Modified conjugated diene-based polymer, production method thereof, rubber composition and tire

Patent metadata

Field	Value
Publication number	US-11091609-B2
Application number	US-201716326533-A
Country	US
Kind code	B2
Filing date	Aug 9, 2017
Priority date	Aug 19, 2016
Publication date	Aug 17, 2021
Grant date	Aug 17, 2021

Abstract

A modified conjugated diene-based polymer having a nitrogen atom, whereina content of the nitrogen atom is 25 mass ppm or more based on a total amount of the modified conjugated diene-based polymer,a shrinking factor (g′) is 0.59 or less in a GPC-light scattering measurement method with a viscosity detector, anda weight average molecular weight is 200,000 or more and 3,000,000 or less.

First claim

The invention claimed is:

1. A modified conjugated diene-based polymer having a nitrogen atom, wherein
a content of the nitrogen atom is 25 mass ppm or more based on a total amount of the modified conjugated diene-based polymer,
a shrinking factor (g′) is 0.59 or less in a GPC-light scattering measurement method with a viscosity detector,
a weight average molecular weight is 200,000 or more and 3,000,000 or less, and
a branching degree is 8 or more.

2. The modified conjugated diene-based polymer according to claim 1 , wherein a Mooney stress relaxation measured at 110° C. is 0.45 or less.

3. The modified conjugated diene-based polymer according to claim 2 , wherein a modification ratio is 75% by mass or more based on a total amount of a conjugated diene-based polymer and a branching degree is 8 or more.

4. The modified conjugated diene-based polymer according to claim 3 , represented by the following general formula (I):

wherein D 1 represents a conjugated diene-based polymer chain having a nitrogen atom; R 1 to R 3 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms; R 4 and R 7 each independently represent an alkyl group having 1 to 20 carbon atoms; R 5 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 6 and R 10 each independently represent an alkylene group having 1 to 20 carbon atoms; R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; m and x each independently represent an integer of 1 to 3 as long as being x≤m; p represents 1 or 2; y represents an integer of 1 to 3, and y≤(p+1); z represents an integer of 1 or 2; each of D 1 , R 1 to R 11 , m, p, x, y and z, if present in a plural number, is respectively independent and may be the same as or different from each other as long as satisfying x≤m and y≤(p+1); i represents an integer of 0 to 6; j represents an integer of 0 to 6; k represents an integer of 0 to 6; (i+j+k) is an integer of 4 to 10; ((x×i)+(y×j)+(z×k)) is an integer of 8 to 30; and A represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom and a phosphorous atom, and not having an active hydrogen

wherein A in the formula (I) is represented by any one of the following general formulae (II) to (V):

wherein B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms; a represents an integer of 1 to 10; and B 1 , if present in a plural number, is respectively independent;

wherein B 2 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms; B 3 represents an alkyl group having 1 to 20 carbon atoms; a represents an integer of 1 to 10; and each of B 2 and B 3 , if present in a plural number, is respectively independent;

wherein B 4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms; a represents an integer of 1 to 10; and B 4 , if present in a plural number, is respectively independent; and

wherein B 5 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms; a represents an integer of 1 to 10; B 5 , if present in a plural number, is respectively independent.

5. A method for producing the modified conjugated diene-based polymer according to claim 3 , comprising:
a polymerization step of polymerizing at least a conjugated diene compound in the presence of an organolithium compound having at least one nitrogen atom in a molecule, or copolymerizing at least a conjugated diene compound and a copolymerizable monomer having at least one nitrogen atom in a molecule in the presence of an organolithium compound to give a nitrogen-containing conjugated diene-based polymer; and
a modification step of modifying the nitrogen-containing conjugated diene-based polymer with a modifier having at least three silicon atoms and at least one nitrogen atom in one molecule and 8 or more reaction active sites.

6. A tire comprising a rubber composition comprising a rubber component and a filler in an amount of 5.0 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the rubber component,
wherein the rubber component comprises the modified conjugated diene-based polymer according to claim 3 in an amount of 10% by mass or more based on a total amount of the rubber component.

7. The modified conjugated diene-based polymer according to claim 1 , wherein a modification ratio is 75% by mass or more based on a total amount of a conjugated diene-based polymer.

8. The modified conjugated diene-based polymer according to claim 1 , wherein
a plurality of conjugated diene-based polymer chains are bonded to a modifier, and
the modified conjugated diene-based polymer has a nitrogen atom in at least one of the conjugated diene-based polymer chains and has a silicon atom in a modifier residue.

9. The modified conjugated diene-based polymer according to claim 1 , represented by the following general formula (I):

wherein D 1 represents a conjugated diene-based polymer chain having a nitrogen atom; R 1 to R 3 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms; R 4 and R 7 each independently represent an alkyl group having 1 to 20 carbon atoms; R 5 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 6 and R 10 each independently represent an alkylene group having 1 to 20 carbon atoms; R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; m and x each independently represent an integer of 1 to 3 as long as being x≤m; p represents 1 or 2; y represents an integer of 1 to 3, and y≤(p+1); z represents an integer of 1 or 2; each of D 1 , R 1 to R 11 , m, p, x, y and z, if present in a plural number, is respectively independent and may be the same as or different from each other as long as satisfying x≤m and y≤(p+1); i represents an integer of 0 to 6; j represents an integer of 0 to 6; k represents an integer of 0 to 6; (i+j+k) is an integer of 4 to 10; ((x×i)+(y×j)+(z×k)) is an integer of 8 to 30; and A represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom and a phosphorous atom, and not having an active hydrogen.

10. The modified conjugated diene-based polymer according to claim 9 , wherein A in the formula (I) is represented by any one of the following general formulae (II) to (V):

wherein B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms; a represents an integer of 1 to 10; and B 1 , if present in a plural number, is respectively independent;

wherein B 2 represen

Assignees

• Asahi Chemical Ind

Inventors

• Kyo Miki
• Hisamura Kenta

Classifications

• C08C19/085

  Devulcanisation · CPC title

• C08C19/00

  Chemical modification of rubber · CPC title

• C08K3/06

  Sulfur · CPC title

• C08L19/006

  Rubber characterised by functional groups, e.g. telechelic diene polymers · CPC title

• C08L91/00

  Compositions of oils, fats or waxes; Compositions of derivatives thereof · CPC title