Catalyst containing oligomeric oxolanyl alkane modifiers and process for the production of polymers having increased 1,2-microstructure

Claim 2

A catalyst system comprising: (a) at least one anionic initiator based on lithium, (b) at least one compound selected from the group consisting of a dialkyl magnesium compound and a trialkyl aluminum compound, and (c) at least one oxolanyl compound selected from the group consisting of: ##STR2## wherein R 1 and R 2 independently are hydrogen or an alkyl group and the total number of carbon atoms in --CR 1 R 2 -- ranges between one and nine inclusive; y is an integer of 1 to 5 inclusive, y' is an integer of 3 to 5 inclusive, R 3 ', R 3 , R 4 and R 5 independently are --H or --C n H 2n+1 wherein n=1 to 6.

Claim 3

The catalyst system of claim 1 wherein the oxolanyl compound (b) is 2,2-bis(2-oxolanyl) propane.

Claim 4

The catalyst system of claim 1 wherein the anionic initiator is n-butyllithium.

Claim 5

The catalyst system of claim 1 wherein the mole ratio of (a) to (b) ranges between 1/0.01 and 1/100 and the mole ratio of [(a)+(b)] to (c) ranges from 20.0/1.0 to 1.0/20.0.

Claim 6

A process for the preparation of a polymer by polymerizing: (A) 15 to 100 percent of at least one 1,3-diene monomer, and (B) 0 to 85 percent of one or more reactive monomers which are copolymerizable with said 1,3-diene monomers, in an inert non-polar solvent in the presence of a catalytically effective amount of catalyst system comprising: (a) at least one anionic initiator based on lithium, (b) at least one compound selected from the group consisting of a dialkyl magnesium compound and a trialkyl aluminum compound, and (c) at least one oxolanyl modifier compound selected from the group consisting of: ##STR3## wherein R 1 and R 2 independently are hydrogen or an alkyl group and the total number of carbon atoms in --CR 1 R 2 -- ranges between one and nine inclusive; y is an integer of 1 to 5 inclusive, y' is an integer of 3 to 5 inclusive, R' 3 , R 3 , R 4 and R 5 independently are --H or --C n H 2n+1 wherein n=1 to 6; in which the mole ratio of (a) to (b) ranges between 1/0.01 and 1/100 and the molar ratio of [(a)+(b)] to (c) ranges between 20.0/1.0 and 1.0/20.0, the millimoles of the [(a)+(b)] per 100 grams of the (A+B) monomers ranges between about 0.2 and about 100, the polymerization temperature is maintained between about 0° C. and 160° C., wherein said polymer contains a 1,2-microstructure in the 1,3-diene monomer contributed units ranging between 20 and 95 percent.

Claim 7

A process for the preparation of a polymer by polymerizing: (A) 15 to 100 percent of at least one 1,3-diene monomer, and (B) 0 to 85 percent of one or more reactive monomers which are copolymerizable with said 1,3-diene monomers, in an inert non-polar solvent in the presence of a catalytically effective amount of catalyst system comprising: (a) at least one anionic initiator based on lithium, (b) at least one compound selected from the group consisting of a dialkyl magnesium compound and a trialkyl aluminum compound, and (c) at least one oxolanyl modifier compound selected from the group consisting of: ##STR3## wherein R 1 and R 2 independently are hydrogen or an alkyl group and the total number of carbon atoms in --CR 1 R 2 -- ranges between one and nine inclusive; y is an integer of 1 to 5 inclusive, y' is an integer of 3 to 5 inclusive, R' 3 , R 3 , R 4 and R 5 independently are --H or --C n H 2n+1 wherein n=1 to 6; in which the mole ratio of (a) to (b) ranges between 1/0.01 and 1/100 and the molar ratio of [(a)+(b)] to (c) ranges between 20.0/1.0 and 1.0/20.0, the millimoles of the [(a)+(b)] per 100 grams of the (A+B) monomers ranges between about 0.2 and about 100, the polymerization temperature is maintained between about 0° C. and 160° C., wherein said polymer contains a 1,2-microstructure in the 1,3-diene monomer contributed units ranging between 20 and 95 percent.

Claim 8

The process as in claim 5 wherein the 1,3-diene is a butadiene.

Claim 9

The process as in claim 5 wherein the 1,3-diene is butadiene and the reactive monomer is styrene.

Claim 10

The process as in claim 5 wherein the anionic initiator (a) is n-butyllithium.

Claim 11

The process as in claim 5 wherein the oxolanyl modifier is 2,2-bis(2-oxolanyl) propane.

Claim 12

The process as in claim 5 wherein the polymer has a 1,2-microstructure in the 1,3-diene monomer contributed units ranging between 30 and 60 percent.

Claim 13

The process as in claim 5 wherein the polymerization temperature is maintained between 115° C. and 140° C.