Handleable, thermosettable epoxide-polyanhydride compositions

Claim 1

A method of forming a handleable, thermosettable composition which comprises forming a homogeneous liquid resin mixture substantially free of active hydrogen comprising (a) about five to about 80 weight percent based on the total resin components of an olefinically unsaturated monomer consisting of (1) one or more alkenes having from about 6 to about 18 carbon atoms and halogen derivatives thereof, and (2) up to 90 mol percent of styrene, ring-substituted chloro-, bromo or lower alkylstyrenes, lower alkylacrylates, lower alkylmethacrylates, vinyl acetate, acrylonitrile, vinyl chloride, vinyl bromide or vinylidene chloride; (b) an anhydride component consisting of (1) an olefinically unsaturated monoanhydride selected from maleic anhydride, chloromaleic anhydride, methylmaleic anhydride, ethylmaleic anhydride, dichloromaleic anhydride, dimethylmaleic anhydride, n-butylmaleic anhydride, phenylmaleic anhydride, diphenylmaleic anhydride, chloromethylmaleic anhydride, bromophenylmaleic anhydride and itaconic anhydride, the molar ratio of the olefinically unsaturated monomer (a) to the olefinically unsaturated monoanhydride (b) (1) being about 1:1; (2) a saturated polyanhydride comprising the copolymer having between two and about 500 repeating units and prepared from one to 10 mols of said olefinically unsaturated monomer (a) (2) per mol of said unsaturated monoanhydride (b) (1) or prepared from equimolar amounts of said unsaturated monoanhydride (b) (1) and one or more two to 20 carbon 1-alkenes or halogen-substituted 1-alkenes; and (3) a saturated monoanhydride selected from phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, chlorendic anhydride, and a mixture of methyl bicyclo(2.2.1)heptane-2,3-dicarboxylic anhydride isomers; (4) the ratio of the anhydride equivalents of said olefinically unsaturated monoanhydride (b) (1) to the sum of the total anhydride equivalents in the resin solution being from about 0.2:1 to about 1:1 and the ratio of anhydride equivalents in said saturated polyanhydride (b) (2) to the anhydride equivalents in said saturated monoanhydride (b) (3) being at least about 1:1; (c) an epoxy component substantially free of active hydrogen selected from (1) a saturated monoepoxy compound having between three and about 20 carbon atoms, or (2) an epoxy resin having a 1,2-epoxy equivalent value greater than one which is soluble in the resin solution or is capable of forming a homogeneous dispersion in the resin solution, or a mixture of said saturated monoepoxy compound and said epoxy resin, (3) said epoxy component having an A/E ratio of total anhydride equivalents to total epoxy equivalents in the resin solution of about 0.1:1 to about 2.5:1; and (d) from about 0.01 to about 10 weight percent of an anhydride accelerator which is substantially inactive during the copolymerization reaction of said olefinically unsaturated monomer (a) and said anhydride component (b); and copolymerizing said olefinically unsaturated monomer (a) with said anhydride component (b) by free radical means at a temperature up to about 150° C. without substantial reaction of the anhydride groups with the epoxide groups present in the resin mixture whereby a handleable, thermosettable composition comprising a homogeneous mixture of polyanhydride molecules, epoxide molecules and anhydride accelerator is obtained.

Claim 2

A method of forming a handleable, thermosettable composition which comprises forming a homogeneous liquid resin mixture substantially free of active hydrogen comprising (a) about five to about 80 weight percent based on the total resin components of an olefinically unsaturated monomer consisting of (1) one or more alkenes having from about 6 to about 18 carbon atoms and halogen derivatives thereof, and (2) up to 90 mol percent of styrene, ring-substituted chloro-, bromo or lower alkylstyrenes, lower alkylacrylates, lower alkylmethacrylates, vinyl acetate, acrylonitrile, vinyl chloride, vinyl bromide or vinylidene chloride; (b) an anhydride component consisting of (1) an olefinically unsaturated monoanhydride selected from maleic anhydride, chloromaleic anhydride, methylmaleic anhydride, ethylmaleic anhydride, dichloromaleic anhydride, dimethylmaleic anhydride, n-butylmaleic anhydride, phenylmaleic anhydride, diphenylmaleic anhydride, chloromethylmaleic anhydride, bromophenylmaleic anhydride and itaconic anhydride, the molar ratio of the olefinically unsaturated monomer (a) to the olefinically unsaturated monoanhydride (b) (1) being about 1:1; (2) a saturated polyanhydride comprising the copolymer having between two and about 500 repeating units and prepared from one to 10 mols of said olefinically unsaturated monomer (a) (2) per mol of said unsaturated monoanhydride (b) (1) or prepared from equimolar amounts of said unsaturated monoanhydride (b) (1) and one or more two to 20 carbon 1-alkenes or halogen-substituted 1-alkenes; and (3) a saturated monoanhydride selected from phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, chlorendic anhydride, and a mixture of methyl bicyclo(2.2.1)heptane-2,3-dicarboxylic anhydride isomers; (4) the ratio of the anhydride equivalents of said olefinically unsaturated monoanhydride (b) (1) to the sum of the total anhydride equivalents in the resin solution being from about 0.2:1 to about 1:1 and the ratio of anhydride equivalents in said saturated polyanhydride (b) (2) to the anhydride equivalents in said saturated monoanhydride (b) (3) being at least about 1:1; (c) an epoxy component substantially free of active hydrogen selected from (1) a saturated monoepoxy compound having between three and about 20 carbon atoms, or (2) an epoxy resin having a 1,2-epoxy equivalent value greater than one which is soluble in the resin solution or is capable of forming a homogeneous dispersion in the resin solution, or a mixture of said saturated monoepoxy compound and said epoxy resin, (3) said epoxy component having an A/E ratio of total anhydride equivalents to total epoxy equivalents in the resin solution of about 0.1:1 to about 2.5:1; and (d) from about 0.01 to about 10 weight percent of an anhydride accelerator which is substantially inactive during the copolymerization reaction of said olefinically unsaturated monomer (a) and said anhydride component (b); and copolymerizing said olefinically unsaturated monomer (a) with said anhydride component (b) by free radical means at a temperature up to about 150° C. without substantial reaction of the anhydride groups with the epoxide groups present in the resin mixture whereby a handleable, thermosettable composition comprising a homogeneous mixture of polyanhydride molecules, epoxide molecules and anhydride accelerator is obtained.