Vinyl ether terminated urethane resins

Abstract

Vinyl ether terminated urethane resins may be prepared by reacting the product obtained by the addition of acetylene to an organic polyol with an isocyanate-containing compound at temperatures ranging from about ambient to about 125° C. The thus prepared resin may then be cured by irradiation from an electron beam, thermally or by exposure to an ultraviolet light to cure the resin and form a coating material.

We claim as our invention: .[.1. A vinyl ether terminated urethane resin having the generic formula:.]. .[. ##STR7## .]..[.in which R and R' are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cycloalkyl and alkyl oxide 
     
        radicals and n is an integer of from 1 to 4..]. .[.2.  The vinyl ether terminated urethane resin as set forth in claim 1 in which said resin possesses a molecular weight in the range of from about 240 to about 10,000..]. .[.3. The vinyl ether terminated urethane resin as set forth in claim 1 in which R is methylene and R' is tolyl..]. .[.4. The vinyl ether terminated urethane resin as set forth in claim 1 in which R is ethylene and R' is tolyl..]. .[.5. The vinyl ether terminated urethane resin as set forth in claim 1 in which R is ethylene and R' is diphenyl-methylene..]. .[.6. The vinyl ether terminated urethane resin as set forth in claim 1 in which R is n-hexylene and R' is dicyclohexylmethylene..]. .[.7. The vinyl ether terminated urethane resin as set forth in claim 1 in which R is 
     
     
        n-butylene and R' is tolyl..]. 8. A process for the preparation of a vinyl ether terminated urethane resin which comprises reacting the .[.product obtained by.]. .Iadd.mixture resulting from .Iaddend.the addition of acetylene to an organic polyol with an isocyanate-containing compound at reaction conditions, and recovering the resultant vinyl ether terminated 
     
     
        urethane resin. 9. The process as set forth in claim 8 in which said reaction conditions include a temperature in the range of from about 
     
     
        ambient to about 125° C. and about atmospheric pressure. 10. The process as set forth in claim 8 in which said reaction is effected in the 
     
     
        presence of a tin-containing catalyst. 11. The process as set forth in claim 10 in which said tin-containing catalyst is dibutyltin dilaurate. 
     
     
            The process as set forth in claim 8 in which said organic polyol comprises triethylene glycol and said isocyanate containing compound comprises 2,4-toluene diisocyanate or a mixture of 2,4- and 2,6-toluene 
     
     
        diisocyanate. 13. The process as set forth in claim 8 in which said organic polyol comprises triethylene glycol and said isocyanate compound 
     
     
        is diphenylmethane diisocyanate. 14. The process as set forth in claim 8 in which said organic polyol comprises triethylene glycol and said 
     
     
        isocyanate compound is dicyclohexylmethane diisocyanate. 15. The process as set forth in claim 8 in which said organic polyol comprises diethylene glycol and said isocyanate compound is 2,4-toluene diisocyanate or a 
     
     
        mixture of 2,4- and 2,6-toluene diisocyanate. 16. The process as set forth in claim 8 in which said organic polyol comprises 1,6-hexanediol and said isocyanate compound is dicyclohexylmethane diisocyanate. .[.17. A polymeric material that results from curing a vinyl ether terminated resin having the generic formula:.]. .[. ##STR8## .]..[.in which R and R' are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cycloalkyl and alkyl oxide radicals and n is an integer of from 1 to 4 which has been cured by a 
     
     
        curing treatment at curing conditions..]. .[.18.  The polymeric material as set forth in claim 17 in which said curing treatment comprises an irradiation of said resin from an electron beam..]. .[.19. The polymeric material as set forth in claim 18 in which the energy dosage from said electron beam is in a range of from about 0.1 to about 10.0 Mrads..]. .[.20. The polymeric material as set forth in claim 18 in which said irradiation is effected in the presence of an onium salt..]. .[.21. The polymeric material as set forth in claim 17 in which said curing treatment comprises exposure to an ultraviolet light source..]. .[.22. The polymeric material as set forth in claim 21 in which said exposure to said ultraviolet light source is effected in the presence of an aryl-onium salt..]. .[.23. The polymeric material as set forth in claim 17 in which said curing is effected by thermal treatment at an elevated temperature in the presence of an or acid organic an onium salt..]. .[.24. The polymeric material as set forth in claim 17 in which R is methylene and R' is tolyl..]. .[.25. The polymeric material as set forth in claim 17 in which R is ethylene and R' is tolyl..]. .[.26. The polymeric material as set forth in claim 17 in which R is ethylene and R' is diphenyl methyl..]. .[.27. The polymeric material as set forth in claim 17 in which R is n-hexylene and R' is dicyclohexylmethyl..]. .[.28. The polymeric material as set forth in claim 17 in which R is n-butylene and R' is tolyl..]. .[.29. A method for obtaining a tack-free coating which comprises subjecting a vinyl ether terminated urethane resin having the generic formula:.]..[. ##STR9## .]..[.in which R and R' are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cycloalkyl and alkyl oxide radicals and n is an integer of from 1 to 4 to a curing treatment at curing conditions, and recovering the resultant tack-free coating..]. 
     
