Polyurethanes, reactive solutions and methods and their production

Abstract

A reactive, stable dispersion can be prepared by the in situ polymerization of an ethylenically unsaturated monomer in an appropriate reactive medium such as a polyol. The in situ polymerization produces a dispersed polymer containing reactive radicals. The stable dispersion can be employed in any of a number of reactions, e.g., polyurethane-forming reactions, to introduce into the resultant product, as an integral part thereof, both the polyol and dispersed polymer.

1.  A method for preparing reactive compositions convertible to elastic polyurethane products .[.by.]. comprising the steps of (a) dispersing a minor amount of ethylenically unsaturated monomer in a major amount of a solvent medium, said solvent medium consisting essentially of at least one normally liquid polyol essentially free from ethylenic unsaturation and having a molecular weight of at least about 2,000 and a hydroxyl number in the range of about 30 to about .[.140.]. .Iadd.600, said hydroxyl number being appropriate to provide an elastic polyurethane, .Iaddend.and   (b) polymerizing said monomer in said solvent by free radical addition polymerization to a substantially linear polymer having a molecular weight of at least 5,000 to provide a liquid, stable dispersion of polymerpolyol having a viscosity of less than 40,000 cps at 10% polymer concentration. said .Iadd.substantially linear .Iaddend.polymer being film-forming and .Iadd.having radicals reactive with isocyanate radicals, .Iaddend.said reactive composition being convertible to an elastic polyurethane product upon reaction with an organic polyisocyanate.     
     
     
       2. A method in accordance with claim 1 wherein said ethylenically unsaturated monomer is free of reactive radicals containing active hydrogen atoms. 
     
     
       3. A method in accordance with claim 1 wherein said monomer and said polyol are selected to provide a polymer in said polymer-polyol mixture containing radicals selected from the group consisting of --COOH, --OH, --SH and organic nitrogen-containing radicals in which all of the nitrogen bonds are satisfied by bonds with at least one member selected from the group consisting of carbon and hydrogen. 
     
     
       4. A method in accordance with claim 1 wherein said monomer is a single species of ethylenically unsaturated monomer. 
     
     
       5. A method in accordance with claim 1 wherein said reactive composition is produced by the in situ polymerization of a plurality of ethylenically unsaturated monomers in said solvent medium. 
     
     
       6. A method in accordance with claim 1 wherein said ethylenically unsaturated monomer contains an organic nitrogen-containing radical in which all of the nitrogen bonds are satisfied by bonds with at least one member selected from the group consisting of carbon and hydrogen. 
     
     
       7. A method as defined in claim 1 wherein said ethylenically unsaturated monomer is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, diglycol esters of itaconic acid, glycol monoesters of itaconic acid, methyl monoester of itaconic acid, allyl alcohol, maleic acid, fumaric acid, acrylamide and substituted acrylamide. 
     
     
       8. A method as defined in claim 1 wherein said film-forming polymer is a copolymer resulting from the polymerization of at least two ethylenically unsaturated monomers at least one of which contains at least one radical reactive with the --N=C=O radical of an isocyanate. 
     
     
       9. A method as defined in claim 8 wherein said ethylenically unsaturated monomer which contains at least one radical reactive with the --N=C=O radical of an isocyanate is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, diglycol esters of itaconic acid, glycol monoesters of itaconic acid, methyl monoester of itaconic acid, allyl alcohol, maleic acid, fumaric acid, acrylamide and substituted acrylamide. 
     
     
       10. A reactive composition comprising the product of the in situ polymerization of an ethylenically unsaturated monomer in a reactive solvent having a plurality of radicals reactive with isocyanato radicals produced in accordance with the method of claim 1. 
     
     
       11. A reactive composition as defined in claim 10 wherein said ethylenically unsaturated monomer is free of reactive radicals containing active hydrogen atoms. 
     
