Crystallizable stereoblock rubbery copolymers

Claim 1

A CRYSTALLIZABLE STEREOBLOCK RUBBERY COPOLYMER, SAID STEREOBLOCK COPOLYMER BEING AMORPHOUS IN THE UNDEFORMED STATE AND CAPABLE OFF CRYSTALLIZATION UPON STRETCHING AND HAVING AT LEAST THREE SUCCESSIVE AND ALTERNATING POLYMERIC BLOCKS, ONE OF SAID POLYMERIC BLOCKS BEING AN AMORPHOUS NONCRYSTALLIZABLE ATACTIC COPOLYMER OF (1) A MONOMER SELECTED FROM THE GROUP CONSISTING OF ETHYLENE AND PROPYLENE AND (2) A DISSIMILAR 1-OLEFIN HAVING FROM 3 TO 12 CARBON ATOMS, THE MOLAR RATION OF SAID MONOMER TO SAID 1-OLEFIN BEING FROM 20:80 TO 80:20, ANOTHER OF SAID POLYMERIC BLOCKS BEING SELECTED FROM THE GROUP CONSISTING OF A CRYSTALLIZABLE HOMOPOLYMER OF A 1OLEFIN HAVING FROM 2 TO 12 CARBON ATOMS AND A CRYSTALLIZABLE COPOLUMER OF (1) A MONOMER SELECTED FROM THE GROUP CONSISTING OF ETHYLENE AND PROPYLENE AND (2) A DISSIMILARR 1-OLEFIN HAVING FROM 3 TO 12 CARBON ATOMS, THE MOLAR RATIO OF SAID MONOMER TO SAID 1-OLEFIN BEING IN THE RANGES FROM 5:95 TO 20:80 OR 80:20 TO 95:5.

Claim 17

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of 1-olefin having from 2 to 12 carbon atoms, which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms with a non-stereospecific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 0* C. and 100* C., sufficient of said monomer and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer from 100 to 2000 monomer units and in which the molar ratio of said monomer to said 1-olefin is from 20:80 to 80: 20, and another such polymeric block being formed by contacting an individual 1-olefin having from 2 to 12 carbon atoms under the same polymerization conditions, sufficient of said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable homopolymer containing from 20 to 200 monomer units in the case of ethylene and from 200 to 1000 monomer units in the case of 1-olefins having from 3 to 12 carbon atoms, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of at least three successive and alternating polymeric blocks, said non-stereospecific catalyst comprising an ionic-coordination complex of the Ziegler-type capable of polymerizing alpha-olefins in atactic isomery.

Claim 18

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of 1-olefin having from 2 to 12 carbon atoms, which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms with a non-stereospecific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 0* C. and 100* C., sufficient of said monomer and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer from 100 to 2000 monomer units and in which the molar ratio of said monomer to said 1-olefin is from 20:80 to 80: 20, and another such polymeric block being formed by contacting an individual 1-olefin having from 2 to 12 carbon atoms under the same polymerization conditions, sufficient of said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable homopolymer containing from 20 to 200 monomer units in the case of ethylene and from 200 to 1000 monomer units in the case of 1-olefins having from 3 to 12 carbon atoms, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of at least three successive and alternating polymeric blocks, said non-stereospecific catalyst comprising an ionic-coordination complex of the Ziegler-type capable of polymerizing alpha-olefins in atactic isomery.

Claim 20

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously ethylene and a higher 1-olefin having from 3 to 12 carbon atoms with a non-stereospecific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 20* C. and 35* C., sufficient of the ethylene and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer containing from 100 to 2000 monomer units and in which the molar ratio of ethylene to said 1-olefin is from 20: 80 to 80:20, and another such polymeric block being formed by contacting an 1-olefin having from 2 to 12 carbon atoms under the same polymerization conditions, sufficient of said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable homopolymer containing from 20 to 200 monomer units in the case Of ethylene and from 200 to 1000 monomer units in the case of 1-olefins having from 3 to 12 carbon atoms, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of from about 7 to about 13 successive and alternating polymeric blocks, said non-stereospecific catalyst comprising a member selected from the group consisting of (1) mixtures of vanadium oxytrihalide and a member selected from the group consisting of aluminum trialkyl, alkyl aluminum dihalide and dialkyl aluminum halide, and (2) mixtures of titanium tetrahalide and a member selected from the group consisting of lithium aluminum tetraalkyl and lithium alkyl-aluminum trialkyl.

