Silicon-functionalized rubber
The compatibility between silica fillers and synthetic rubbers which are synthesized utilizing lanthanide-based catalyst systems, such as neodymium catalyst systems can be improved by terminating the polymerization with a vinyl silane terminating agent. In doing so the vinyl silane is allowed to react with the polymer chain ends of the neodymium rubber to functionalize the chain ends of the polymer chains with silicon containing groups. This results in the rubber having better characteristics for utilization in tire rubber formulations, such a tire tread formulations, that exhibit improved wear characteristics and lower rolling resistance. The process for the synthesis of such functionalized polydiene rubber comprises (1) polymerizing a diene monomer in the presence of a lanthanide-based catalyst system, and (2) terminating the polymerization with a vinyl silane terminator. The functionalized polydiene rubber composition made by this method is comprised of a polydiene rubber which is functionalized at its chain ends with a silicon containing group.
1 . A process for the synthesis of a functionalized polydiene rubber which comprises (1) polymerizing a diene monomer in the presence of a lanthanide-based catalyst system, and (2) terminating the polymerization with a vinyl silane terminator, wherein the vinyl silane terminator is a compound of the structural formula:
wherein R
1 represents an alkyl group containing from 1 to 8 carbon atoms and wherein the R 2 groups can be the same or different and represent alkyl groups containing from 1 to 8 carbon atoms.
2 . The process of claim 1 wherein the diene monomer is 1,3-butadiene and wherein the polydiene rubber is polybutadiene rubber which is functionalized at its chain ends with a silicon containing group.
3 . The process of claim 1 wherein the diene monomer is isoprene and wherein the polydiene rubber is polyisoprene rubber which is functionalized at its chain ends with a silicon containing group.
4 . The process of claim 1 wherein the diene monomer is 1,3-butadiene and wherein a vinyl aromatic monomer is copolymerized with the diene monomer.
5 . The process of claim 4 wherein the vinyl aromatic monomer is styrene and wherein the polydiene rubber is styrene-butadiene rubber which is functionalized at its chain ends with a silicon containing group.
6 . The process of claim 1 wherein lanthanide-based catalyst system is a neodymium based catalyst system.
7 . The process of claim 1 wherein R 1 represents an alkyl group containing from 1 to 4 carbon atoms and wherein R 2 represents alkyl groups containing from 1 to 4 carbon atoms.
8 . The process of claim 1 wherein R 1 represents an alkyl group containing 1 carbon atom and wherein R 2 represents alkyl groups containing 2 carbon atoms.
9 . The process of claim 1 wherein the termination step is carried out after a monomer conversion of at least 95% has been attained.
10 . The process as specified in claim 9 further comprising adding a shortstop after the termination step to quench any remaining active catalyst.
11 . The process of claim 1 wherein the termination step is carried out after a monomer conversion of at least 97% has been attained.
12 . The functionalized polydiene rubber made by the process specified in claim 1 .
13 . A rubber formulation which is comprised of (1) the functionalized polydiene rubber composition of claim 12 and (2) a reinforcing silica filler.
14 . The rubber formulation of claim 13 wherein said rubber formulation is further comprised of carbon black.
15 . The rubber formulation of claim 13 wherein said rubber formulation is further comprised of a silica coupling agent.
16 . A tire which is comprised of a generally toroidal-shaped carcass with an outer circumferential tread, two spaced beads, at least one ply extending from bead to bead and sidewalls extending radially from and connecting said tread to said beads, wherein said circumferential tread is adapted to be ground-contacting, wherein the circumferential tread is comprised of the rubber formulation as specified in claim 13 .
17 . A process for the synthesis of a functionalized polydiene rubber which comprises (1) polymerizing a diene monomer in the presence of a lanthanide-based catalyst system, and (2) terminating the polymerization with a vinyl silane terminator, wherein the vinyl silane terminator is VPOS.
18 . The process of claim 17 wherein the diene monomer is 1,3-butadiene and wherein the polydiene rubber is polybutadiene rubber which is functionalized at its chain ends with a silicon containing group.
19 . The process of claim 17 wherein the diene monomer is isoprene and wherein the polydiene rubber is polyisoprene rubber which is functionalized at its chain ends with a silicon containing group.
20 . The process of claim 17 wherein the diene monomer is 1,3-butadiene, wherein a styrene is copolymerized with the 1,3-butadiene monomer, and wherein the polydiene rubber is styrene-butadiene rubber which is functionalized at its chain ends with a silicon containing group.