     
        .[.  .  The method as set forth in claim 29 in which said curing treatment comprises irradiation of said resin from an electron beam in which the energy dosage from said electron beam is in a range of from about 0.1 to about 10.0 Mrads in the presence of an onium salt..]. .[.31. The method as set forth in claim 29 in which said curing treatment comprises exposure to an ultraviolet light source in the presence of an aryl-onium salt..]. .[.32. The method as set forth in claim 29 in which said curing treatment is effected by a thermal treatment at an elevated temperature in the presence of an organic acid or an onium salt..]. .[.33. The vinyl ether terminated resin of claim 1 in which R is 1,4-cyclohexane dimethanol..]. .[.34. The process of claim 8 in which said organic polyol comprises 1,4-cyclohexane dimethanol..]. .[.35. The polymeric material of claim 17 
     
     
        in which R is 1,4-cyclohexane dimethanol..]. .Iadd.36.  A polymer resulting from the reaction of (a) a hydroxy mono vinyl ether;   (b) a diisocyanate;   (c) an organic polyol in the presence of a solvent under suitable reaction   
     
     
        conditions. .Iaddend. .Iadd.37.  The polymer of claim 36 where the solvent is a divinyl ether. .Iaddend. .Iadd.38. The polymer of claim 36 wherein said hydroxy mono vinyl ether of (a) is the product of the reaction of acetylene with at least one polyol selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylol propane, pentaerythritol, 1,4-cyclohexane dimethanol, tris(2-hydroxyethyl) trimethylol propane, 1,4-bis(2-hydroxyethyl) phenylether, 1,2-bis(2-hydroxyethyl) phenyl ether, 1,3-bis(2-hydroxyethyl) phenylether, and bis(2-hydroxyethyl) bisphenol-A. .Iaddend. .Iadd.39. The polymer of claim 36 wherein said diisocyanate of (b) is at least one member of the group consisting of 2,4-toluene diisocyanate, mixtures of 2,4 and 2,6-toluene diisocyanate, diphenylmethane diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenyl propane diisocyanate, and dicyclohexylmethane diisocyanate. .Iaddend. .Iadd.40. The polymer of claim 36 wherein the polyol of (c) is the same as the polyol reacted with acetylene to prepare the hydroxy mono vinyl ether of (a). .Iaddend. .Iadd.41. The polymer of claim 36 wherein said polyol of (c) is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylol propane, pentaerythritol, 1,4-cyclohexane dimethanol, tris(2-hydroxyethyl) trimethylol propane, 1,4-bis(2-hydroxyethyl) phenylether, 1,2-bis(2-hydroxyethyl) phenyl ether, 1,3-bis(2-hydroxyethyl) phenylether, and bis(2-hydroxyethyl) bisphenol-A. 
     
     
        .Iaddend. .Iadd.42.  The polymer of claim 37 wherein the hydroxy monovinyl ether, polyol, and divinyl ether are the products of the reaction of acetylene with an excess of said polyol. .Iaddend. .Iadd.43. The polymeric material that results from curing the polymer of claim 36. .Iaddend. .Iadd.44. The polymeric material of claim 43 cured by irradiation with an electron beam. .Iaddend. .Iadd.45. The polymeric material of claim 44 wherein the energy dosage of said electron beam is in the range of from about 0.1 to about 10.0M rads. .Iaddend. .Iadd.46. The polymeric material of claim 44 cured in the presence of an effective onium salt. .Iaddend. .Iadd.47. The polymeric material of claim 43 cured by exposure to an ultraviolet light source. .Iaddend. .Iadd.48. The polymeric material claim 47 cured in the presence of an effective aryl-onium salt. .Iaddend. .Iadd.49. The polymeric material of claim 43 cured by thermal treatment at an elevated temperature in the presence of an effective organic acid or an onium salt. .Iaddend. .Iadd.50. The polymeric material of claim 36 where said polyol is triethylene glycol and said diisocyanate is 2,4 toluene diisocyanate. .Iaddend. .Iadd.51. The polymeric material of claim 36 where said polyol is triethylene glycol and diisocyanate is a 2,4 toluene diisocyanate ester prepolymer. .Iaddend. .Iadd.52. The polymeric material of claim 36 where said polyol is triethylene glycol and said diisocyanate 
     
     
        is diphenylmethyl diisocyanate. .Iaddend. .Iadd.53.  A method of obtaining tack-free coating which comprises subjecting the polymer of claim 36 curing conditions and recovering the resultant tack-free coating. .Iaddend. .Iadd.54. The method of claim 53 wherein said curing conditions comprise irradiation of said polymer with an electron beam in which the energy dosage is in the range of from about 0.1 to about 10M rads in the presence of an effective onium salt. .Iaddend. .Iadd.55. The method of claim 53 wherein said curing conditions comprise exposure to an ultraviolet light source in the presence of an effective aryl-onium salt. .Iaddend. .Iadd.56. The method of claim 53 wherein said curing conditions comprise thermal treatment at an elevated temperature in the presence of an effective organic acid or an onium salt. .Iaddend. .Iadd.57. The polymer of claim 36 wherein the mol ratio of hydroxy and isocyanate moieties- is within the range of about 0.8:1 to about 1.2:1. .Iaddend. .Iadd.58. The polymer of claim 36 wherein the mol ratio of hydroxy moieties from the hydroxy mono vinyl ether of (a) to the hydroxy moieties from the polyol of (c) is within the range of about 2:3 to about 1:1. .Iaddend.