End group functionalization agents for polydiene

A compound having the structure of Formula (II):

• wherein
• A is selected from the group consisting of
• C1-15 alkyl, C1-15 alkylene, C3-8 cycloalkyl, aryl, arylene, and
• wherein C1-15 alkyl, C1-15 alkylene, C3-8 cycloalkyl, aryl, and arylene can be optionally substituted from 1 to 4 times with a substituent independently selected from the group consisting of H, halogen, C1-6 alkyl, and —NR7R8;
• is a point of attachment of A to
• group;
• R1 is C1-6 alkyl;
• R2 is H or C1-6 alkyl;
• R3 is H or C1-6 alkyl;
• R4 is C1-6 alkyl;
• R5 is H or C1-6 alkyl;
• R6 is H or C1-6 alkyl;
• R7 is H or C1-6 alkyl;
• R8 is H or C1-6 alkyl;
• R9 is C1-6 alkyl;
• R10 is C1-6 alkyl;
• X1 is C2-6 alkylene;
• X2 is C1-15 alkyene;
• Y is O or N;
• Z is H, R9, or Si(R10)3;
• a is 0 to 1;
• b is 1 or 2;
• n is 1 to 3;
• and
• wherein 1) if a is 0;
• R1 and R3 are Et, then A cannot be —Si(OEt)3, n-Bu, i-Pr, t-Bu, or Ph, 2) if a is 0;
• R1 and R3 are Me, then A cannot be C2-8 alkylene.

A modified polymer having the structure of Formula (IV):

• wherein
• each indicates a bond with cis and/or trans geometric isomerism;
• is a polymer of formula
• R is H or C1-6 alkyl;
• R′ is selected from the group consisting of H and —NRaRb;
• R″ is H or C1-6 alkyl;
• Ra is H or C1-6 alkyl;
• Rb is H or C1-6 alkyl;
• W is a repeating unit of the polymer;
• m is 1000 to 55000;
• k is 1 or 500;
• and
• x is 0 to 3.

A process for polymerizing unsaturated hydrocarbon monomers, said process comprising:

• providing unsaturated hydrocarbon monomers;
• providing a compound of Formula (V):
• wherein
• R is H or C1-6 alkyl;
• R′ is selected from the group consisting of H, C1-6 alkyl, —OC1-6 alkyl;
• and —NRaRb,
• R″ is H or C1-6 alkyl;
• Ra is H or C1-6 alkyl;
• Rb is H or C1-6 alkyl;
• and
• x is 0 to 3;
• and
• providing a catalyst selected from the group consisting of:
• (1) a mixture of (A) a compound of Formula M2(HA2)A23;
• (B) a halogen containing compound;
• and (C) an organometallic compound, wherein M2 is a lanthanide metal;
• A2 is C8-20 carboxylate;
• and (2) a compound of Formula (III):
• MC(SiHAlk2)3(R11)2 (III), wherein M is a lanthanide or a transition metal;
• Alk is C1-6 alkyl;
• R11 is halide, bis(oxazolinato), carboxylate, acetyl acetonate, amidate, alkoxide, amide, BR124, AlR124, or alkyl aluminate;
• R12 is independently selected at each occurrence thereof from the group consisting of H, C6F5, phenyl, and C1-6 alkyl;
• and
• polymerizing the unsaturated hydrocarbon monomers in the presence of the catalyst and the compound of Formula (V) under conditions effective to produce the modified polymer.

A process for producing a modified polymer, said process comprising:

• providing a polymer;
• providing a compound of Formula (V):
• wherein
• R is H or C1-6 alkyl;
• R′ is selected from the group consisting of H, C1-6 alkyl, —OC1-6 alkyl;
• and —NRaRb,
• R″ is H or C1-6 alkyl;
• Ra is H or C1-6 alkyl;
• Rb is H or C1-6 alkyl;
• x is 0 to 2;
• and
• reacting the polymer with the compound of Formula (V) under conditions effective to produce the modified polymer.