Block copolymers including high vinyl segments

1. A method for the preparation of block copolymers including at least one high vinyl segment the method comprising steps of:

(i) charging into a reactor 1,3-butadiene monomer in a hydrocarbon solvent, a catalytically effective amount of anionic initiator, and an oligomeric oxolanyl propane, where the concentration of the oligomeric oxolanyl propane is at least 0.1 and less than 20 moles per mole of initiator, whereby the reactor is optionally cooled;

(ii) allowing the 1,3-butadiene monomer to polymerize at a peak polymerization temperature of at least about 18° C. and less than about 60° C. to form a first polybutadiene block characterized by a vinyl content of at least 70 percent by weight, the first polybutadiene block having less than 180 mer units;

(iii) after step (ii), charging into the reactor a vinyl aromatic monomer, whereby the reactor is optionally heated to a temperature up to about 60° C.;

(iv) allowing the vinyl aromatic monomer to polymerize to form a second block;

(v) after step (iv), charging additional monomer into the reactor, wherein the additional monomer is conjugated diene monomer;

(vi) allowing the additional conjugated diene monomer to polymerize to thereby form a third block; and

(vii) charging into the reactor a quenching agent;

where the method produces a block copolymer having an overall vinyl content that is greater than 70 percent by weight.

2. The method of claim 1 , where the concentration of the oligomeric oxolanyl propane in step (i) is at least 0.1 and less than 5 moles per mole of initiator.

3. The method of claim 1 , where step (ii) includes allowing the 1,3-butadiene monomer to polymerize at a peak polymerization temperature of at least about 18° C. and less than about 46° C.

4. The method of claim 1 , further comprising, between step (iv) and step (v), a step of dropping to a temperature below 30° C.

5. The method of claim 1 , where the peak polymerization temperature achieved during step (vi) is at least 18° C. and less than 55° C.

6. The method of claim 1 , further comprising, between steps (vi) and (vii), steps of:

a. further charging into the reactor additional vinyl aromatic monomer; and

b. allowing the additional vinyl aromatic monomer to polymerize to thereby form a fourth block.

7. The method of claim 1 , where step (iii) includes the reactor being heated to a temperature up to about 60° C.

8. The method of claim 1 , where the first polybutadiene block is characterized by a vinyl content of at least 80 percent by weight.

9. The method of claim 1 , where the first polybutadiene block is characterized by a vinyl content of at least 85 percent by weight.

10. The method of claim 1 , where the method produces a block copolymer having an overall vinyl content that is greater than 80 percent by weight.

11. The method of claim 1 , where the method produces a block copolymer having an overall vinyl content that is greater than 85 percent by weight.

12. The method of claim 1 , where the third block is characterized by a vinyl content of at least 70 percent by weight.

13. A method for the preparation of block copolymers including at least one high vinyl segment the method comprising steps of:

(i) charging into a reactor conjugated diene monomer in a hydrocarbon solvent, a catalytically effective amount of anionic initiator, and an oligomeric oxolanyl propane, where the concentration of the oligomeric oxolanyl propane is at least 0.1 and less than 20 moles per mole of initiator, whereby the reactor is optionally cooled;

(ii) allowing the conjugated diene monomer to polymerize at a peak polymerization temperature of at least about 18° C. and less than about 60° C. to form a first block characterized by a vinyl content of at least 70 percent by weight, the first block having less than 180 mer units;

(iii) after step (ii), charging into the reactor a vinyl aromatic monomer, whereby the reactor is optionally heated to a temperature up to about 60° C.;

(iv) allowing the vinyl aromatic monomer to polymerize to form a second block;

(v) after step (iv), charging additional conjugated diene monomer into the reactor;

(vi) allowing the additional conjugated diene monomer to polymerize to thereby form a third block; and

(vii) charging into the reactor a quenching agent;

where the method produces a block copolymer having an overall vinyl content that is greater than 70 percent by weight.

14. A method for the preparation of block copolymers including at least one high vinyl segment the method comprising steps of:

(i) charging into a reactor conjugated diene monomer in a hydrocarbon solvent, a catalytically effective amount of anionic initiator, and an oligomeric oxolanyl propane, whereby the reactor is optionally cooled;

(ii) allowing the conjugated diene monomer to polymerize to form a first block, the first block having less than 180 mer units;

(iii) after step (ii), charging into the reactor a vinyl aromatic monomer, whereby the reactor is optionally heated to a temperature up to about 60° C.;

(iv) allowing the vinyl aromatic monomer to polymerize to form a second block;

(v) after step (iv), charging additional conjugated diene monomer into the reactor;

(vi) allowing the additional conjugated diene monomer to polymerize to thereby form a third block;

(vii) after step (vi), further charging into the reactor additional vinyl aromatic monomer;

(viii) allowing the additional vinyl aromatic monomer to polymerize to thereby form a fourth block; and

(ix) charging into the reactor a quenching agent.