Conjugated diene polymer, process for its production and rubber compositions containing the same
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08C-019/25
C08C-019/34
C08F-036/04
출원번호
UP-0496983
(2002-11-27)
등록번호
US-7781533
(2010-09-13)
우선권정보
JP-2001-361354(2001-11-27)
국제출원번호
PCT/JP2002/012390
(2002-11-27)
§371/§102 date
20041105
(20041105)
국제공개번호
WO03/046020
(2003-06-05)
발명자
/ 주소
Ozawa, Youichi
Kondou, Hajime
Endou, Noriko
출원인 / 주소
Bridgestone Corporation
대리인 / 주소
Sughrue Mion, PLLC
인용정보
피인용 횟수 :
7인용 특허 :
4
초록▼
A process for producing a conjugated diene-based polymer which comprises, in the first modification, modifying a conjugated diene-based polymer having active chain ends, which is obtained by polymerizing a diene-based monomer singly or with other monomers and has a content of a cis-1,4 unit of 75% b
A process for producing a conjugated diene-based polymer which comprises, in the first modification, modifying a conjugated diene-based polymer having active chain ends, which is obtained by polymerizing a diene-based monomer singly or with other monomers and has a content of a cis-1,4 unit of 75% by mole or greater in the conjugated diene portion of the main chain, by reacting the active chain ends with a hydrocarbyloxysilane compound and reacting the modified polymer with a specific compound such as a hydrocarbyloxysilane compound, and a rubber composition containing the polymer modified in accordance with the above process and, preferably, 10 to 100 parts by weight of silica and/or carbon black per 100 parts by weight of the rubber component containing the modified polymer, are provided. The rubber composition containing silica and/or carbon black exhibits improved fracture properties, abrasion resistance, low heat buildup property and excellent workability. A process for producing a conjugated diene-based polymer exhibiting improved cold flow, a polymer produced in accordance with the process, and a rubber composition and a tire using the polymer are also provided.
대표청구항▼
The invention claimed is: 1. A process for producing a conjugated diene-based polymer which comprises conducting a first modification of a conjugated diene-based polymer having active chain ends, which is obtained by polymerizing a diene-based monomer singly or in combination with other monomers an
The invention claimed is: 1. A process for producing a conjugated diene-based polymer which comprises conducting a first modification of a conjugated diene-based polymer having active chain ends, which is obtained by polymerizing a diene-based monomer singly or in combination with other monomers and has a content of a cis-1,4 unit of 75% by mole or greater in a conjugated diene portion of a main chain, by bringing the active chain ends into reaction with a hydrocarbyloxysilane compound, and conducting a second modification of a polymer obtained by the first modification by adding a hydrocarbyloxysilane compound in a presence of a condensation accelerator, further comprising bringing a polymer obtained by the second modification into reaction with a partial ester of a polyhydric alcohol with a carboxylic acid. 2. A process for producing a conjugated diene-based polymer which comprises conducting a first modification of a conjugated diene-based polymer having active chain ends, which is obtained by polymerizing a diene-based monomer singly or in combination with other monomers and has a content of a cis-1,4 unit of 75% by mole or greater in a conjugated diene portion of a main chain, by bringing the active chain ends into reaction with a hydrocarbyloxysilane compound, and bringing a polymer obtained by the first modification into reaction with a partial ester of a polyhydric alcohol with a carboxylic acid; wherein a polymerization catalyst used for the polymerization to obtain the conjugated diene-based polymer having active chain ends comprises a combination of at least one compound selected from each of elements shown in (A), (B) and (C): (A) Rare earth compounds selected from following (A1) to (A4), which may be directly used as a solution in an inert organic solvent or in a form supported with an inert solid, (A1) Compounds of rare earth elements having an oxidation number of 3 and having three ligands selected from carboxyl groups having 2 to 30 carbon atoms, alkoxyl groups having 2 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms and α,γ-diketonyl groups having 5 to 30 carbon atoms and complex compounds of these compounds with Lewis base compounds; (A2) Complex compounds of trihalides of rare earth elements with Lewis acids; (A3) Organic compounds of rare earth elements having an oxidation number of 3 in which at least one (substituted) allyl group