Method of preparing polyurethanes from liquid, stable, reactive, film-forming polymer/polyol mixtures formed by polymerizing an ethylenically unsaturated monomer in a polyol

• US RE29,118 E
• Filed: 02/19/1974
• Issued: 01/18/1977
• Est. Priority Date: 02/06/1963
• Status: Expired due to Term

• Current Assignee: Paul Stamberger
• Original Assignee: Paul Stamberger
• Inventors: Stamberger, Paul
• Primary Examiner(s): Ivy, C. Warren
• Application Number:
  US05/443,774
• Re-issue Of: US 3,938,277 A
• Time in Patent Office: 1,064 Days
• Field of Search: 260/2.5 A, 260/77.5 A, 260/77.5 C, 260/77.5 AP, 260/859 R, 260/859 PV, 260/33.2 R, 260/33.4 R, 260/33.4 UR, 260/2.5 BE , 260/77.5 AM, 260/858
• US Class Current: 521/137
• CPC Class Codes: C08G 18/638 characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles

Abstract

.Iadd.This invention provides a method for preparing elastic polyurethanes from organic polyisocyanates and polymer-polyol mixtures, wherein the polymer is obtained by polymerizing an ethylenically unsaturated monomer in a polyol. This invention further provides a method for preparing cellular polyurethanes from organic polyisocyanates and polymer-polyol mixtures, wherein the polymer is obtained by polymerizing an ethylenically unsaturated monomer in a polyol. This invention still further provides polyurethanes produced by the aforementioned methods. .Iaddend.

Claims

1. A method for preparing .Iadd.elastic .Iaddend.polyurethanes comprising reacting

(A) a liquid, stable reactive polymer-polyol mixture .Iadd.convertible to an elastic polyurethane product .Iaddend.having a viscosity of less than about 40,000 cps. at 10% polymer concentration and having a combining weight in a range yielding elastic .[.-to-rigid.]. polyurethane products, the essential components of said reactive mixture consisting of

(1) a substantial but minor amount of film forming polymer having a molecular weight of at least 5,000 and having a plurality of radicals containing active hydrogen atoms which are reactive with the --N=C=O radicals of an organic polyisocyanate

and

(2) a major amount of a solvent medium for said polymer consisting essentially of at least one normally liquid polyol essentially free from ethylenic unsaturation and having a molecular weight of at least about .[.500.]. .Iadd.1000.Iaddend., said polymer (1) being the polymerizate obtained by polymerizing, to a molecular weight of at least 5,000 and to a solids concentration of about 10% to about 50% by weight, an ethylenically unsaturated monomer in such polyol,

with

(B) an organic polyisocyanate to form such polyurethane, the ratio of the --N=C=O equivalents of (B) to the equivalents of reactive radicals of (A) being in the range of about 1-5 to 1.

2. A method in accordance with claim 1 for the production of a cellular polyurethane in which mixture (A) and polyisocyanate (B) are reacted while in intimate admixture with a blowing agent to provide simultaneously reaction of said mixture (A) and polyisocyanate (B) and formation of cells in the polyurethane reaction product.

3. A polyurethane comprising the reaction product of claim 2.

4. A method in accordance with claim 1 wherein said film-forming polymer is a polymer of an ethylenically unsaturated monomer containing an organic, nitrogen-containing radical in whih all of the nitrogen bonds are satisfied by bonds with at least one member selected from the group consisting of carbon and hydrogen.

5. A method in accordance with claim 4 in which said organic nitrogen-containing radical is an amino radical.

6. A polyurethane comprising the reaction product of claim 4.

7. A method in accordance with claim 4 for the production of a cellular polyurethane in which mixture (A) and polyisocyanate (B) are reacted while in intimate admixture with a blowing agent to provide simultaneously reaction of said mixture (A) and polyisocyanate (B) and formation of cells in the polyurethane reaction product.

8. A method in accordance with claim 7 in which the polymer concentration in reactive polymer-polyol mixture (A) is at least 10% by weight of said mixture.

