Modified polymer compositions

1. A composition comprising a modified polymer comprising:

at least one branched modified polymer macromolecule comprising at least one of structure (ib1), (ib2), (ib3), or (ib4); and

at least one linear modified polymer macromolecule comprising at least one of structure (iib1) or (iib2);

wherein the at least one branched modified polymer macromolecule and the at least one linear modified polymer macromolecule each, independently, further comprise at least one amine group selected from the group consisting of:

and combinations thereof;

where,

N is a nitrogen atom;

C is carbon atom;

H is a hydrogen atom;

E is at least divalent, comprises at least one heteroatom, and is selected from the group consisting of: a) a (C 1 -C 18 ) alkyl, which is substituted with one or more of the following groups: amine group, or R 39 R 40 R 41 Si-amine group; b) an oxygen atom (O); c) a sulfur atom (S); d) N—CHR 8 —CR 9 ═CR 10 ; e) N—CHR 8 —C═CHR 10 ; f) N—CR 8 —CR 9 ═CHR 10 ; g) N—CHR 8 —CR 9 ═CHR 10 ; h) a H—N group; i) a tertiary amine group; and j) a R 42 R 43 R 44 SiN group;

R 39 , R 40 and R 41 are each independently selected from the group consisting of: (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 42 , R 43 and R 44 are each independently selected from the group consisting of (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 6 is (C 1 -C 18 ) alkyl substituted with an amine group which is a tertiary amine or a R 45 R 46 R 47 SiN group;

R 45 , R 46 and R 47 are each independently selected from the group consisting of (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 8 , R 9 , R 10 are each independently selected from the group consisting of hydrogen, (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 11 and R 12 are each at least divalent, and each independently selected from the group consisting (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

a is the number 2;

b is the number 0; and

where

(ib1) is a four valent silicon or tin atom selected from the group consisting of a (R ′″ ) t M group, a (R ′″ ) t M(X) p group, and a M(X) z —(O) x -M(X) z group, wherein

M is a tin or a silicon atom;

O is an oxygen atom;

X is a halide atom, an alkoxy group or a hydroxyl group (—OH group);

R′″ is a (C 1 -C 6 )-alkyl group;

z is the number 2;

x is the number 0 or 1;

t is the number 0 or 1;

p is the number 1 or 2; and

wherein the remaining free valences on M are each linked to an alpha-modified polymer macromolecule;

(ib2) is a group according to Formula 2A:

(R 24 O) q (R 25 ) r Si—R 29 —S—Si′R 26 R 27 R 28   Formula 2A

(ib3) is a group according to Formula 2B:

(R 24 O) q (R 25 ) r Si—R 29 —S—H  Formula 2B

(ib4) is a group according to Formula 2C:

(R 30 O) s (R 31 ) t Si—R 35 —N(H) u (Si′R 32 R 33 R 34 ) v   Formula 2C

(iib1) is a sulfanylsilane moiety according to Formula 4A:

(R 18 O) c (R 19 ) d Si—R 20 —S—Si′R 21 R 22 R 23   Formula 4A

(iib2) is a sulfanylsilane compound moiety according to Formula 4B:

(R 18 O) c (R 19 ) d Si—R 20 —S—H  Formula 4B

wherein,

Si and Si′ are each a silicon atom;

S is a sulfur atom;

O is an oxygen atom;

R 18 is hydrogen or (C 1 -C 6 ) alkyl;

R 19 is selected from the group consisting of hydrogen, (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 20 is a divalent group selected from the group consisting of a di-(C 2 -C 20 ) alkylether (alkyl-O-alkyl), an (C 6 -C 18 ) aryl, a (C 7 -C 18 ) alkylaryl, and a (C 1 -C 18 ) alkyl; where R 20 may be substituted with a substituent selected from the group consisiting of a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 7 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, a nitrile, an amine, —NO 2 , and a thioalkyl;

R 21 , R 22 and R 23 are each independently selected from the group consisting of hydrogen, (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 24 is hydrogen or (C 1 -C 6 ) alkyl;

