Process for the preparation of graft copolymers

Abstract

Process for the preparation of thermoplastic graft copolymers which comprises heating for about 15 seconds to 60 minutes, with mixing, a trunk copolymer of at least two monomers, at least one of said monomers providing amine-reactive sites taken from the group consisting of the anhydride group, e.g., maleic anhydride; a vicinal pair of carboxylic groups and a carboxylic acid adjacent to an alkoxycarbonyl group, wherein the alkoxy group contains up to 20 carbon atoms, and at least one of said monomers containing no amine-reactive sites, and at least one side chain polymer having per chain one active amine site taken from the group consisting of primary and secondary amines, the remainder of said side chain polymer being substantially unreactive with the reactive sites, e.g., amino-substituted polycaprolactam, polylaurolactam, polyethylene oxide, etc., of the trunk copolymer. The process provides control of the type and length of the side chain polymer grafted onto the trunk copolymer. Plastic graft copolymers are included, specifically those containing one or more side chain polymer types with the priviso that when only one type side chain polymer is present the side chain polymer contains only one nitrogen atom, said atom being found in the active amine site.

We claim: .[.1. Process for the preparation of thermoplastic graft copolymers which comprises heating for about 15 seconds to 60 minutes, with mixing, (1) a trunk copolymer of at least two monomers, at least one of said monomers providing amine-reactive sites taken from the group consisting of an anhydride group, a vicinal pair of carboxylic groups and a carboxylic group adjacent to an alkoxycarbonyl group, wherein the alkoxy group contains up to 20 carbon atoms, and at least one of said monomers containing no aminereactive sites, and (2) at least one side chain polymer ranging in length from about 25 to 1000 chain atoms, having per chain one active amine site taken from the group consisting of primary and secondary amines, the remainder of said side chain polymer being substantially unreactive with the reactive sites of the trunk copolymer..]. .[.2. A process according to claim 1 wherein the active amine site of the side 
     
        chain polymer is a primary amine..]. 3. A process according to claim .[.1.]. .Iadd.68 .Iaddend.wherein the process is conducted in the melt. 
     
     
           A process according to claim .[.1.]. .Iadd.68 .Iaddend.wherein the 
     
     
        process is conducted in solution. 5. A process according to claim .[.1.]. .Iadd.68 .Iaddend.wherein the heating temperature is above the melting 
     
     
        points of the trunk copolymer and side chain polymer. 6. A process according to claim .[.1.]. .Iadd.68 .Iaddend.wherein the heating is 
     
     
        conducted for about 15 seconds to 10 minutes. 7. A process according to claim .[.1.]. .Iadd.68 .Iaddend.wherein the trunk copolymer is derived from an α-olefin and at least one monomer providing amine-reactive sites taken from the group consisting of an anhydride, diacid and 
     
     
        half-esters derived therefrom. 8. A process according to claim 7 wherein 
     
     
        the α-olefin is ethylene. 9. A process according to claim 8 wherein there is present at least one additional polymerizable monomer which 
     
     
        contains no amine-reactive sites and no anhydride reactive sites. 10. A process according to claim 9 wherein the additional polymerizable monomer 
     
     
        is 3-methylbutene. 11. A process according to claim 9 wherein the 
     
     
        additional polymerizable monomer is vinyl acetate. 12. A process according to claim 9 wherein the additional polymerizable monomer is methyl 
     
     
        acrylate. 13. A process according to claim 9 wherein the additional polymerizable monomer is methyl methacrylate. .[.14. A process according to claim 1 wherein the trunk copolymer is derived from styrene and at least one monomer providing amine-reactive sites taken from the group consisting of an anhydride, diacid and half-esters derived therefrom..]. .[.15. A process according to claim 14 wherein there is present at least one additional polymerizable monomer containing no amine-reactive sites 
     
     
        and no anhydride reactive sites..]. 16. A process according to claim 7 wherein the monomer providing amine-reactive sites is maleic anhydride wherein the maleic anhydride is present in an amount of 1.0 to 25.0 parts 
     
     
        by weight. 17. A process according to claim .[.14.]. .Iadd.68 .Iaddend.wherein the monomer providing amine-reactive sites is maleic anhydride wherein the maleic anhydride is present in an amount of 1.0 to 
     