     
       12. A reactive composition as defined in claim 10 wherein the polymeric product contains radicals selected from the group consisting of --COOH, --OH, NH 2 , =NH, --SH, and CONH 2 . 
     
     
       13. A reactive composition as defined in claim 10 wherein said monomer is a single species of ethylenically unsaturated monomer. 
     
     
       14. A reactive composition in accordance with claim 10 produced by the in situ polymerization of a plurality of ethylenically unsaturated monomers in said solvent. 
     
     
       15. A reactive composition as defined in claim 10 wherein said monomer contains a radical reactive with isocyanato radicals. 
     
     
       16. A reactive composition in accordance with claim 10 produced by the in situ polymerization of styrene in said solvent. 
     
     
       17. A reactive composition in accordance with claim 10 produced by the in situ polymerization of styrene and acrylic ester in said solvent. 
     
     
       18. A reactive composition in accordance with claim 10 produced by the in situ polymerization of a lower alkyl methacrylate in said solvent. 
     
     
       19. A reactive composition in accordance with claim 10 produced by the in situ polymerization of a lower alkyl acrylate in said solvent. 
     
     
       20. A reactive composition in accordance with claim 10 produced by the in situ polymerization of a vinyl ester in said solvent. 
     
     
       21. A reactive composition in accordance with claim 10 produced by the in situ polymerization of a vinyl ester and an acrylic ester in said solvent. 
     
     
       22. A reactive composition in accordance with claim 10 produced by the in situ polymerization of a polymerizable tertiary amine in said solvent. 
     
     
       23. A composition in accordance with claim 10 comprising the in situ polymerizate of a polymerizable ethylenically unsaturated monomer in a polyether polyol. .Iadd. 24. A reactive composition as defined in claim 10 in which the polymer concentration in the composition (A) is from about 20% to about 50% by weight of said composition. .Iaddend. .Iadd.25. A reactive composition as defined in claim 10 in which the polyol is a polyoxypropylene polyol..Iaddend. .Iadd.26. A reactive composition as defined in claim 10 in which the polyol is a polyoxypropylene glycol..Iaddend. .Iadd.27. A reactive composition as defined in claim 10 in which the polyol is a polyoxypropylene triol..Iaddend. .Iadd.28. A reactive composition as defined in claim 10 in which the polymer has a molecular weight of at least 10,000..Iaddend. .Iadd.29. A reactive composition as defined in claim 10 in which the polymerization of the ethylenically unsaturated monomer in the polyol is carried out in the presence of azobisbutyronitrile as a catalyst..Iaddend..Iadd. 30. A reactive composition convertible to an elastic polyurethane product having improved load bearing properties by reaction with an organic polyisocyanate, said reactive composition being produced by a method comprising the steps of (a) dispersing a minor amount of ethylenically unsaturated monomer in a major amount of a solvent medium, said solvent medium consisting essentially of at least one normally liquid polyoxypropylene polyol essentially free from ethylenic unsaturation and having a molecular weight of at least about 2,000 and a hydroxyl number in the range of about 30 to about 600, said hydroxyl number being appropriate to provide an elastic polyurethane, and   (b) polymerizing said monomer in said solvent by free radical addition polymerization to a substantially linear polymer having a molecular weight of at least 10,000 to provide a liquid, stable dispersion of polymer polyol having a viscosity of less than 40,000 cps at 10% polymer concentration, said substantially linear polymer being film-forming and having radicals reactive with isocyanate radicals, said reactive composition having a combining weight in the range providing an elastic polyurethane product upon reaction with an organic polyisocyanate. .Iaddend. .Iadd.31. A composition as claimed in claim 30 in which the polymerization of the ethylenically unsaturated monomer in the polyol is carried out in the presence of azobisisobutyronitrile as a catalyst..Iaddend..Iadd. 32. A composition as claimed in claim 30 in which the polymer concentration in the composition is from about 20% to about 50% by weight of said mixture.