Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams

Abstract

White graft polymer dispersions in polyoxyalkylene polyether polyols are employed together with flame retardant compounds to prepare flame retardant polyurethane foams. The polymer dispersions employ less than 0.1 mole of induced unsaturation per mole of polyol mixture. Improved processes for the reparation of these polymer dispersions employ either isomerized maleate containing polyetherester polyols or polyetherester polyols prepared by reacting a polyoxyalkylene polyether polyol, a polycarboxylic acid anhydride and an alkylene oxide in the presence of salts and oxides of divalent metals.

The embodiments of the invention in which an exclusive privilege or property is claimed are defined as follows: .[.1. In a process for the preparation of a white stable, low viscosity graft polymer dispersion which comprises the polymerization in a polyol mixture of from 5 to 60 weight percent based on the total weight of the polymer dispersion of an ethylenically unsaturated monomer, or mixture of said monomers, the improvement which comprises conducting the polymerization in a polyol mixture containing from 0.001 to 0.09 mole of induced unsaturation per mole of said polyol mixture..]. .[.2. In a process for the preparation of a graft polymer dispersion which comprises the polymerization of an ethylenically unsaturated monomer or mixture of said monomers in the presence of an effective amount of a free radical initiator in an unsaturation containing polyol mixture containing from 0.001 to 0.09 mole of unsaturation per mole of polyol mixture, the improvement which comprises conducting the polymerization in an isomerized polyether-ester polyol prepared by the reaction of a polyoxyalkylene polyether polyol with 
     
        maleic anhydride and an alkylene oxide..]. 3. In a process for the preparation of polyether-ester polyols by the reaction of a polyoxyalkylene polyether polyol and a polycarboxylic acid anhydride to form a half acid ester followed by the reaction of the half acid ester with an alkylene oxide to obtain a product having an acid number of less than 5 mg KOH/gm the improvement which comprises conducting the reaction between the polyether polyol and the anhydride and the following reaction with the alkylene oxide in the presence of an effective amount of a catalyst selected from the group consisting of zinc, neodeconoate, calcium 
     
     
        naphthenate, copper naphthenate and cobalt naphthenate. 4. A white stable, .Iadd.low viscosity .Iaddend.graft polymer dispersion comprising .[.a polymerized.]. .Iadd.from about 25 to 60 weight percent based on the total weight of the polymer dispersion of an .Iaddend.ethylenically unsaturated monomer or mixture of monomers .Iadd.polymerized in situ .Iaddend.in a .Iadd.polyol .Iaddend.mixture .Iadd.initially .Iaddend.containing from 
     
     
        0.001 to 0.09 mole of induced unsaturation per mole of said mixture. 5. A white stable.Iadd., low viscosity .Iaddend.graft polymer dispersion comprising .[.a polymerized.]. .Iadd.from 25 to 60 weight percent based on the total weight of the polymer dispersion of an .Iaddend.ethylenically unsaturated monomer or mixture of monomers .Iadd.polymerized in situ .Iaddend.in .Iadd.a polyol mixture containing .Iaddend.a macromer said macromer prepared by the reaction of a conventional polyol with an organic compound having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, isocyanate or epoxy group said .[.macromer.]. .Iadd.polyol mixture initially .Iaddend.containing from 0.001 to 0.09 mole of induced unsaturation per mole of said .[.macromer.]. .Iadd.polyol 
     
     
        mixture.Iaddend.. 6. A white stable.Iadd., low viscosity .Iaddend.graft polymer dispersion comprising .Iadd.from about 25 to 60 weight percent based on the total weight of the polymer dispersion of .Iaddend.a polymerized ethylenically unsaturated monomer or mixture of monomers in a polyol mixture .Iadd.initially .Iaddend.containing 0.001 to 0.09 mole of unsaturation per mole of the polyol mixture wherein the polyol mixture comprises an isomerized polyether-ester polyol prepared by the reaction of a polyoxyalkylene-polyether polyol with maleic anhydride and an alkylene 
     
     
        oxide. .[.7.  In a process for the preparation of a flame retardant polyurethane foam prepared by the reaction of an organic polyisocyanate, a polyol, a blowing agent and flame retardants the improvement which comprises employing the graft polymer dispersion of claim 4..]. .[.8. In a process for the preparation of a flame retardant polyurethane foam prepared by the reaction of an organic polyisocyanate, a polyol, a blowing agent, and flame retardants the improvement which comprises employing the graft polymer dispersion of claim 5..]. .[.9. In a process for the preparation of a flame retardant polyurethane foam prepared by the reaction of an organic polyisocyanate, a polyol, a blowing agent, and flame retardants the improvement which comprises employing the graft 
     
     
        polymer dispersion of claim 6..]. .Iadd.10.  The dispersion of claim 4 wherein the viscosity of the dispersion is from 2000 to 8000 cps at 25° C. .Iaddend. .Iadd.11. The dispersion of claim 4 wherein the monomer content is from about 30 to about 45 weight percent based on the total weight of the polymer dispersion. .Iaddend. .Iadd.12. The dispersion of claim 5 wherein the viscosity of the dispersion is from 2000 to 8000 cps at 25° C. .Iaddend. .Iadd.13. The dispersion of claim 5 wherein the monomer content is from about 30 to about 45 weight percent based on the total weight of the polymer dispersion. .Iaddend. .Iadd.14. The dispersion of claim 6 wherein the viscosity of the dispersion is from 2000 to 8000 cps at 25° C. .Iaddend. .Iadd.15. The dispersion of claim 6 wherein the monomer content is from about 30 to about 45 weight percent 
     
