Amino silane-modified polymers

Patent metadata

Field	Value
Publication number	US-9458253-B2
Application number	US-201214427021-A
Country	US
Kind code	B2
Filing date	Sep 14, 2012
Priority date	Sep 14, 2012
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

Modified macromolecular compounds obtainable by using specific amino silane polymerization initiator compounds and optionally chain end-modifying compounds are described. Polymer compositions including such modified macromolecular compounds and the use of such compositions in the preparation of vulcanized (crosslinked) elastomeric polymer compositions and articles are described.

First claim

The invention claimed is:

1. A modified macromolecular compound of the following Formula A:

wherein
R 3 and R 4 are each independently selected from —OH, (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl;
R 5 and R 6 are each independently selected from hydrogen, (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl;
P is an elastomeric diene polymer chain comprising monomer units derived from at least one of the following monomers: butadiene, isoprene, styrene and alpha-methylstyrene; and
K represents a hydrogen atom or

wherein
R 1 is independently selected from a hydrogen atom and (C 1 -C 4 ) alkyl;
R 2 is independently selected from (C1-C18) alkyl;
Y is at least divalent and is (C1-C18) alkyl, which may be substituted with one or more of the following groups: tertiary amine group, silyl group, (C7-C18) aralkyl group and (C6-C 18 ) aryl group; and
Z represents hydrogen or

wherein
M 1 is a silicon atom or a tin atom; R 7 and R 8 are independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl; and T represents R 11 or

wherein
Y is as defined above;
R 9 is independently selected from (C 1 -C 18 ) alkyl;
R 10 is independently selected from a hydrogen atom and (C 1 -C 4 ) alkyl;
R 11 is selected from (C1-C18) alkyl, (C6-C18) aryl and (C7-C18) aralkyl; and
D represents OR 1 or

wherein
R 1 , P, R 3 , R 4 , R 5 and R 6 are as defined above; and
p and o are each independently selected from an integer of 1, 2 and 3; m, n, t and u are each independently selected from an integer of 0, 1 and 2; and wherein p is 1 if K is H and otherwise p+m+n=3 and t+u+o=3.

2. The modified macromolecular compound according to claim 1 , which has the following Formula 1:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Y, P and Z; and n, m and p are as defined in claim 1 .

3. The modified macromolecular compound according to claim 2 , wherein R 3 is selected from —OH and (C 1 -C 18 ) alkyl; Z is represented by —M 1 (R 7 )(R 8 )(T); M 1 is a silicon atom or a tin atom; R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl; and T is represented by

wherein Y, R 9 , R 10 and D, and t, u and o are as defined in claim 1 .

4. The modified macromolecular compound according to claim 2 , wherein R 3 is selected from —OH and (C 1 -C 18 ) alkyl; Z is represented by —M 1 (R 7 )(R 8 )(T); M 1 is a silicon atom or a tin atom; R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl; and T is represented by R 11 , wherein R 11 is selected from (C 1 -C 18 ) alkyl.

5. The modified macromolecular compound according to claim 1 , wherein M 1 is a silicon atom.

6. The modified macromolecular compound according to claim 1 , wherein M 1 is a tin atom.

7. The modified macromolecular compound according to claim 1 , wherein Y is divalent and is (C 1 -C 18 ) alkyl.

8. The modified macromolecular compound according to claim 1 , wherein R 3 and R 4 are each independently selected from —OH and (C 1 -C 18 ) alkyl; R 5 and R 6 are each independently selected from hydrogen and (C 1 -C 18 ) alkyl; and R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl.

9. The modified macromolecular compound according to claim 8 , wherein R 3 , R 4 , R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl; and R 5 and R 6 are each independently selected from hydrogen and (C 1 -C 18 ) alkyl.

10. The modified macromolecular compound according to claim 1 , wherein p and o are each independently selected from an integer of 1 and 2; m and u are each independently selected from an integer of 2 and 3; and n and t are each independently selected from and integer of 0 and 1.

11. A method of making the modified macromolecular compound as defined in claims 1 , comprising the steps of:
(i) polymerizing in solution at least one elastomeric diene monomer with at least one amino silane polymerization initiator compound of Formula 4 or Formula 5

or Lewis base adducts thereof, wherein
R 3a is independently selected from —N(R 28 )R 29 , (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl;
R 4a is independently selected from —N(R 30 )R 31 , (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl;
R 5 and R 6 are as defined in claim 1 ;
M 2 is lithium, sodium or potassium;
R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently selected from hydrogen, (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl;
R 26 , R 27 , R 28 , R 29 , R 30 and R 31 are each independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl;
q is selected from an integer of 1, 2, 3, 4 and 5; and
r is selected from an integer of 1, 2 and 3;
(ii) optionally reacting the polymer resulting from step (i) in solution with a chain end-modifying compound of Formula 6

wherein
R 1a is independently selected from (C 1 -C 4 ) alkyl;
R 2 is independently selected from (C 1 -C 18 ) alkyl;
R 7 and R 8 are independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) aralkyl;
Y is at least divalent and is (C 1 -C 18 ) alkyl, which may be substituted with one or more of the following groups: tertiary amine group, silyl group, (C 7 -C 18 ) aralkyl group and (C 6 -C 18 ) aryl group; R 2 , R 7 , R 8 and n are as defined above;
M 1 is a silicon atom or a tin atom;
n is an integer selected from 0, 1 and 2; s is an integer selected from 1, 2 and 3; and n+s=3; and
T represents R 11 or

wherein
Y is as defined above;
R 9 is independently selected from (C 1 -C 18 ) alkyl;
R 10a is independently selected from (C 1 -C 4 ) alkyl;
t is an integer selected from 0, 1 and 2; v is an integer selected from 1, 2 and 3; and t+v=3; and
contacting the polymer resulting from step (i) or (ii) with water.

12. The method according to claim 11 , further comprising the following step for making the amino silane polymerization initiator compound of Formula 4 or Formula 5:
(ia) reacting a compound of the following Formula 9

wherein
X is a chlorine atom, a bromine atom or a iodine atom; and
R 3a , R 4a , R 5 , R 6 , R 26 and R 27 are as defined in claim 11 ;
an alkali metal selected from lithium, sodium and potassium; and
a compound selected from Formula 10 and Formula 11

Assignees

• Döring Christian
• Knoll Susanne
• Heidenreich Daniel
• Thiele Sven
• Trinseo Europe Gmbh

Inventors

• Döring Christian
• Knoll Susanne
• Heidenreich Daniel
• Thiele Sven

Classifications

• C08C19/44

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title

• C08L9/06

  Copolymers with styrene · CPC title

• C08L9/00

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title

• C08L15/00

  Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) · CPC title

• C08F4/46

  selected from alkali metals · CPC title