Claim 21

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously ethylene and a higher 1-olefin having from 3 to 12 carbon atoms with a non-stereospecific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 20* C. and 35* C., sufficient of the ethylene and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer containing from 100 to 2000 monomer units and in which the molar ratio of ethylene to said 1-olefin is from 20: 80 to 80:20, and another such polymeric block being formed by contacting an 1-olefin having from 2 to 12 carbon atoms under the same polymerization conditions, sufficient of said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable homopolymer containing from 20 to 200 monomer units in the case Of ethylene and from 200 to 1000 monomer units in the case of 1-olefins having from 3 to 12 carbon atoms, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of from about 7 to about 13 successive and alternating polymeric blocks, said non-stereospecific catalyst comprising a member selected from the group consisting of (1) mixtures of vanadium oxytrihalide and a member selected from the group consisting of aluminum trialkyl, alkyl aluminum dihalide and dialkyl aluminum halide, and (2) mixtures of titanium tetrahalide and a member selected from the group consisting of lithium aluminum tetraalkyl and lithium alkyl-aluminum trialkyl.

Claim 23

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of 1-olefins having from 2 to 12 carbon atoms, which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms with a non-stereo-specific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 0* C. and 100* C., sufficient of said monomer and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer containing from 100 to 2000 monomer units and in which the molar ratio of said monomer to said 1-olefin is from 20:80 to 80:20, and another such polymeric block being formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms under the same polymerization conditions, sufficient of said monomer and said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable copolymer containing from 100 to 2000 monomer units and in which the molar ratio of said monomer to said 1-olefin is in the ranges from 5:95 to 20:80 or 80:20 to 95:5, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of at least two successive and alternating polymeric blocks, said non-stereo-specific catalyst comprising an ionic-coordination complex of the Ziegler-type capable of polymerizing alpha-olefins in atactic isomery.

Claim 24

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of 1-olefins having from 2 to 12 carbon atoms, which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms with a non-stereo-specific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 0* C. and 100* C., sufficient of said monomer and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer containing from 100 to 2000 monomer units and in which the molar ratio of said monomer to said 1-olefin is from 20:80 to 80:20, and another such polymeric block being formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms under the same polymerization conditions, sufficient of said monomer and said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable copolymer containing from 100 to 2000 monomer units and in which the molar ratio of said monomer to said 1-olefin is in the ranges from 5:95 to 20:80 or 80:20 to 95:5, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of at least two successive and alternating polymeric blocks, said non-stereo-specific catalyst comprising an ionic-coordination complex of the Ziegler-type capable of polymerizing alpha-olefins in atactic isomery.

Claim 25

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of ethylene and a higher 1-olefin having from 3 to 12 carbon atoms which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously ethylene and said higher 1-olefin with a non-stereospecific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 20* C. and 35* C., sufficient ethylene and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer containing from 100 to 2000 monomer units and in which the molar ratio of ethylene to said 1-olefin is from 20:80 to 80:20, and another such polymeric block being formed by contacting simultaneously ethylene and a higher 1-olefin having from 3 to 12 carbon atoms under the same polymerization conditions, sufficient ethylene and said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable copolymer containing from 100 to 2000 monomer units and in which the molar ratio of ethylene to said 1-olefin is in the ranges from 5:95 to 20:80 or 80:20 to 95: 5, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of from about 5 to about 11 successive and alternating polymeric blocks, said non-stereospecific catalyst comprising a member selected from the group consisting of (1) mixtures of vanadium oxytrihalide and a member selected from the group consisting of aluminum trialkyl, alkyl aluminum dihalide and dialkyl aluminum halide, and (2) mixtures of titanium tetrahalide and a member selected from the group consisting of lithium aluminum tetraalkyl and lithium alkyl-aluminum trialkyl.