9. A polyurethane comprising the reaction product of claim 7.

10. A polyurethane comprising the reaction product of claim 1.

11. A method in accordance with claim 1 in which the polymer concentration in reactive polymer-polyol mixture (A) is at least 10% by weight of said mixture.

12. A method in accordance with claim 1 comprising the additional step of diluting without substantial precipitation the reactive mixture (A) with additional reactants for the organic polyisocyanate prior to reaction with (B).

13. A method as defined in claim 1 wherein said film-forming polymer is a homopolymer resulting from the polymerization of an ethylenically unsaturated monomer containing at least one radical reactive with the

14. A method as defined in claim 13 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.

15. 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 said isocyanate.

16. A method as defined in claim 15 wherein said ethylenically unsaturated monomer which contains at least one radical reactive with the --N=C=O radical of said 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.

17. A method as defined in claim 15 wherein one of said ethylenically unsaturated monomers is selected from the group consisting of styrenes, butadienes, acrylic esters and vinyl esters.

18. A method in accordance with claim 1 in which a plasticizer for said film-forming polymer is added to the reactive mixture prior to reaction of said reactive mixture with the organic polyisocyanate.

19. A method in accordance with claim 18 in which said plasticizer contains at least one radical reactive with the isocyanato group.

22. A polyurethane which comprises the reaction product of (i) the in situ polymerizate of a mixture of styrene and acrylic acid in a polypropyleneoxy glycol, and (ii) an organic polyisocyanate. .Iadd.23. A method for preparing cellular polyurethanes comprising reacting

(A) a liquid, stable reactive polymer-polyol mixture having a viscosity of less than about 40,000 cps. at 10% polymer concentration and having a combining weight in a range yielding elastic-to-rigid polyurethane products, the essential components of said reactive mixture consisting of

(1) a substantial but minor amount of film-forming polymer having a molecular weight of at least 5,000 and having a plurality of radicals containing active hydrogen atoms which are reactive with the --N=C=O radicals of an organic polyisocyanate, and

(2) a major amount of a solvent medium for said polymer consisting essentially of at least one normally liquid polyol essentially free from ethylenic unsaturation and having a molecular weight of at least about 500, said polymer (1) being the polymerizate obtained by polymerizing, to a molecular weight of at least 5,000 and to a solids concentration of about 10% to about 50% by weight, an ethylenically unsaturated monomer in such polyol, with

(B) an organic polyisocyanate to form such polyurethane, the ratio of the --N=C=O equivalents of (B) to the equivalents of reactive radicals of (A) being in the range of about 1-5 to 1, wherein mixture (A) and polyisocyanate (B) are reacted while in intimate admixture with a blowing agent to provide simultaneously reaction of said mixture (A) and polyisocyanate (B) and formation of cells in the polyurethane reaction product. .Iaddend. .Iadd.24. A polyurethane comprising the reaction product of claim 23. .Iaddend..Iadd.25. A method for preparing polyurethanes comprising reacting

(A) a liquid, stable reactive polymer-polyol mixture having a viscosity of less than about 40,000 cps. at 10% polymer concentration and having a combining weight in a range yielding elastic-to-rigid polyurethane products, the essential components of said reactive mixture consisting of

(1) a substantial but minor amount of film-forming polymer having a molecular weight of at least 5,000 and having a plurality of radicals containing active hydrogen atoms which are reactive with the --N=C=O radicals of an organic polyisocyanate, said film-forming polymer is a polymer of an ethylenically unsaturated monomer containing 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, and

(2) a major amount of a solvent medium for said polymer consisting essentially of at least one normally liquid polyol essentially free from ethylenic unsaturation and having a molecular weight of at least about 500, said polymer (1) being the polymerizate obtained by polymerizing, to a molecular weight of at least 5,000 and to a solids concentration of about 10% to about 50% by weight, an ethylenically unsaturated monomer in such polyol, with

