Method for preparing terminal-modified conjugated diene polymer, terminal-modified conjugated diene polymer, rubber composition and tire

Patent metadata

Field	Value
Publication number	US-10131722-B2
Application number	US-201515503884-A
Country	US
Kind code	B2
Filing date	Jul 2, 2015
Priority date	Aug 20, 2014
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

This disclosure is to provide a method for preparing a terminal-modified conjugated diene polymer which achieves an extremely high compounding amount of cis-1,4 without complicated preparing conditions, a terminal-modified conjugated diene polymer obtained via the method, a rubber composition containing the terminal-modified conjugated diene polymer, and a tire using the rubber composition. This disclosure is A method for preparing a terminal-modified conjugated diene polymer comprising: polymerizing a conjugated diene compound by using a polymerization catalyst composition and modifying a polymer obtained via the polymerization by using a modifier, wherein the polymerization catalyst composition contains a rare earth element compound, and a coordination compound having a cyclopentadiene skeleton selected from substituted or unsubstituted cyclopentadienes, substituted or unsubstituted indenes, and substituted or unsubstituted fluorenes, and wherein the polymerization and modification is performed in a one-pot way.

First claim

The invention claimed is:

1. A method for preparing a terminal-modified conjugated diene polymer comprising: polymerizing a conjugated diene compound by using a polymerization catalyst composition and modifying a polymer obtained via the polymerization by using a modifier,
wherein the polymerization catalyst composition contains a rare earth element compound, and a coordination compound having a cyclopentadiene skeleton selected from substituted or unsubstituted cyclopentadienes, substituted or unsubstituted indenes, and substituted or unsubstituted fluorenes, and
wherein the polymerization and modification is performed in a one-pot way.

2. The method for preparing a terminal-modified conjugated diene polymer according to claim 1 , wherein the rare-earth element compound is represented by general formula (a-1):
M-(AQ 1 )(AQ 2 )(AQ 3 )  (a-1)

in the formula, M is scandium, yttrium or lanthanides; (AQ) 1 , (AQ) 2 and (AQ) 3 are the same or different functional groups having at least one M-A bonds, where A is nitrogen, oxygen or sulfur.

3. The method for preparing a terminal-modified conjugated diene polymer according to claim 1 , wherein the catalyst composition further contains a compound represented by general formula (X):
YR 31 a R 32 b R 33 c   (X)

in the formula, Y is a metallic element selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, R 31 and R 32 are C1 to C10 hydrocarbon groups or hydrogen atom, R 33 is a C1 to C10 hydrocarbon group, where R 31 , R 32 and R 33 may be the same or different from each other; in addition, in the case that Y is a metallic element selected from Group 1 of the Periodic Table, a=1 and b, c=0; in the case that Y is a metallic element selected from Group 2 and Group 12 of the Periodic Table, a, b=1 and c=0; and in the case that Y is a metallic element selected from Group 13 of the Periodic Table, a, b, c=1.

4. The method for preparing a terminal-modified conjugated diene polymer according to claim 1 , wherein the coordination compound having a cyclopentadiene skeleton has an indenyl group.

5. The method for preparing a terminal-modified conjugated diene polymer according to claim 1 , wherein the polymerization catalyst composition further contains an aluminoxane composition.

6. The method for preparing a terminal-modified conjugated diene polymer according to claim 1 , wherein the polymerization catalyst composition further contains a halogen compound.

7. The method for preparing a terminal-modified conjugated diene polymer according to claim 1 , wherein the modifier is at least one selected from the following compounds (a) to (j):
(a) is a compound represented by general formula (V):

where X 1 to X 5 each represent a monovalent functional group containing at least one selected from the group consisting of a hydrogen atom, a halogen atom, carbonyl groups, thiocarbonyl groups, isocyanate groups, thioisocyanate groups, epoxy groups, thioepoxy groups, halogenated silyl groups, hydrocarbyloxysilyl groups, and sulfonyloxy groups, and containing no active proton nor onium salt; X 1 to X 5 may be the same or different with proviso that at least one of X 1 to X 5 is not a hydrogen atom; R 1 to R 5 independently represent a single bond or a divalent C1 to C18 hydrocarbon group; and a plurality of aziridine rings may be bonded via any of X 1 to X 5 and R 1 to R 5 ;
(b) is a halogenated organic metal compound, halogenated metal compound, or organic metal compound represented by R 6 n M′Z 4-n , M′Z 4 , M′Z 3 , R 7 n M′(—R 8 —COOR 9 ) 4-n or R 7 n M′(—R 8 —COR 9 ) 4-n ,
where R 6 to R 8 may be the same or different and are each a C1 to C20 hydrocarbon group; R 9 is a C1 to C20 hydrocarbon group and optionally containing a carbonyl or ester group on a side chain; M′ is a tin, silicon, germanium, or phosphorus atom; Z is a halogen atom; and n is an integer of 0 to 3;
(c) is a heterocumulene compound containing a Y═C═Y′ bond in the molecule, where Y is a carbon, oxygen, nitrogen, or sulfur atom; and Y′ is an oxygen, nitrogen, or sulfur atom;
(d) is a heterotricyclic compound having a bond represented by general formula (VI):

where Y′ is an oxygen or sulfur atom;
(e) is a halogenated isocyano compound;
(f) is a carboxylic acid, acid halide, ester, carbonic ester, or acid anhydride represented by R 10 —(COOH) m , R 11 (COZ) m , R 12 —(COO—R 13 ), R 14 —OCOO—R 15 , R 16 —(COOCO—R 17 ) m , or general formula (VII):

where R 10 to R 18 may be the same or different and are each a C1 to C50 hydrocarbon group; Z is a halogen atom; and m is an integer of 1 to 5;
(g) is a carboxylic acid metal salt represented by R 19 k M″(OCOR 20 ) 4-k , R 21 k M″(OCO—R 22 —COOR 23 ) 4-k , or general formula (VIII):

where R 19 to R 25 may be the same or different and are each a C1 to C20 hydrocarbon group; M″ is a tin, silicon, or germanium atom; p=1; and k is an integer of 0 to 3;
(h) is an N-substituted aminoketone, an N-substituted aminothioketone, an N-substituted aminoaldehyde, an N-substituted aminothioaldehyde, or a compound having a C-(=M)-N<bond in the molecule, where M represents an oxygen or sulfur atom;
(i) is a compound having a N≡C— bond; and
(j) is a compound having a phosphate residue represented by general formula (I):

in general formula (I), R 1 and R 2 independently represent a monovalent hydrocarbon group selected from straight or branched chain C1 to C20 alkyl groups, monovalent C3 to C20 alicyclic hydrocarbon groups and monovalent C6 to C20 aromatic hydrocarbon groups, or a hydrogen atom.

Assignees

• Bridgestone Corp

Inventors

• Hirata Narukuni
• Yamagata Yusuke
• Tanabe Tomoe
• Kaita Shojiro

Classifications

• C08F8/18

  Introducing halogen atoms or halogen-containing groups · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title

• C08F8/40

  Introducing phosphorus atoms or phosphorus-containing groups · CPC title

• C08F36/02 Primary

  the radical having only two carbon-to-carbon double bonds · CPC title

• C08J2353/02

  of vinyl aromatic monomers and conjugated dienes · CPC title