Crosslinked polymers made from 1,3,7-octatriene and like conjugated polyenes

A polymeric foam which absorbs aqueous fluids, said polymeric foam comprising a hydrophilic, flexible, nonionic foam structure of interconnected open cells and which is made by polymerizing a water-in-oil emulsion having:

• 1) an oil phase comprising:
• a) from about 65 to about 98% by weight of a monomer component comprising:
• i) from about 30 to about 98% by weight of a polyene having at least 6 carbon atoms and having the formula:
• ##STR10## wherein R.sub.1 are H, halo, amino, cyano, carboxy, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 ester, C.sub.6 -C.sub.12 aryl, C.sub.6 -C.sub.12 heteroaryl, or mixtures thereof;
• R.sub.2 are, H, halo, amino, hydroxy, cyano, carboxy, C.sub.1 -C.sub.16 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 ester, C.sub.6 -C.sub.12 aryl, C.sub.4 -C.sub.12 heteroaryl or C.sub.2 -C.sub.12 alkenyl;
• ii) from about 2 to about 70% by weight of a crosslinking agent having at least 2 activated double bonds;
• iii) up to about 25% by weight other compatible comonomers;
• b) from about 2 to about 35% by weight of an emulsifier component which is soluble in the oil phase and which forms a stable water-in-oil emulsion;
• and
• 2) a water phase comprising from about 0.2 to about 20% by weight of a water-soluble electrolyte,
• 3) a weight ratio of water phase to oil phase of from about 12:1 to about 100:1.

A polymer which made by polymerizing a monomer mixture comprising:

• A. from about 30 to about 98% by weight of a polyene having from 6 to 10 carbon atoms and having the formula:
• ##STR11## wherein R.sub.1 is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkenyl, or C.sub.1 -C.sub.4 alkoxy;
• R.sub.2 is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkenyl or C.sub.1 -C.sub.4 alkoxy;
• B. from about 2 to about 70% by weight of a crosslinking agent having the formula:
• ##STR12## wherein each A is a cleavable linking group;
• R.sub.3 is C.sub.1 -C.sub.12 alkylene, C.sub.2 -C.sub.12 alkenylene, C.sub.6 -C.sub.12 arylene, C.sub.7 -C.sub.18 arylalkylene, C.sub.4 -C.sub.12 heteroarylene, C.sub.6 -C .sub.18 heteroarylalkylene, C.sub.8 -C.sub.18 arylalkenylene, or C.sub.8 -C.sub.18 heteroarylalkenylene;
• R.sub.4 is H, halo, carboxy, C.sub.1 C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 ester, C.sub.6 -C.sub.12 aryl or C.sub.4 -C.sub.12 heteroaryl;
• n is at least 2;
• C. up to about 25% by weight a compatible comonomer selected from the group consisting of chloroprene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, styrene, o-methoxystyrene, p-methoxystyrene, m-methoxystyrene, o-methyl styrene, o-phenyl styrene, vinyl naphthalene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinylidene bromide, acrylic acid, chloroacrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-dimethyl-methacrylamide, acrylonitrile, methacrylonitrile, maleic anhydride, dimethyl maleate, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, methyl vinyl ketone, ethyl vinyl ketone, and isobutyl vinyl ketone;
• butadiene, isoprene, piperylene, cyclopentadiene, norbornadiene, dicyclopentadiene, vinylpyridine, N-vinylcarbazole, N-vinylpyrrolidine, acrolein, vinylferrocene, vinyltitanocene, methyl vinylsulfone, vinylpyridine, 2-vinylbutadiene, and mixtures thereof.

A polymeric foam which absorbs aqueous body fluids, said polymeric foam comprising a hydrophilic, flexible, nonionic foam structure of interconnected open cells and which is made by polymerizing a water-in-oil emulsion having:

• 1) an oil phase comprising:
• a) from about 80 to about 97% by weight of a monomer component comprising:
• i) from about 60 to about 90% by weight of a polyene selected from the group consisting of 1,3-hexadiene, 1,3-octadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-amyl-1,3-butadiene, 7-methyl-3-methylene-1,6-octadiene, 1,3,7-octatriene and mixtures thereof;
• ii) from about 10 to about 40% by weight of a crosslinking agent selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 2-butenediol dimethacrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate and trimethacrylate, and mixtures thereof;
• iii) up to about 20% by weight a compatible comonomer selected from the group consisting of chloroprene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, styrene, o-methoxystyrene, p-methoxystyrene, m-methoxystyrene, o-methyl styrene, o-phenyl styrene, vinyl naphthalene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinylidene bromide, acrylic acid, chloroacrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, acrylonitrile, methacrylonitrile, maleic anhydride, dimethyl maleate, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, methyl vinyl ketone, ethyl vinyl ketone, and isobutyl vinyl ketone;
• butadiene, isoprene, piperylene, cyclopentadiene, norbornadiene, dicyclopentadiene, vinylpyridine, N-vinylcarbazole, N-vinylpyrrolidine, acrolein, vinylferrocene, vinyltitanocene, methyl vinylsulfone, vinylpyridine, 2-vinylbutadiene, and mixtures thereof;
• b) from about 3 to about 25% by weight of an emulsifier component which is soluble in the oil phase and which forms a stable water-in-oil emulsion;
• and
• 2) a water phase comprising from about 0.2 to about 20% by weight of a water-soluble electrolyte;
• 3) a weight ratio of water phase to oil phase of from about 25:1 to about 50:1.

A process for producing a crosslinked polymer comprising polymerizing monomer component comprising from about 30 to about 98% by weight of a polyene having at least 6 carbon atoms and having the formula:

• ##STR13## wherein R.sub.1 are H, halo, amino, cyano, carboxy, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 ester, C.sub.6 -C.sub.12 aryl, C.sub.6 -C.sub.12 heteroaryl, or mixtures thereof;
• R.sub.2 is H, halo, amino, hydroxy, cyano, carboxy, C.sub.1 -C.sub.16 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 ester, C.sub.6 -C.sub.12 aryl, C.sub.4 C.sub.12 heteroaryl or C.sub.2 -C.sub.12 alkenyl;
• from about 2 to about 70% by weight of a crosslinking agent having the formula:
• ##STR14## wherein A is a linking group;
• R.sub.3 is C.sub.1 -C.sub.12 alkylene, C.sub.2 -C.sub.12 alkenylene, C.sub.6 -C.sub.12 arylene, C.sub.7 -C.sub.18 arylalkylene, C.sub.4 -C.sub.12 heteroarylene, C.sub.6 -C.sub.18 heteroarylalkylene, C.sub.8 -C.sub.18 arylalkenylene, or C.sub.8 -C.sub.18 heteroarylalkenylene;
• R.sub.4 is H, halo, carboxy, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 ester, C.sub.6 -C.sub.12 aryl or C.sub.4 -C.sub.12 heteroaryl;
• n is at least 2;
• and
• optionally up to about 25% by weight other compatible comonomers, in the presence of a polymerization initiator and an antioxidant.