is directly bonded to a rare earth atom; and (A4) Organic compounds of rare earth elements having an oxidation number of 2 or 3 and having at least one (substituted) cyclopentadienyl group directly bonded to a rare earth atom and reaction products of the organic rare earth compounds and trialkylaluminums or ionic compounds comprising a non-coordinating anion and a counter cation; (B) Organoaluminum compounds selected from compounds shown in (B1) to (B3); (B1) Trihydrocarbylaluminum compounds represented by a formula R123Al, wherein R12 represents a hydrocarbon group having 1 to 30 carbon atoms and may represent a same group or different groups; (B2) Hydrocarbylaluminum hydride represented by a formula R132AlH or R13AlH2, wherein R13 represents a hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R13 may represent a same group or different groups when the plurality of R13 are present; and (B3) Hydrocarbylaluminoxane compound having hydrocarbon groups having 1 to 20 carbon atoms; and (C) Compounds selected from compounds shown in (C1) to (C4): (C1) Inorganic and organic compounds of elements of Groups II, III and IV having at least one hydrolyzable halogen atom and complex compounds thereof with Lewis bases; (C2) Organic halogen compounds having at least one structure selected from tertiary alkyl halides, benzyl halides and allyl halides; (C3) Zinc halides and complex compounds thereof with Lewis acids; and (C4) Ionic compounds comprising a non-coordinating anion and a counter cation; the element shown in (C) being not essential when element (A) comprises a halogen or a non-coordinating anion or element (B) comprises an aluminoxane. 3. A process for producing a conjugated diene-based polymer which comprises conducting a first modification of a conjugated diene-based polymer having active chain ends, which is obtained by polymerizing a diene-based monomer singly or in combination with other monomers and has a content of a cis-1,4 unit of 75% by mole or greater in a conjugated diene portion of a main chain, by bringing the active chain ends into reaction with a hydrocarbyloxysilane compound, adding a condensation accelerator, and conducting condensation of a residue group of the hydrocarbyloxysilane compound introduced at the active chain ends and the unreacted hydrocarbyloxysilane compound. 4. A process for producing a conjugated diene-based polymer according to claim 3, which further comprises bringing a polymer obtained by the condensation into reaction with a partial ester of a polyhydric alcohol with a carboxylic acid. 5. A process for producing a conjugated diene-based polymer according to any one of claims 1 to 3 and 4, wherein at least one of hydrocarbyloxysilane compounds represented by general formula (I) and partial condensation products thereof is used as the hydrocarbyloxysilane compound, general formula (I) being: wherein A1 represents a monovalent group having at least one functional group selected from (thio)epoxy group, (thio)isocyanate group, (thio)ketone group, (thio)aldehyde group, imine group, amide group, trihydrocarbyl ester group of isocyanuric acid, (thio)carboxylic acid ester groups, alkali metal salts and alkaline earth metal salts of (thio)carboxylic acid ester groups, carboxylic acid anhydride groups, carboxylic acid halide groups and dihydrocarbyl ester groups of carbonic acid; R1 represents a single bond or a divalent inert hydrocarbon group, R2 and R3 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; n represents an integer of 0 to 2; a plurality of OR3 may represent a same group or different groups when the plurality of OR3 are present; and no active protons nor onium salts are present in a molecule. 6. A process for producing a conjugated diene-based polymer according to any one of claims 1 to 3 and 4, wherein at least one of hydrocarbyloxysilane compounds represented by general formula (II) and partial condensation products thereof is used in combination with the hydrocarbyloxysilane compound represented by general formula (I), general formula (II) being: wherein A2 represents a monovalent group having at least one functional group selected from cyclic tertiary amine groups, acyclic tertiary amine groups, pyridine groups, sulfide groups, polysulfide groups and nitrile groups; R4 represents a single bond or a divalent inert hydrocarbon group, R5 and R6 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic group having 6 to 18 carbon atoms; m represents an integer of 0 to 2; a plurality of OR6 may represent a same group or different groups when the plurality of OR6 are present; and no active protons nor onium salts are present in a molecule. 