METHOD FOR PRODUCING MODIFIED POLYMERS AND RUBBER COMPOSITIONS USING THE SAME
In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to a method for making branched polymers. In one aspect the method comprises reacting a first elastomeric polymer (1EP) with a molar excess of a second elastomeric polymer (2EP) to produce a first mixture comprising a third elastomeric polymer (3EP) and 2EP. 1EP and 2EP each individually comprise a polymer with a first terminus and a second terminus, where a residue of a silane polymerization initiator is covalently bonded to the first terminus of the polymer and where the polymers and silane polymerization initiators of 1EP and 2EP can be the same or different. 1EP further comprises a residue of a silane polymerization terminator covalently bonded to the second terminus of the polymer. The method further comprises hydrolyzing the first mixture so that 2EP and 3EP react with one another to produce a branched polymer. Polymers produced by this method can be included in articles comprising rubber compositions, such as tires or components of tires.
1 . A method for making a branched polymer, comprising:
(a) reacting a first elastomeric polymer (1EP) with a molar excess of a second elastomeric polymer (2EP) to produce a first mixture comprising a third elastomeric polymer (3EP) and 2EP, wherein
the first elastomeric polymer (1EP) comprises a first polymer with a first terminus and a second terminus, wherein a residue of a first silane polymerization initiator is covalently bonded to the first terminus of the first polymer and a residue of a silane polymerization terminator is covalently bonded to the second terminus of the first polymer, and
the second elastomeric polymer (2EP) comprises a second polymer with a first terminus and a second terminus, wherein a residue of a second silane polymerization initiator is covalently bonded to the first terminus of the second polymer,
wherein the first silane polymerization initiator is the same or different from the second polymerization initiator,
wherein the first polymer and the second polymer are the same or different polymer; and
(b) hydrolyzing the first mixture so that 2EP and 3EP react with one another to produce the branched polymer.
2 . The method of claim 1 , wherein the molar ratio of 2EP to 1EP is greater than 1:1 to about 2:1.
3 . The method of claim 1 , wherein 1EP has the structure
wherein R 1 , R 2 , and R 3 are independently selected from an alkyl group, a primary amine, a secondary amine, a tertiary amine, and a hydrolysable group, wherein at least one of R 1 , R 2 , and R 3 is a hydrolysable group;
R 4 is an alkene or an epoxy group;
R 5 is an aryl group or an alkyl group directly bonded to Si;
P is an unsaturated polymer;
X is a halide directly bonded to Si;
m is 1, 2, or 3;
n is 0, 1, or 2; and
the sum of n and m is not greater than 3.
4 . The method of claim 1 , wherein 1EP is produced by (1) reacting a conjugated diene with an anionic first silane polymerization initiator to produce a first initiator polymer (1IP), and (2) reacting 1IP with Si(R 5 ), X 4−n to produce 1EP, wherein each R 5 is independently selected from an aryl group or an aliphatic group, X is a halide, and n is 0, 1, or 2.
5 . The method of claim 4 , wherein the conjugated diene is selected from one or more of butadiene, isoprene, pentadiene, octadiene, and any combination thereof.
6 . The method of claim 4 , where the conjugated diene is copolymerized with a vinyl-substituted aromatic monomer selected from one or more of styrene and vinylnapthalene.
7 . The method of claim 4 , wherein the anionic first silane polymerization initiator is a silane compound comprising at least one deprotonated vinyl group or epoxy group.
8 . The method of claim 4 , wherein the anionic first silane polymerization initiator has the structure
wherein R 1 , R 2 , and R 3 are independently selected from an alkyl group, a primary amine, a secondary amine, a tertiary amine, and a hydrolysable group, wherein at least one of R 1 , R 2 , and R 3 is a hydrolysable group, and
R 4 is a deprotonated vinyl group or a deprotonated epoxy group.
9 . The method of claim 8 , wherein R 2 is a C1-C6 alkyl group and R 1 and R 3 are —N(R 6a ) (R 6b ), wherein R 6a and R 6b are selected from hydrogen and a C1-C6 alkyl group.
10 . The method of claim 1 , wherein 2EP is produced by reacting a conjugated diene with an anionic second silane polymerization initiator.
11 . The method of claim 10 , wherein the conjugated diene is selected from one or more of butadiene, isoprene, pentadiene, octadiene, and any combination thereof.
12 . The method of claim 10 , where the conjugated diene is copolymerized with a vinyl-substituted aromatic monomer selected from one or more of styrene and vinylnapthalene.
13 . The method of claim 10 , wherein the anionic second silane polymerization initiator is a silane compound comprising at least one deprotonated vinyl group or epoxy group.
14 . The method of claim 10 , wherein the anionic second silane polymerization initiator has the following structure:
wherein R 1 , R 2 , and R 3 are independently an alkyl group, a primary amine, a secondary amine, and a tertiary amine, or a hydrolysable group, wherein at least one of R 1 , R 2 , and R 3 is a hydrolysable group, and
R 4 is a deprotonated vinyl group or a deprotonated epoxy group.
15 . The method of claim 14 , wherein R 2 is a C1-C6 alkyl group and R 1 and R 3 are —N(R 6a ) (R 6b ), wherein R 6a and R 6b are selected from hydrogen and a C1-C6 alkyl group.
16 . The method of claim 1 , wherein the residue of the first and second silane polymerization initiator have the structure
wherein,
R 1 and R 3 are independently selected from a primary amine, a secondary amine, and a tertiary amine; and
R 2 is selected from hydrogen and a C1-C6 alkyl group.
17 . A polymer produced by the method of claim 1 .
18 . A rubber composition comprising the polymer of claim 17 .
19 . An article comprising the rubber composition of claim 18 .
20 . The article of claim 19 , wherein the article comprises a tire or a component of a tire.