     
        30.0 parts by weight. 18. A process according to claim 9 wherein the trunk copolymer is composed of ethylene, monoalkyl maleate, whrein alkyl is in the range of 1 to 4 carbon atoms, in addition to an additional 
     
     
        polymerizable monomer. 19. A process according to claim 9 wherein the trunk copolymer is composed of ethylene, monalkyl fumarate wherein alkyl is in the range of 1 to 4 carbon atoms, in addition to an additional 
     
     
        polymerizable monomer. 20. A process according to claim 9 wherein the trunk copolymer is composed of ethylene, monoalkyl itaconate wherein alkyl is in the range of 1 to 4 carbon atoms, in addition to an additional polymerizable monomer. .[.21. A process according to claim 1 wherein the side chain polymer is selected from the group consisting of polymers of lactams containing 3 to 12 carbon atoms, copolymers of lactams containing 3 to 12 carbon atoms, polymers of organic oxides containing 2 to 16 carbon atoms, copolymers of organic oxides containing 2 to 16 carbon atoms, polymers of styrene, polymers of substituted styrenes, copolymers of styrene and substituted styrene, polymers of acrylates, polymers of methacrylates, copolymers of acrylates and methacrylates, and polymers of lactones..]. .[.22. A process according to claim 21 wherein a side chain polymer present is a polycaprolactam..]. .[.23. A process according to claim 21 wherein a side chain polymer present is a polylaurolactam..]. .[.24. A process according to claim 21 wherein a side chain polymer 
     
     
        present is a copolymer of caprolactam and laurolactam..]. 25. A process according to claim .[.21.]. .Iadd.68 .Iaddend.wherein a side chain polymer 
     
     
        present is polyethylene oxide. 26. A process according to claim .[.21.]. .Iadd.68 .Iaddend.wherein a side chain polymer present is polypropylene 
     
     
        oxide. 27. A process according to claim .[.21.]. .Iadd.68 .Iaddend.wherein 
     
     
        a side chain polymer present is polystyrene. 28. A process according to claim .[.21.]. .Iadd.70 .Iaddend.wherein the side chain polymers are short chains having repeat units from about 5 to 50 in which at least 80 percent of the side chain polymers have one active amine site and the remainder of said side chain polymer is substantially unreactive with the 
     
     
        amine-reactive sites on the trunk copolymer. 29. A process according to claim 28 wherein the side chain polymers contain substituent alkyl groups 
     
     
        of 1 to 18 carbon atoms. 30. A process according to claim .[.28.]. .Iadd.68 .Iaddend.wherein the side chain polymers contain substituent aryl 
     
     
        groups. 31. A process according to claim .[.1.]. .Iadd.68 .Iaddend.wherein the trunk copolymers contain, on the average, about 300 to 50,000 chain atoms and the number of reactive sites occur, on the average, at a frequency of 1 to 50 sites per thousand chain atoms of the main chain. 
     
     
            A process according to claim .[.31.]. .Iadd.68 .Iaddend.wherein trunk copolymers contain, on the average, about 500 to 2,000 chain atoms of the 
     
     
        main chain. 33. A process according to claim .[.31.]. .Iadd.68 .Iaddend.wherein the side chain polymer reactive with the amine-reactive sites on the trunk copolymer range in length from 25 to 1,000 chain atoms. .[.34. A thermoplastic graft copolymer consisting essentially of a trunk copolymer derived from at least two monomers, at least one of said monomers providing amine-reactive sites selected from the group consisting of an anhydride group, a vicinal pair of carboxylic groups and a carboxylic group adjacent to an alkoxycarbonyl group, wherein the alkoxy group contains up to 20 carbon atoms, and at least one of said monomers containing no amine-reactive sites; and at least one type side chain polymer linked to said reactive sites through amide or imide linkages, said side chain polymer being derived from a short chain polymer having from about 5 to 50 repeat units and containing one active amine site selected from the group consisting of primary and secondary amines, the remainder of the side chain polymer being substantially unreactive with the amine-reactive sites of the trunk copolymer with the proviso that when only one type of side chain polymer is present the side chain polymer contains only one nitrogen atom, said atom being found in the active amine site..]. .[.35. A graft copolymer according to claim 34 wherein the trunk copolymer and side chain polymers are linked through imide linkages..]. 
     
     
            A graft copolymer according to claim .[.34.]. .Iadd.69 .Iaddend.wherein solely one type of side chain polymer is linked to the trunk copolymer, said side chain polymer being selected from the group consisting of polymers of organic oxides containing 2 to 16 carbon atoms, copolymers of organic oxides containing 2 to 16 carbon atoms, polymers of styrene, polymers of substituted styrenes, copolymers of styrene and substituted styrene, polymers of acrylates, polymers of methacrylates, 
     
     
        copolymers of acrylates and methacrylates, and polymers of lactones. 37. A graft copolymer according to claim 36 wherein the side chain polymer is 
     
     
        polyethylene oxide. 38. A graft copolymer according to claim 36 wherein 
     
     
        the side chain polymer is polypropylene oxide. 39. A graft copolymer according to claim 36 wherein the side chain polymer is a 
     