7. A process for producing a conjugated diene-based polymer according to any one of claims 1, 2, and 4, wherein the partial ester of a carboxylic acid with a polyhydric alcohol is a monoester, a diester or a triester of a fatty acid and sorbitan. 8. A process for producing a conjugated diene-based polymer according to any one of claims 1 and 3, wherein the condensation accelerator comprises at least one compound selected from a group consisting of metal compounds shown in (1) to (3) and water, (1) to (3) being: (1) Salts of tin having an oxidation number of 2 with carboxylic acids having 3 to 30 carbon atoms represented by a following general formula: Sn(OCOR10)2 wherein R10 represents an organic group having 2 to 19 carbon atoms, and a plurality of R10 may represent a same group or different groups when the plurality of R10 are present; (2) Compounds of tin having an oxidation number of 4 and represented by a following general formula: R11rSnA4tB1(4−t−r) wherein r represents an integer of 1 to 3, t represents an integer of 1 or 2 and t+r represents an integer of 3 or 4; R11 represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms; B1 represents hydroxyl group or a halogen atom; and A4 represents a group selected from (a) carboxyl groups having 2 to 30 carbon atoms, (b) α,γ-dionyl groups having 5 to 30 carbon atoms, (c) hydrocarbyloxyl groups having 3 to 30 carbon atoms and (d) siloxyl groups having three substituents which are selected from hydrocarbyl groups having 1 to 20 carbon atoms and hydrocarbyloxyl groups having 1 to 20 carbon atoms, the three substituents being same with or different from each other, and a plurality of A4 may represent a same group or different groups when the plurality of A4 are present; and (3) Compounds of titanium having an oxidation number of 4 and represented by a following general formula: A5xTiB2(4−x) wherein x represents an integer of 2 or 4; A5 represents (a) a hydrocarbyloxyl group having 3 to 30 carbon atoms or (b) a siloxyl group having three substituents which are selected from alkyl groups having 1 to 30 carbon atoms and hydrocarbyloxyl groups having 1 to 20 carbon atoms, and a plurality of A5 may represent a same group or different groups when the plurality of A5 are present; and B2 represents an α,γ-dionyl group having 5 to 30 carbon atoms. 9. A process for producing a conjugated diene-based polymer according to any one of claims 1, 3 and 4, wherein a polymerization catalyst used for the polymerization to obtain the conjugated diene-based polymer having active chain ends comprises a combination of at least one compound selected from each of elements shown in (A), (B) and (C): (A) Rare earth compounds selected from following (A1) to (A4), which may be directly used as a solution in an inert organic solvent or in a form supported with an inert solid, (A1) Compounds of rare earth elements having an oxidation number of 3 and having three ligands selected from carboxyl groups having 2 to 30 carbon atoms, alkoxyl groups having 2 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms and α,γ-diketonyl groups having 5 to 30 carbon atoms and complex compounds of these compounds with Lewis base compounds; (A2) Complex compounds of trihalides of rare earth elements with Lewis acids; (A3) Organic compounds of rare earth elements having an oxidation number of 3 in which at least one (substituted) allyl group is directly bonded to a rare earth atom; and (A4) Organic compounds of rare earth elements having an oxidation number of 2 or 3 and having at least one (substituted) cyclopentadienyl group directly bonded to a rare earth atom and reaction products of the organic rare earth compounds and trialkylaluminums or ionic compounds comprising a non-coordinating anion and a counter cation; (B) Organoaluminum compounds selected from compounds shown in (B1) to (B3): (B1) Trihydrocarbylaluminum compounds represented by a formula R123Al, wherein R12 represents a hydrocarbon group having 1 to 30 carbon atoms and may represent a same group or different groups; (B2) Hydrocarbylaluminum hydride represented by a formula R132AlH or R13 AlH2, wherein R13 represents a hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R13 may represent a same group or different groups when the plurality of R13 are present; and (B3) Hydrocarbylaluminoxane compound having hydrocarbon groups having 1 to 20 carbon atoms; and (C) Compounds selected from compounds shown in (C1) to (C4): (C1) Inorganic and organic compounds of elements of Groups II, III and IV having at least one hydrolyzable halogen atom and complex compounds thereof with Lewis bases; (C2) Organic halogen compounds having at least one structure selected from tertiary alkyl halides, benzyl halides and allyl halides; (C3) