Patent GB-990427-A (GB)
Title: Improvements in and relating to polymers
IPC: C08F236/04
Filed: 1962-05-16
Abstract: An oxirane-containing condensation product is prepared by condensing an aliphatic conjugated diene with a polyalkyl-substituted aromatic compound, the diene being present in at least a two molar excess over the aromatic compound in the presence of a catalyst for the reaction, and the product epoxidized to at least one per cent of oxirane oxygen. Heterocyclic aromatic compounds are included in the term "aromatic compounds."  Specified dienes are butadiene, isoprene, 2-3-dimethyl butadiene, cyclopentadiene, methyl cyclopentadiene, cyclohexadiene and cyclooctadienes while xylene, mesitylene, tetralin, diethylbenzene, o-,m-and p-cymene, polymethyl naphthalenes, durene, butidine and dimethylpyrrole are specified polyalkyl substituted compounds. Specified catalysts are finely-divided alkali metals, their mixtures and alloys as well as alkaline metal hydrides. The condensation reaction may take place at 75 DEG  to 200 DEG  C., the epoxidizing agent may be a peracid, a per salt or a peroxide or hydroperoxide and the peracid may be formed in situ.  Specified epoxidizing agents are performic, peracetic, perpropionic and perbutyric acids.  The oxirane-containing condensation product may be reacted with a curing agent e.g. polycaboxylic acids or anhydrides, polycarboxy polyesters, polyhydric phenols with or without such materials as hexamethylene tetramine, primary or secondary amines, urea-formaldehyde and substituted urea-formaldehyde resins, Lewis acids both free and complexes, and polymercaptans while polymerizable vinyl and allyl monomers may also be present.  In examples (1) a mixture of m-xylene, benzene and a sodium dispersion in benzene is heated with butadiene in an autoclave and the product epoxidized with hydrogen peroxide (3) and (13) a mixture of benzene, sodium and commercial mixed xylenes is heated with butadiene in an autoclave and the product epoxidized with hydrogen peroxide (9) an oil prepared by copolymerizing butadiene with p-xylene is epoxidized with hydrogen peroxide (11) a mixture of m-xylene, benzene and sodium in kerosene is heated in an autoclave with isoprene and the product epoxidized with hydrogen peroxide (17) a mixture of o-xylene, benzene and sodium dispersed in benzene is heated in an autoclave with butadiene and epoxidized with hydrogen peroxide (19) one mol. of mesitylene and four mols. butadiene are copolymerized and epoxidized with hydrogen peroxide (21) 6 mols. butadiene and one mol. durene are polymerized and then epoxidized with peracetic acid and sodium acetate (23) 20 parts butadiene and 10 parts of 2,4-butidine are copolymerized and then epoxidized with hydrogen peroxide (25) a mixture of dimethylnaphthalene, benzene and sodium dispersed in benzene is heated in an autoclave with butadiene and then epoxidized with hydrogen peroxide and (31) a mixture of m-xylene, benzene and lithium dispersed in iso-octane is heated with butadiene and then epoxidized with peracetic acid.ALSO:An oxirane-containing condensation product is prepared by condensing an aliphatic conjugated diene with a polyalkyl-substituted aromatic compound, the diene being present in at least a two-molar excess over the aromatic compound in the presence of a catalyst for the reaction and the product epoxidized to at least one per cent of oxirane oxygen.  Heterocyclic aromatic compounds are included in the term "aromatic compounds." Specified dienes are butadiene, isoprene, 2,3-dimethyl butadiene, cyclopentadiene, methyl cyclopentadiene, cyclohexadiene and cyclo-octadienes while xylene, mesitylene, tetralin, diethylbenzene, o-, m- and p-cymene, polymethylnaphthalenes, durene, butidine and dimethylpyrrole are specified polyalkyl-substituted compounds. Specified catalysts are finely-divided alkali metals, their mixtures and alloys as well as alkaline metal hydrides.  The condensation reaction may take place at 75 DEG  to 200 DEG  C., the epoxidizing agent may be a peracid, a per salt or a peroxide or hydroperoxide and the peracid may be formed in situ.  Specified epoxidizing agents are performic, peracetic, perpropionic and perbutyric acids.  The oxirane-containing product may be reacted with a curing agent, e.g. polycarboxylic acids or anhydrides, polycarboxypolyesters, polyhydric phenols with or without such materials as hexamethylene tetramine, primary or secondary amines, urea-formaldehyde and substituted urea-formaldehyde resins, lewis acids both free and complexes, and polymercaptans while polymerizable vinyl and allyl monomers, e.g. styrene, alpha-methyl styrene, vinyl toluene, divinyl benzene, dicyclopentadiene, methyl methacrylate, acrylonitrile, triallylphosphate, diallyl phthalate, and dimethallyl maleate.