Silyl-diamine initiators for anionic polymerization of 1,3-butadiene and styrene, and rubber compositions

A polymerization initiator characterized by the following formula (V):

• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• M1 is an alkali metal, an alkaline earth metal salt or an alkaline earth metal alkyl group.

A polymerization initiator solution resulting from the addition of a diamine compound represented by the following formula (VI):

• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a hydrogen atom;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• a part of R1, R2 and R3 may be bonded to each other to form a cyclic structure, with a silyl compound represented by the following formula (VII):
• Y2—X2 (VII)
• wherein Y2 is a substituted silyl group;
• X2 is one selected from the group consisting of a halogen atom, a thioalkyl group having a carbon number of 1-20, cyano group and trifluoromethylsulfonyl group, and the subsequent addition of an organic alkali metal compound or an organic alkaline earth metal compound thereto.

A method of producing a polymerization initiator, characterized in that (i) a diamine compound represented by the following formula (VI):

• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a hydrogen atom;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hereto atom provided that it does not have an active proton;
• a part of R1, R2 and R3 may be bonded to each other to form a cyclic structure, is added with a silyl compound of represented by the following formula (VII):
• Y2—X2 (VII)
• wherein Y2 is a substituted silyl group;
• X2 is one selected from the group consisting of a halogen atom, a thioalkyl group having a carbon number of 1-20, cyano group and trifluoromethylsulfonyl group, to form a silylated diamine compound represented by the following formula (VIII):
• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• and
• (ii) the said silylated diamine compound is added with an organic alkali metal compound or an organic alkaline earth metal compound to form a polymerization initiator represented by the following formula (V)
• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• M1 is an alkali metal, an alkaline earth metal salt or an alkaline earth metal alkyl group.

A method of producing a modified conjugated diene polymer, characterized in that (i) a diamine compound represented by the formula (VI):

• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a hydrogen atom;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hereto atom provided that it does not have an active proton;
• a part of R1, R2 and R3 may be bonded to each other to form a cyclic structure, is added with a silyl compound represented by the following formula (VII):
• Y2—X2 (VII)
• wherein Y2 is a substituted silyl group;
• X2 is one selected from the group consisting of a halogen atom, a thioalkyl group having a carbon number of 1-20, cyano group and trifluoromethylsulfonyl group, to form a silylated diamine compound represented by the following formula (VIII);
• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• (ii) the silylated diamine compound is added with an organic alkali metal compound or the organic alkaline earth metal compound to form the polymerization initiator represented by the following formula (V);
• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• M1 is an alkali metal, an alkaline earth metal salt or an alkaline earth metal alkyl group, and
• (iii) the polymerization initiator is used to polymerize a conjugated diene compound or polymerize a conjugated diene compound and aromatic vinyl compound.

A method of producing a modified conjugated diene polymer, characterized in that (i) a diamine compound represented by the following formula (VI):

• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a hydrogen atom;
• R3 is having a carbon number of 1-12 provided that it may include a hereto atom provided that it does not have an active proton;
• a part of R1, R2 and R3 may be bonded to each other to form a cyclic structure, is added with a silyl compound represented by the following formula (VII):
• Y2—X2 (VII)
• wherein Y2 is a substituted silyl group;
• X2 is one selected from the group consisting of a halogen atom, a thioalkyl group having a carbon number of 1-20, cyano group and trifluoromethylsulfonyl group, to form a silylated diamine compound represented by the following formula (VIII);
• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• (ii) the silylated diamine compound is added with an organic alkali metal compound or the organic alkaline earth metal compound to form the polymerization initiator of the formula (V):
• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• M1 is an alkali metal, an alkaline earth metal salt or an alkaline earth metal alkyl group;
• (iii) the polymerization initiator is added to a solution containing a conjugated diene compound to produce a low molecular weight polymer represented by the following formula (IX):
• wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group M1 is an alkali metal, an alkaline earth metal salt or an alkaline earth metal alkyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure;
• Oli is an oligomer or polymer portion formed by polymerizing 3-300 conjugated diene compounds;
• and
• (iv) the low molecular weight polymer is added to a solution containing a conjugated diene compound or a solution containing a conjugated diene compound and an aromatic vinyl compound.

A method of producing a modified conjugated diene polymer, characterized in that (i) a diamine compound represented by the following formula (VI):

• (wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a hydrogen atom;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hereto atom provided that it does not have an active proton;
• a part of R1, R2 and R3 may be bonded to each other to form a cyclic structure) is added with a silyl compound represented by the following formula (VII):
• Y2—X2 (VII)
• (wherein Y2 is a substituted silyl group;
• X2 is one selected from the group consisting of a halogen atom, a thioalkyl group having a carbon number of 1-20, cyano group and trifluoromethylsulfonyl group) to form a silylated diamine compound represented by following formula (VIII):
• (wherein R1 and R2 are independently an alkyl or aryl group having a carbon number of 1-20 or a substituted silyl group;
• R3 is an alkylene or arylene group having a carbon number of 1-12 provided that it may include a hetero atom provided that it has does not have an active proton;
• Y2 is a substituted silyl group;
• a part of R1, R2, R3 and Y2 may be bonded to each other to form a cyclic structure);
• (ii) the silylated diamine compound is added to a solution containing a conjugated diene compound or a solution containing a conjugated diene compound and an aromatic vinyl compound;
• and
• (iii) the solution is further added with an organic alkali metal compound or an organic alkaline earth metal compound.