R 25 , R 26 , R 27 and R 28 are each independently selected from the group consisting of hydrogen, (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 29 is a divalent group selected from the group consisting of a di-(C 2 -C 20 ) alkylether (alkyl-O-alkyl), a (C 6 -C 18 ) aryl, a (C 7 -C 18 ) alkylaryl, and a (C 1 -C 18 ) alkyl; where R 29 may be substituted with a substituent selected from the group consisting of a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 7 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, a nitrile, an amine, an NO 2 , and a thioalkyl;

R 30 is hydrogen or (C 1 -C 6 ) alkyl;

R 31 , R 32 , R 33 and R 34 are each independently selected from the group consisting of hydrogen, (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 35 is a divalent group selected from the group consisting of a di-(C 2 -C 20 ) alkylether (alkyl-O-alkyl), an (C 6 -C 18 ) aryl, a (C 7 -C 18 ) alkylaryl, and a (C 1 -C 18 ) alkyl; where R 35 may be substituted with a substituent selected from the group consisting of a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 7 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, a nitrile, an amine, —NO 2 , and a thioalkyl;

c is a number selected from 0, 1 and 2;

d is a number selected from 0, 1, and 2;

c+d=2;

q is the number 0 or 1;

r is the number 0 or 1;

q+r is 0 or 1;

s is the number 0 or 1;

t is the number 0 or 1;

s+t is 0 or 1;

u is the number 0, 1 or 2;

v is the number 0, 1 or 2;

u+v is 2; and

the remaining free valences of the four valent silicon atom are each linked to an alpha-modified polymer macromolecule.

2. The composition of claim 1 , wherein the amine group is selected from the group consisting of the Formula 1 D, Formula 1 E, and Formula 1 F.

3. The composition of claim 2 , wherein E is selected from the group consisting of (i) (C 1 -C 18 ) alkyl which is substituted with an amine group which is a tertiary amine, or R 39 R 40 R 41 Si-amine group; (ii) a tertiary amine group; (iii) a R 42 R 43 R 44 SiN group; (iv) an oxygen atom; (v) a sulfur atom; (vi) N—CHR 8 —CR 9 ═CR 10 ; (vii) N—CHR 8 —C═CHR 10 ; (viii) N—CR 8 —CR 9 ═CHR 10 ; (ix) N—CHR 8 —CR 9 ═CHR 10 ; and (x) a H—N group.

4. The composition of claim 2 , wherein E is a (C 1 -C 18 ) alkyl substituted with a tertiary amine group or R 42 R 43 R 44 SiN group.

5. The composition of claim 2 , wherein E is an oxygen atom (O) or a sulfur atom (S).

6. The composition of claim 2 , wherein E is N—CHR 8 —CR 9 ═CR 10 , N—CHR 8 —C═CHR 10 , N—CR 8 —CR 9 ═CHR 10 or N—CHR 8 —CR 9 ═CHR 10 .

7. The composition of claim 2 , wherein E is an H—N group or a R 42 R 43 R 44 SiN group.

8. The composition of claim 1 , further comprising an oil.

9. The composition of claim 1 , wherein the composition further comprises a filler.

10. The composition of claim 1 , wherein the at least one branched modified polymer macromolecule and the at least one linear modified polymer macromolecule each independently comprise a monomer unit derived from at least one monomer selected from the group consisting of butadiene, isoprene, styrene, alpha-methylstyrene, and combinations thereof.

11. The composition of claim 1 , wherein the composition further comprises a polymer selected from the group consisting of polybutadiene, butadiene-styrene copolymers, butadiene-isoprene copolymers, polyisoprene, and butadiene-styrene-isoprene terpolymers.

12. An article comprising at least one component formed from the composition of claim 1 , wherein the article is selected from the group consisting of a tire, a tire tread, a tire side wall, a tire carcass, a belt, a hose, a vibration damper, and a footwear component.

13. An article comprising at least one component formed from a vulcanized composition comprising the reaction product of the composition of claim 1 with a filler or a vulcanizing agent.

14. The article of claim 13 , wherein the article is selected from the group consisting of a tire, a tire tread, a tire side wall, a tire carcass, a belt, a hose, a vibration damper, and a footwear component.

