Vulcanizable liquid compositions

A liquid star-branched block copolymer, each branch comprising at least two (2) alternating blocks

• A--D
• wherein each free end of the branches is an A block and
• A is a copolymer of at least one aryl-substituted olefin and at least one conjugated diene having at least five (5) carbon atoms and the following formula ##STR17## wherein R.sup.1 -R.sup.6 are each hydrogen or a hydrocarbyl group, provided that at least one of R.sup.1 -R.sup.6 is a hydrocarbyl group and provided that the structure of the residual double bond in the polymerized block A has the following formula ##STR18## wherein R.sup.I, R.sup.II, R.sup.III and R.sup.IV are each hydrogen or a hydrocarbyl group, provided that either both R.sup.I and R.sup.II are hydrocarbyl groups or both R.sup.III and R.sup.IV are hydrocarbyl groups;
• D is a block polymer of a conjugated diene, different from the diene used to polymerize the block A, having at least four (4) carbon atoms and the following formula ##STR19## wherein R.sup.7 -R.sup.12 are each hydrogen or a hydrocarbyl group, provided that the structure of the residual double bond in the polymerized block D has the following formula ##STR20## wherein R.sup.a, R.sup.b, R.sup.c and R.sup.d are each hydrogen (H) or a hydrocarbyl group, provided that one of R.sup.a or R.sup.b is hydrogen, one of R.sup.c or R.sup.d is hydrogen, and at least one of R.sup.a, R.sup.b, R.sup.c or R.sup.d is a hydrocarbyl group;
• said polymerized block D containing at least about 25 wt. % of 1,2- units if it is a polymer of predominantly 1,3-butadiene;
• said copolymer being selectively hydrogenated so that each of the blocks D is substantially completely hydrogenated and thereby contains substantially none of the original unsaturation, while each of the blocks A retains a sufficient amount of its original unsaturation to vulcanite said copolymer.

A liquid star-branched block polymer, each branch comprising at least three alternating blocks.

• I--D--A
• wherein each free end of the branches is either an I or an A block and
• I is a block of at least one polymerized conjugated diene having at least five (5) carbon atoms and the following formula ##STR21## wherein R.sup.1 -R.sup.6 are each hydrogen or a hydrocarbyl group, provided that at least one of R.sup.1 -R.sup.6 is a hydrocarbyl group and provided that the structure of the residual double bond in the polymerized block I has the following formula ##STR22## wherein R.sup.I, R.sup.II, R.sup.III and R.sup.IV are each hydrogen or a hydrocarbyl group, provided that either both R.sup.I and R.sup.II are hydrocarbyl groups or both R.sup.III and R.sup.IV are hydrocarbyl groups;
• D is a block polymer of a conjugated diene, different from that used to polymerize the blocks I or A, having at least four (4) carbon atoms and the following formula ##STR23## wherein R.sup.7 -R.sup.12 are each hydrogen or a hydrocarbyl group, provided that the structure of the residual double bond in the polymerized block D has the following formula ##STR24## wherein R.sup.a, R.sup.b, R.sup.c and R.sup.d are each hydrogen (H) or a hydrocarbyl group, provided that one of R.sup.a or R.sup.b is hydrogen, one of R.sup.c or R.sup.d is hydrogen, and at least one of R.sup.a, R.sup.b, R.sup.c or R.sup.d is a hydrocarbyl group;
• A is a copolymer of about 30 to about 70% by mole of at least one aryl-substituted olefin and about 30 to about 70% by mole of at least one conjugated diene of formula (1), different from that used to polymerize the block D, having at least five (5) carbon atoms and the following formula ##STR25## wherein R.sup.1 -R.sup.6 are each hydrogen or a hydrocarbyl group, provided that at least one of R.sup.1 -R.sup.6 is a hydrocarbyl group and provided that the structure of the residual double bond in the polymerized block I has the following formula ##STR26## wherein R.sup.I, R.sup.II, R.sup.III and R.sup.IV are each hydrogen or a hydrocarbyl group, provided that either both R.sup.I and R.sup.II are hydrocarbyl groups or both R.sup.III and R.sup.IV are hydrocarbyl groups;
• said polymerized block D containing at least about 25 wt. % of 1,2- units if it is a polymer of predominantly 1,3-butadiene;
• said copolymer being selectively hydrogenated so that each of the blocks D is substantially completely hydrogenated and thereby contains substantially none of the original unsaturation, while each of the blocks I and A retains a sufficient amount of its original unsaturation to vulcanize said copolymer.

A liquid star-branched copolymer wherein each branch comprises two (2) alternating blocks bonded to each other, the free end of each branch being a block of at least one polymerized hydrocarbon conjugated diene (I) monomer containing at least five (5) carbon atoms, with at least one carbon atom of each pair of residual double-bonded carbon atoms of polymerized conjugated diene (I) units being additionally single-bonded to two carbon atoms, or a copolymer of at least one diene (I) at least one aryl-substituted olefin, the blocks adjacent to said polymerized diene (I) containing blocks being a polymer of at least one polymerized hydrocarbon conjugated diene (B), which is different from conjugated diene (I) and contains at least four (4) carbon atoms, with each residual double-bonded carbon atom of polymerized conjugated diene (B) units being additionally bonded to a hydrogen atom, the latter polymerized diene (B)-containing blocks additionally comprising at least about 25 wt. % of 1,2-units if they area polymer of predominantly 1,3-butadiene, said block copolymer being selectively hydrogenated so that said polymerized conjugated diene (B) units are substantially completely hydrogenated and contain substantially none of the original unsaturation, while said polymerized conjugated diene (I) units retain sufficient amount of their original unsaturation to vulcanize said copolymer.