Granted Patent B2

US 12,410,264 · App. 17/761,384 · Granted Sep 9, 2025

Inventors: Yoshikazu Ueno (Kamisu, JP); Hiroshi Kanbara (Kamisu, JP); Atsushi Inatomi (Tsukuba, JP); Junya Takai (Tsukuba, JP); Zhaoming Ma (Tsukuba, JP)

Assignee: KURARAY CO., LTD.

C08C19/25C08C19/00C08C19/26C08L15/00

Abstract

Claims (60)

1. A method for producing a conjugated diene graft polymer in which a side chain (b) comprising a polymer comprising at least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit is bonded to a main chain (a) comprising a polymer comprising a conjugated diene unit, via a hetero atom Z serving as a branching point and having a valence of not less than 3, the method comprising:

(A-1) reacting an active end polymer represented by the following formula (I):

P—X  (I)

wherein P represents a polymer chain including at least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit, and X represents an active end of anionic polymerization;

with a functional group-modified conjugated diene polymer having, as a branched chain, a moiety comprising a functional group represented by the following formula (II) to thereby produce a conjugated diene graft polymer,

wherein V represents an alkoxy group or a hydroxyl group; Z is Si, Sn, Ge, Pb, P, B, or Al; R 1 represents a C 6-12 aryl group, a C 1-12 alkyl group, or a hydrogen atom; N represents the valence of Z; and n is an integer satisfying the following expression (1):

1≤ n≤N− 1  (1)

wherein V(s) may be the same or different when n is not less than 2; R 1 (s) may be the same or different when N-n-1 is not less than 2; and Z(s) may be the same or different when a plurality of the branched chains relative to the main chain are comprised; and

(B) recovering the conjugated diene graft polymer obtained.

2. The method of claim 1 , further comprising:

(A-2) at least partially deactivating at least one remaining functional group selected from the group consisting of an alkoxy group and a hydroxyl group in the conjugated diene graft polymer; before the recovering (B).

3. The method of claim 1 , wherein Z in the formula (II) is Si.

4. The method of claim 1 , wherein V in the formula (II) is an alkoxy group.

5. The method of claim 1 , wherein the average number of the side chains (b) bonded to one branching point is not less than 0.5.

6. A conjugated diene graft polymer composition, obtained by the method of claim 1 , the conjugated diene graft polymer, comprising:

a main chain (a) comprising, in polymerized form, a conjugated diene unit; and

a side chain (b) comprising a polymer comprising, in polymerized form, a conjugated diene unit and/or an aromatic vinyl compound unit;

wherein the side chain (b) is bonded to a main chain (a) via one hetero atom serving as a branching point and having a valence of not less than 3,

wherein the main chain (a) is bonded to the branching point directly or through a linking chain,

wherein the side chain (b) is directly bonded to the branching point,

wherein the hetero atom of the branching point comprises Si, Sn, Ge, Pb, P, B, and/or Al,

wherein a halogen content of a by-product in the composition, the byproduct comprising a lithium salt, is not more than 1000 ppm, and

wherein an average number X of a functional groups (c) directly bonded to the branching point per molecule of the conjugated diene graft polymer is in a range of from 0 to 10.

7. The polymer of claim 6 , wherein the by-product is lithium chloride.

8. A conjugated diene graft polymer composition, comprising:

a conjugated diene graft polymer, comprising: (a) a main chain comprising, in polymerized form, a conjugated diene unit; and (b) a side chain comprising, in polymerized form, a conjugated diene unit and/or an aromatic vinyl compound unit; and

a lithium salt,

wherein the side chain (b) of the conjugated diene graft polymer is bonded to the main chain (a) via one hetero atom serving as a branching point and having a valence of not less than 3,

wherein the main chain (a) is bonded to the branching point directly or through a linking chain,

wherein the side chain (b) is directly bonded to the branching point,

wherein the hetero atom of the branching point comprises Si, Sn, Ge, Pb, P, B, and/or Al,

wherein a halogen content of a by-product in the conjugated diene graft polymer composition, comprising the lithium salt, is not more than 1000 ppm, and

wherein an average number X of a functional groups (c) directly bonded to the branching point per molecule of the conjugated diene graft polymer is in a range of from 0 to 10.

9. The polymer of claim 8 , wherein the hetero atom as the branching point is Si.

10. The polymer of claim 8 , wherein the average number of the side chains (b) directly bonded to one branching point is not less than 0.5.

11. A polymer composition, comprising:

the conjugated diene graft polymer of claim 6 ; and

an additional polymer other than the conjugated diene graft polymer.

12. A molded product, comprising, in molded form:

the conjugated diene graft polymer composition of claim 6 .

13. The polymer of claim 8 , wherein the by-product is lithium chloride.

14. The polymer of claim 8 , wherein the halogen content of the by-product in the conjugated diene graft polymer composition is not more than 100 ppm.

15. A method for producing a conjugated diene graft polymer, the method comprising:

(A-1) reacting an active end polymer of formula (I):

P—X  (I)

P being a polymer chain comprising, in polymerized form, a conjugated diene unit and/or an aromatic vinyl compound unit, and X being an active end of anionic polymerization,

with a functional group-modified conjugated diene polymer comprising, as a branched chain, a moiety comprising a functional group of formula (II):

V being independently a C 1-5 alkoxy group or a hydroxyl group, Z independently being Si, P, or Al, R 1 independently being a C 6-12 aryl group, a C 1-12 alkyl group, or a hydrogen atom, N being a valence of Z, and n being an integer satisfying expression (1):

1≤ n≤N− 1  (1),

to thereby produce a conjugated diene graft polymer comprising a side chain (b) comprising a polymer comprising, in polymerized form, the conjugated diene unit and/or the aromatic vinyl compound unit, bonded to the main chain (a) via Z, a hetero atom serving as a branching point, the valence of Z being not less than 3 and identical to n, the main chain (a) comprising, in polymerized form, the conjugated diene unit; and

(B) recovering the conjugated diene graft polymer obtained.

16. The method of claim 15 , further comprising:

(A-2) at least partially deactivating at least one remaining functional group selected from the group consisting of an alkoxy group and a hydroxyl group in the conjugated diene graft polymer; before the recovering (B).

17. The method of claim 15 , wherein Z in the formula (II) is Si.

18. The method of claim 15 , wherein V in the formula (II) is an alkoxy group.

19. The method of claim 15 , wherein the average number of the side chains (b) bonded to one branching point is not less than 0.5.

20. The method of claim 15 , wherein

Z in the formula (II) is Si, and

V in the formula (II) is an alkoxy group, and

wherein the average number of the side chains (b) bonded to one branching point is not less than 0.5.

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (28)