     
        polymethacrylate. 40. A graft copolymer according to claim 36 wherein the 
     
     
        side chain polymer is a polyacrylate. 41. A graft copolymer according to 
     
     
        claim 36 wherein the side chain polymer is polystyrene. 42. A graft copolymer according to claim .[.34.]. .Iadd.69 .Iaddend.wherein at least two different type side chain polymers are present. .[.43. A graft copolymer according to claim 42 wherein the side chain polymers are selected from the group consisting of polymers of lactams containing 3 to 12 carbon atoms, copolymers of lactams containing 3 to 12 carbon atoms, polymers of organic oxides containing 2 to 16 carbon atoms, copolymers of organic oxides containing 2 to 16 carbon atoms, polymers of styrene, polymers of substituted styrenes, copolymers of styrene and substituted styrene, polymers of acrylates, polymers of methacrylates, copolymers of 
     
     
        acrylates and methacrylates, and polymers of lactones..]. 44. A graft copolymer according to claim .[.43.]. .Iadd.71 .Iaddend.wherein the side 
     
     
        chain polymers are polyethylene oxide and polycaprolactam. 45. A graft copolymer according to claim .[.43.]. .Iadd.69 .Iaddend.wherein the side 
     
     
        chain polymers are polyethylene oxide and polymethyl methacrylate. 46. A graft copolymer according to claim .[.43.]. .Iadd.69 .Iaddend.wherein the 
     
     
        side chain polymers are polystyrene and polyethylene oxide. 47. A graft copolymer according to claim .[.43.]. .Iadd.69 .Iaddend.wherein the side 
     
     
        chain polymers are polystyrene and polymethyl methacrylate. 48. A graft copolymer according to claim .[.34.]. .Iadd.69 .Iaddend.wherein the trunk copolymer is derived from ethylene and at least one monomer providing amine-reactive sites taken from the group consisting of an anhydride, 
     
     
        diacid and half-esters derived therefrom. 49. A graft copolymer according to claim 48 wherein there is present at least one additional polymerizable monomer which contains no amine-reactive sites and no anhydride reactive 
     
     
        sites. 50. A graft copolymer according to claim 48 wherein the side chain 
     
     
        is polyethylene oxide. 51. A graft copolymer according to claim 48 wherein the side chain is a polymer selected from the group consisting of 
     
     
        polyacrylate, polymethacrylate or copolymers thereof. 52. A graft copolymer according to claim 48 wherein the monomer providing amine-reactive sites is maleic anhydride wherein the maleic anhydride is 
     
     
        present in an amount of 1.0 to 25 parts by weight. 53. A graft copolymer according to claim .[.34.]. .Iadd.69 .Iaddend.wherein the trunk copolymer is derived from styrene and at least one monomer providing amine-reactive sites taken from the group consisting of an anhydride, diacid and 
     
     
        half-esters derived therefrom. 54. A graft copolymer according to claim 53 wherein there is present at least one additional polymerizable monomer 
     
     
        containing no amine-reactive sites and no anhydride reactive sites. 55. A graft copolymer according to claim 53 wherein the monomer providing amine-reactive sites is maleic anhydride wherein the maleic anhydride is 
     
     
        present in an amount of 1.0 to 30 parts by weight. 56. A graft copolymer according to claim 49 wherein the trunk copolymer is composed of ethylene, monoalkyl maleate, wherein alkyl is in the range of 1 to 4 carbon atoms, 
     
     
        in addition to an additional polymerizable monomer. 57. A graft copolymer according to claim 49 wherein the trunk copolymer is composed of ethylene, monoalkyl fumarate wherein alkyl is in the range of 1 to 4 carbon atoms, 
     
     
        in addition to an additional polymerizable monomer. 58. A graft copolymer according to claim 49 wherein the trunk copolymer is composed of ethylene, monoalkyl itaconate wherein alkyl is in the range of 1 to 4 carbon atoms, 
     
     
        in addition to an additional polymerizable monomer. 59. A graft copolymer according to claim .[.34.]. .Iadd.69 .Iaddend.wherein the trunk copolymer contains, on a number average, about 300 to 50,000 chain atoms and the number of reactive sites occur, on the average, at a frequency of about 1 to 200 reactive sites per thousand chain atoms of the trunk copolymer, there being on the average at least about one active site per trunk 
     
     
        copolymer chain. 60. A graft copolymer according to claim 59 wherein the trunk copolymer contains, on the average, about 500 to 2,000 chain atoms. 
     
