking agents, chain extenders and mixtures thereof, with the sum of the %'s by weight of (1) and (2) totaling 100% by weight of component (II). ### Claim 19 (depends on 18) The process of claim 18, wherein (II) said isocyanate-reactive component comprises (1) from 10 to 75% by weight of the hybrid polymer polyol, and (2) from 25 to 75% by weight of one or more conventional isocyanate-reactive components selected from the group consisting of polyether polyols, polyester polyols, polyoxyalkylene polyols, crosslinking agents, chain extenders and mixtures thereof, with the sum of the %'s by weight of (1) and (2) totaling 100% by weight of component (II). ### Claim 20 (depends on 17) The process of claim 17, wherein said process additionally comprises reacting (V) at least one silicon surfactant. ### Claim 21 (depends on 1) A polyurethane foam comprising the reaction product of: (I) a polyisocyanate component, with (II) an isocyanate-reactive component comprising the stable, low viscosity hybrid polyol of claim 1: in the presence of (III) a blowing agent, and (IV) at least one catalyst. ### Claim 22 (depends on 21) The foam of claim 21, wherein (II) said isocyanate-reactive component comprises (1) from 5 to 100% by weight of the hybrid polymer polyol, and (2) from 0 to 95% by weight of one or more conventional isocyanate-reactive components selected from the group consisting of polyether polyols, polyester polyols, polyoxyalkylene polyols, crosslinking agents, chain extenders and mixtures thereof, with the sum of the %'s by weight of (1) and (2) totaling 100% by weight of component (II). ### Claim 23 (depends on 22) The foam of claim 22, wherein (II) said isocyanate-reactive component comprises (1) from 10 to 75% by weight of the hybrid polymer polyol, and (2) from 25 to 75% by weight of one or more conventional isocyanate-reactive components selected from the group consisting of polyether polyols, polyester polyols, polyoxyalkylene polyols, crosslinking agents, chain extenders and mixtures thereof, with the sum of the %'s by weight of (1) and (2) totaling 100% by weight of component (II). ### Claim 24 (depends on 21) The foam of claim 21, which additionally comprises (V) at least one silicon surfactant.