     
        based on the total weight of the polymer dispersion. .Iaddend. .Iadd.16. A process for the preparation of a white, stable, low viscosity, high solids content graft polymer dispersion which comprises polymerizing in situ an ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers in a polyol mixture containing from 0.001 to 0.09 moles of induced unsaturation per mole of said polyol mixture in the presence of an effective amount of a reaction moderator and a free radical 
     
     
        initiator. .Iaddend. .Iadd.17.  The process of claim 16 wherein the solids content is from 25 to 60 percent, based on the total weight of the dispersion. .Iaddend. .Iadd.18. The process of claim 16 wherein the solids content is from 30 to 50 percent, based on the total weight of the dispersion. .Iaddend. .Iadd.19. The process of claim 16 wherein 55 to 100 weight percent of the monomer is styrene. .Iaddend. .Iadd.20. The process of claim 16 wherein the viscosity is from 2000 to 8000 cps at 25° 
     
     
        C. .Iaddend. .Iadd.21.  The process of claim 16 wherein the viscosity is from 3000 to 5000 cps at 25° C. .Iaddend. .Iadd.22. The process of claim 16 wherein the polyol mixture contains an isomerized maleate-containing macromer. .Iaddend. .Iadd.23. The process of claim 16 wherein the polyol mixture contains an isomerized maleate-containing macromer, wherein 55 to 100 weight percent of the monomer is styrene, and wherein the viscosity is 3000 to 5000 at 25° C. .Iaddend. .Iadd.24. The process of claim 22 wherein the maleate-containing macromer is prepared in the presence of a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.25. The process of claim 23 wherein the macromer is prepared in the presence of a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.26. The process of claim 24 wherein the divalent metal salt is calcium naphthenate. .Iaddend. .Iadd.27. The process of claim 25 wherein the divalent metal salt is calcium naphthenate. .Iaddend. 
     
     
        .Iadd.     The process of claim 16 wherein the polyol mixture contains a macromer prepared from a compound containing fumarate unsaturation. .Iaddend. .Iadd.29. A white, stable, low viscosity, high solids content graft polymer dispersion prepared by a process comprising polymerizing in situ an ethylenically unsaturated monomer or mixture of ethylenically unsaturated monomers in a polyol mixture containing from 0.001 to 0.09 moles of induced unsaturation per mole of said polyol mixture in the presence of an effective amount of free-radical initiator and a reaction moderator. .Iaddend. .Iadd.30. The product of claim 29 wherein the solids content is from 25 to 60 percent, based on the total weight of the dispersion. .Iaddend. .Iadd.31. The product of claim 29 wherein the solids content is from 30 to 50 percent, based on the total weight of the dispersion. .Iaddend. .Iadd.32. The product of claim 29 wherein 55 to 100 weight percent of the monomer is styrene. .Iaddend. .Iadd.33. The product of claim 29 wherein the viscosity is less than 10,000 cps at 25° C. 
     
     
        .Iaddend. .Iadd.34.  The product of claim 29 wherein the viscosity is from 3000 to 5000 cps at 25° C. .Iaddend. .Iadd.35. The product of claim 29 wherein the polyol mixture contains an isomerized maleate-containing macromer. .Iaddend. .Iadd.36. The product of claim 31 wherein the polyol mixture contains an isomerized maleate-containing macromer, wherein 55 to 100 weight percent of the monomer is styrene, and wherein the viscosity is 3000 to 5000 at 25° C. .Iaddend. .Iadd.37. The product of claim 35 wherein the maleate-containing macromer is prepared in the presence of a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.38. The product of claim 36 wherein the macromer is prepared in the presence of a divalent metal salt or oxide catalyst. .Iaddend. .Iadd.39. The product of claim 37 wherein the divalent metal salt is calcium naphthenate. .Iaddend. 
     
     
        .Iadd.     The product of claim 38 wherein the divalent metal salt is calcium naphthenate. .Iaddend. .Iadd.41. The product of claim 29 wherein the polyol mixture contains a macromer prepared from a compound containing fumarate unsaturation. .Iaddend. .Iadd.42. The process of claim 3 wherein the catalyst is calcium naphthenate. .Iaddend. .Iadd.43. A polyurethane foam characterized by flame retardancy prepared by a process comprising reacting the graft polymer dispersion of claim 29 with an organic polyisocyanate. .Iaddend. .Iadd.44. A polyurethane foam characterized by flame retardancy prepared by a process comprising reacting the graft polymer dispersion of claim 30 with an organic polyisocyanate. .Iaddend. 
     
     
        .Iadd.45.  A polyurethane foam characterized by flame retardancy prepared by a process comprising reacting the graft polymer dispersion of claim 34 with an organic polyisocyanate. .Iaddend. .Iadd.46. A polyurethane foam characterized by flame retardancy prepared by a process comprising reacting the graft polymer dispersion of claim 35 with an organic 
     
     
        polyisocyanate. .Iaddend. .Iadd.47.  A polyurethane foam characterized by flame retardancy prepared by a process comprising reacting the graft polymer dispersion of claim 36 with an organic polyisocyanate. .Iaddend. .Iadd.48. A polyurethane foam characterized by flame retardance prepared by a process comprising reacting the graft polymer dispersion of claim 41 with an organic polyisocyanate. .Iaddend.