     
         1. A graft copolymer according to claim 59 wherein any side chain polymer reactive with the amine-reactive sites on the trunk copolymer range in length from 25 to 1,000 chain atoms. .[.62. A process according to claim 1 wherein the side chain polymer has an average degree of polymerization of 5 to 60..]. .[.63. A process according to claim 62 wherein the average degree of polymerization of the side chain polymer is 6 to 8..]. .Iadd..[.64. A graft copolymer according to claim 34 wherein the side chain polymer has an average degree of polymerization of 5 to 60..]..Iaddend. .[.65. A graft copolymer according to claim 64 wherein the average degree of polymerization of the side chain polymer is 6 to 8..]. 
     
     
          . A graft copolymer according to claim .[.64.]. .Iadd.70 .Iaddend.wherein the non-reactive end of the side chain polymer has 
     
     
        substituent alkyl groups of 1 to 18 carbon atoms. 67. A graft copolymer according to claim .[.64.]. .Iadd.70 .Iaddend.wherein the non-reactive end of the side chain polymer has substituent aryl groups. .Iadd. 68. Process for the preparation of graft copolymers which comprises heating for about 15 seconds to 60 minutes, with mixing, (1) a trunk copolymer of at least two monomers at least one of said monomers providing amine-reactive sites taken from the group consisting of an anhydride, a vicinal pair of carboxylic groups, and a carboxylic group adjacent to an alkoxycarbonyl group, where the alkoxy group contains up to 20 carbon atoms, and at least one of said monomers contains no amine-reactive sites, and (2) at least one side chain polymer ranging in length from about 25 to 1,000 chain atoms having per chain one active amine site taken from the group consisting of primary and secondary amines, the remainder of said side chain polymer being selected from the group consisting of polymeric organic oxides containing 2 to 16 carbon atoms, copolymers of organic oxides containing 2 to 16 carbon atoms, polymers of styrene, polymers of substituted styrenes, copolymers of styrene and substituted styrene, polymers of acrylates, polymers of methacrylates, copolymers of acrylates and methacrylates, and polymers of lactones. .Iaddend..Iadd. 69. A thermoplastic graft copolymer consisting essentially of a trunk copolymer derived from at least two monomers, at least one of said monomers providing amine-reactive sites selected from the group consisting of an anhydride group, a vicinal pair of carboxylic groups, and a carboxylic group adjacent to an alkoxycarbonyl group, where the alkoxy group contains up to 20 carbon atoms, and at least one of said monomers contains no amine-reactive sites; and at least one type side chain polymer linked to said reactive sites through amide or imide linkages, said side chain polymer being derived from a short chain polymer having about 5 to 50 repeating units and containing one active amine site selected from the group consisting of primary and secondary amines, the remainder of the side chain polymer being selected from the group consisting of polymeric organic oxides containing 2 to 16 carbon atoms, copolymers of organic oxides containing 2 to 16 carbon atoms, polymers of styrene, polymers of substituted styrenes, copolymers of styrene and substituted styrene, polymers of acrylates, polymers of methacrylates, copolymers of acrylates and methacrylates, and polymers of lactones. .Iaddend. .Iadd. 70. Process for the preparation of graft copolymers which comprises heating for about 15 seconds to 60 minutes, with mixing, (1) a trunk copolymer of at least two monomers, at least one of said monomers providing amine-reactive sites taken from the group consisting of an anhydride, a vicinal pair of carboxylic groups, and a carboxylic group adjacent to an alkoxycarbonyl group, where the alkoxy group contains up to 20 carbon atoms, and at least one of said monomers contains no amine-reactive sites, and (2) two types of side chain polymers ranging in length from about 25 to 1000 chain atoms, having per chain one active amine site taken from the group consisting of primary and secondary amines, said polymers being selected from the group consisting of the following pairs: polycarpolactam and polyethylene oxide, polymethyl methacrylate and polyethylene oxide, polystyrene and polyethylene oxide, and polymethyl   
     
     
        methacrylate and polystyrene. .Iaddend..Iadd. 71.  A thermoplastic graft copolymer consisting essentially of (1) a trunk copolymer derived from at least two monomers, at least one of said monomers providing amine-reactive sites, selected from the group consisting of an anhydride group, a vicinal pair of carboxylic groups, and a carboxylic group adjacent to an alkoxycarbonyl group where the alkoxy group contains up to 20 carbon atoms, and at least one of said monomers contains no amine-reactive sites; and (2) two types of side chain polymers linked to said reactive sites through amide or imide linkages, said side chain polymers being derived from a short chain polymer having about 5 to 50 repeating units and containing one active amine site selected from the group consisting of primary and secondary amines, which amines form said amide or imide linkages with the amine-reactive sites of the trunk copolymer, said side chain polymers being selected from the group consisting of the following pairs: polycaprolactam and polyethylene oxide, polymethyl methacrylate and polyethylene oxide, polystyrene and polyethylene oxide, and polymethyl methacrylate and polystyrene. .Iaddend.