15. A method for making a modified polymer, comprising:

A) reacting an amine polymerization initiator with a monomer in a polymerization solvent to form Composition A; where the amine polymerization initiator is selected from the group consisting of:

where

M is lithium, sodium or potassium;

N is a nitrogen atom;

C is carbon atom;

H is a hydrogen atom;

E comprises at least one heteroatom and is selected from the group consiting of an oxygen atom (O), a sulfur atom (S), N—CHR 8 —CR 9 ═C(M)R 10 , N—CHR 8 —C(M)═CHR 10 , N—C(M)R 8 —CR 9 ═CHR 10 , and N—CHR 8 —CR 9 ═CHR 10 ;

R 6 is (C 1 -C 18 ) alkyl substituted with an amine group which is a tertiary amine;

R 8 , R 9 , R 10 , R 12 are each independently selected from the group consisting of (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

a is the number 2; and

b is the number 0; and

the monomer is selected from the group consisting of butadiene, styrene, isoprene, and combinations thereof;

B) reacting Composition A with at least one coupling agent selected from the group consisting of SnCl 4 , (R 1 ) 3 SnCl, (R 1 ) 2 SnCl 2 , R 1 SnCl 3 , SiCl 4 , (R 1 ) 3 SiCl, (R 1 ) 2 SiCl 2 , R 1 SiCl 3 , Cl 3 Si—SiCl 3 , Cl 3 Si—O—SiCl 3 , Cl 3 Sn—SnCl 3 , Cl 3 Sn—O—SnCl 3 , Sn(OMe) 4 , Si(OMe) 4 , Sn(OEt) 4 , Si(OEt) 4 , (R 24 O) q (R 25 ) r Si—R 29 —S—Si′R 26 R 27 R 28 (Formula 2A), (R 30 O) s (R 31 ) t Si—R 35 —N(H) u (Si′R 32 R 33 R 34 ) v , (Formula 2C), and combinations thereof, to form Composition B;

where R 1 is a hydrocarbyl group;

Si and Si′ are silicon atoms;

S is a sulfur atom;

N is a nitrogen atom;

O is an oxygen atom;

H is a hydrogen atom;

R 24 and R 30 are each independently hydrogen or (C 1 -C 6 ) alkyl;

R 25 , R 26 , R 27 , R 28 , R 31 , R 32 , R 33 , and R 34 are the same or different, and are each independently selected from the group consisting of hydrogen, (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 29 and R 35 are each divalent groups independently selected from the group consisting of a di-(C 2 -C 20 ) alkylether (alkyl-O-alkyl), a (C 6 -C 18 ) aryl, a (C 7 -C 18 ) alkylaryl, and a (C 1 -C 18 ) alkyl; where each of R 29 and R 35 may independently be substituted with at least one substituent selected from the group consisting of (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 7 -C 16 ) aryl, (C 7 -C 16 ) aralkyl, an amine, and thioalkyl;

q and s are independently the number 2 or 3;

r and u are independently the number 0 or 1;

q+r=3; and

u+v=3;

C) reacting Composition B with at least one chain-end modifying agent of Formula 4C to form the modified polymer:

(R 18 O) c (R 19 ) d Si—R 20 —S—Si′(R 21 )(R 22 )R 23   (Formula 4C)

where

Si and Si′ are silicon atoms;

S is sulfur;

O is oxygen;

c is an integer selected from the group consisting of 1, 2 and 3;

d is an integer selected from the group consisting of 0, 1, and 2;

c+d=3;

R 18 is (C 1 -C 6 ) alkyl;

R 19 is selected from the group consisting of (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl;

R 20 is a divalent group selected from the group consisting of (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl, and (C 1 -C 18 ) alkyl; where R 20 may be substituted with at least one substituent selected from the group consisting of (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 7 -C 16 ) aryl, (C 7 -C 16 ) aralkyl, and thioalkyl;

R 21 , R 22 and R 23 are each independently selected from the group consisting of (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl, and (C 7 -C 18 ) aralkyl.