(B) an organic polyisocyanate to form such polyurethane, the ratio of the --N=C=O equivalents of (B) to the equivalents of reactive radicals of (A) being in the range of about 1-5 to 1. .Iaddend. .Iadd.26. A method in accordance with claim 25 in which said organic nitrogen-containing radical is an amino radical. .Iaddend..Iadd.27. A polyurethane comprising the reaction product of claim 25. .Iaddend..Iadd.28. A method in accordance with claim 25 for the production of a cellular polyurethane in which mixture (A) and polyisocyanate (B) are reacted while in intimate admixture with a blowing agent to provide simultaneously reaction of said mixture (A) and polyisocyanate (B) and formation of cells in the polyurethane reaction product. .Iaddend..Iadd.29. A method in accordance with claim 28 in which the polymer concentration in reactive polymer-polyol mixture (A) is at least 10% by weight of said mixture. .Iaddend..Iadd.30. A polyurethane comprising the reaction product of claim 28. .Iaddend..Iadd.31. A method in accordance with claim 1 in which the polymer concentration in reactive polymer-polyol mixture (A) is about 20% to 50% by weight of said mixture. .Iaddend..Iadd.32. A method in accordance with claim 1 in which the polyol is a polyoxypropylene polyol. .Iaddend..Iadd.33. A method in accordance with claim 1 in which the polyol is a polyoxypropylene glycol. .Iaddend..Iadd.34. A method in accordance with claim 1 in which the polyol is a polyoxypropylene triol. .Iaddend. .Iadd.35. A method in accordance with claim 1 in which the polymer has a molecular weight of 10,000 or greater. .Iaddend. .Iadd.36. A method in accordance with claim 1 in which the polymer in the reactive polymer-polyol mixture (A) is dispersed in the polyol of said mixture to form a stable dispersion. .Iaddend..Iadd.37. A method in accordance with claim 1 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.38. A method for preparing cellular, elastic polyurethanes having improved load-bearing properties comprising reacting

(A) a liquid, stable reactive polymer-polyol mixture convertible to an elastic polyurethane product having a viscosity of less than about 40,000 cps. at 10% polymer concentration and having a combining weight in a range yielding elastic polyurethane products, the essential components of said reactive mixture consisting of

(1) a substantial but minor amount of film-forming polymer having a molecular weight of at least 10,000 and having a plurality of radicals containing active hydrogen atoms which are reactive with the --N=C=O radicals of an organic polyisocyanate, and

(2) a major amount of a solvent medium for said polymer consisting essentially of at least one normally liquid polyoxypropylene polyol essentially free from ethylenic unsaturation and having a molecular weight of at least about 1000, said polymer (1) being the polymerizate obtained by polymerizing, to a molecular weight of at least 10,000 and to a solids concentration of about 10% to about 50% by weight, an ethylenically polyol (2) to form a dispersion with

(B) an organic polyisocyanate to form such polyurethane, the ratio of the --N=C=O equivalents of (B) to the equivalents of reactive radicals of (A) being in the range of about 1-5 to 1, wherein mixture (A) and polyisocyanate (B) are reacted while in intimate admixture with a blowing agent to provide simultaneously reaction of said mixture (A) and polyisocyanate (B) and formation of cells in the polyurethane reaction product. .Iaddend..Iadd.39. A method as claimed in claim 38 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.40. A method as claimed in claim 29 in which the polymer concentration in the polymer-polyol mixture (A) is about 20% to 50% by weight of said mixture. .Iaddend..Iadd.41. A method in accordance with claim 38 wherein said film former is made from an ethylenically unsaturated monomer containing 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. .Iaddend..Iadd.42. A method in accordance with claim 1 in which the polyol in the reactive polymer-polyol mixture (A) has a molecular weight of at least about 2,000. .Iaddend.

20. A polyurethane which comprises the reaction product of (i) the in situ polymerizate of a mixture of styrene and ethylhexyl acrylate in a polypropyleneoxy glycol, and (ii) an organic polyisocyanate.

21. A polyurethane which comprises the reaction product of (i) the in situ polymerizate of acrylic acid in a polypropylenoxy glycol, and (ii) an organic polyisocyanate.