Claim 26

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of ethylene and a higher 1-olefin having from 3 to 12 carbon atoms which comprises forming successive and alternating polymeric blocks, one such polymeric block being formed by contacting simultaneously ethylene and said higher 1-olefin with a non-stereospecific catalyst in an inert liquid hydrocarbon solvent at a suitable polymerization temperature between 20* C. and 35* C., sufficient ethylene and said 1-olefin being charged so that the polymeric block thus formed is an amorphous non-crystallizable atactic copolymer containing from 100 to 2000 monomer units and in which the molar ratio of ethylene to said 1-olefin is from 20:80 to 80:20, and another such polymeric block being formed by contacting simultaneously ethylene and a higher 1-olefin having from 3 to 12 carbon atoms under the same polymerization conditions, sufficient ethylene and said 1-olefin being charged so that said other polymeric block thus formed is a crystallizable copolymer containing from 100 to 2000 monomer units and in which the molar ratio of ethylene to said 1-olefin is in the ranges from 5:95 to 20:80 or 80:20 to 95: 5, and recovering a solid crystallizable stereoblock rubbery copolymer thus produced of from about 5 to about 11 successive and alternating polymeric blocks, said non-stereospecific catalyst comprising a member selected from the group consisting of (1) mixtures of vanadium oxytrihalide and a member selected from the group consisting of aluminum trialkyl, alkyl aluminum dihalide and dialkyl aluminum halide, and (2) mixtures of titanium tetrahalide and a member selected from the group consisting of lithium aluminum tetraalkyl and lithium alkyl-aluminum trialkyl.

Claim 28

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of 1-olefins having from 2 to 12 carbon atoms which comprises forming successive and alternating polymeric blocks, one of said polymeric blocks being an amorphous non-crystallizable atactic copolymer, in which the molar ratio of said monomer to said 1-olefin is from 20:80 to 80:20, formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms with a nonstereospecific catalyst in an inert liquid hydrocarbon solvent at a polymerization temperature between 0* C. and 100* C., another of said polymeric blocks being selected from the group consisting of crystallizable homopolymers formed by contacting an individual 1-olefin having from 2 to 12 carbon atoms under the same polymerization conditions and crystallizable copolymers, in which the molar ratio of said monomer to said 1-olefin is in the ranges from 5:95 to 20:80 or 80:20 to 95:5, formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms under the same polymerization conditions, said non-stereospecific catalyst comprising an ionic-coordination complex of the Ziegler type capable of polymerizing alpha-olefins in atactic isomery.

Claim 29

A method of making crystallizable stereoblock rubbery copolymers, said stereoblock copolymers being amorphous in the undeformed state and capable of crystallization upon stretching, by block polymerization of 1-olefins having from 2 to 12 carbon atoms which comprises forming successive and alternating polymeric blocks, one of said polymeric blocks being an amorphous non-crystallizable atactic copolymer, in which the molar ratio of said monomer to said 1-olefin is from 20:80 to 80:20, formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms with a nonstereospecific catalyst in an inert liquid hydrocarbon solvent at a polymerization temperature between 0* C. and 100* C., another of said polymeric blocks being selected from the group consisting of crystallizable homopolymers formed by contacting an individual 1-olefin having from 2 to 12 carbon atoms under the same polymerization conditions and crystallizable copolymers, in which the molar ratio of said monomer to said 1-olefin is in the ranges from 5:95 to 20:80 or 80:20 to 95:5, formed by contacting simultaneously (1) a monomer selected from the group consisting of ethylene and propylene and (2) a dissimilar 1-olefin having from 3 to 12 carbon atoms under the same polymerization conditions, said non-stereospecific catalyst comprising an ionic-coordination complex of the Ziegler type capable of polymerizing alpha-olefins in atactic isomery.