Initiator systems for polymerization of 1,3-dienes or copolymers containing 1,3-dienes

Claim 2

A catalyst system comprising: (a) 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 inclusively; 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, and (b) at least one anionic initiator selected from the group consisting of: (i) Na(R" 1 )(R" 2 )(R" 3 )Mg, (ii) Na(R" 1 )(R" 2 )(R" 3 )Mg and an organolithium compound, and (iii) K(R" 1 )(R" 2 )(R" 3 )Mg and an organolithium compound, wherein R" 1 , R" 2 and R" 3 are independently selected from the group consisting of C 2 -C 14 organo radicals, 2-pyridyl and 2-thienyl.

Claim 3

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

Claim 4

The catalyst system of claim 1 wherein the Na(R" 1 )(R" 2 )(R" 3 )Mg compound is selected from the group consisting of sodium tri-n-hexyl magnesiate, sodium tributyl magnesiate, sodium dibutylhexyl magnesiate, sodium dibutyl 2-ethylhexyl magnesiate.

Claim 5

The catalyst system of claim 1 wherein the K(R" 1 )(R" 2 )(R" 3 )Mg compound is selected from the group consisting of potassium tri-n-hexyl magnesiate, potassium tributyl magnesiate, potassium dibutylhexyl magnesiate, and potassium dibutyl 2-ethylhexyl magnesiate.

Claim 6

The catalyst system of claim 1 wherein the organolithium compound is n-butyllithium.

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 a catalyst system comprising: (a) 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, and (b) at least one anionic initiator selected from the group consisting of: (i) Na(R" 1 )(R" 2 )(R" 3 )Mg (ii) Na(R" 1 )(R" 2 )(R" 3 )Mg and an organolithium compound, and (iii) K(R" 1 )(R" 2 )(R" 3 )Mg and an organolithium compound; wherein R" 1 , R" 2 and R" 3 are independently selected from the group consisting of C 2 -C 14 organo radicals, 2-pyridyl and 2-thienyl, in which the molar ratio (a) to (b) ranges between 1/20 to 20/1, the millimoles of anionic initiator per 100 grams of the (A+B) monomers ranges between 0.2 and about 100, wherein said polymer contains a 1,2-microstructure in the 1,3-diene monomer contributed units ranging between 30 and 90 percent and has a number average molecular weight ranging from 1,000 to 500,000.

Claim 8

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 a catalyst system comprising: (a) 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, and (b) at least one anionic initiator selected from the group consisting of: (i) Na(R" 1 )(R" 2 )(R" 3 )Mg (ii) Na(R" 1 )(R" 2 )(R" 3 )Mg and an organolithium compound, and (iii) K(R" 1 )(R" 2 )(R" 3 )Mg and an organolithium compound; wherein R" 1 , R" 2 and R" 3 are independently selected from the group consisting of C 2 -C 14 organo radicals, 2-pyridyl and 2-thienyl, in which the molar ratio (a) to (b) ranges between 1/20 to 20/1, the millimoles of anionic initiator per 100 grams of the (A+B) monomers ranges between 0.2 and about 100, wherein said polymer contains a 1,2-microstructure in the 1,3-diene monomer contributed units ranging between 30 and 90 percent and has a number average molecular weight ranging from 1,000 to 500,000.

Claim 9

The process as in claim 6 wherein the 1,3-diene is butadiene.

Claim 10

The process as in claim 6 wherein the diene is butadiene and the reactive monomer is styrene.

Claim 11

The process as in claim 6 wherein the oxolanyl compound is 2,2-bis(2-oxolanyl)propane.

Claim 12

The catalyst system of claim 1 wherein the oxolanyl compound is 2,2-bis(2-oxolanyl)propane, the anionic initiator is (iii) and the molar ratio of the oxolanyl compound to total anionic initiator ranges from 1.0/20 to 20/1.0.

Claim 13

The catalyst system of claim 10 wherein the anionic initiator consists of potassiumn tri-n-magnesiate and n-butyllithium in a ratio such that the milliequivalents of lithium to milliequivalents of potassium is 1/1 and the molar ratio of oxolanyl compound to total anionic initiator ranges from 1/2 to 10/1.

Claim 14

The catalyst system of claim 1 wherein the oxolanyl compound is 2,2-bis(2-oxolanyl)propane, the anionic initiator is (i) and the molar ratio of the oxolanyl compound to anionic initiator ranges from 1.0/20 to 20/1.0.

Claim 15

The catalyst system of claim 12 wherein the anionic initiator is sodium tri-n-hexyl magnesiate and the molar ratio of the oxolanyl compound to anionic initiator ranges from 1/2 to 10/1.

Claim 16

The process as in claim 6 for preparation of polybutadiene containing a 1,2-microstructure in the 1,3-diene monomer contributed units ranging between 35 and 60% wherein in the catalyst system the oxolanyl compound is 2,2-bis(2-oxolanyl)propane, the anionic initiator is (iii) and the molar ratio of the oxolanyl compound to total anionic initiator ranges from 1.0/20 to 20/1.0.

Claim 17

The process as in claim 14 wherein in the catalyst system the anionic initiator consists of potassium tri-n-hexyl magnesiate and n-butyllithium in a ratio such that the milliequivalents of lithium to milliequivalents of potassium is 1/1 and the molar ratio of oxolanyl compound to total anionic initiator ranges from 1/2 to 10/1.

Claim 18

The process as in claim 1 for preparation of styrene butadiene containing a 1,2-microstructure in the 1,3-diene monomer contributed units ranging between 35 and 60% wherein in the catalyst system the oxolanyl compound is 2,2-bis(2-oxolanyl)propane, the anionic initiator is (i) and the molar ratio of the oxolanyl compound to anionic initiator ranges from 1.0/20 to 20/1.0.

Claim 19

The process as in claim 16 wherein in the catalyst system the anionic initiator is sodium tri-n-hexyl magnesiate and the molar ratio of the oxolanyl compound to anionic initiator ranges from 1/2 to 10.1.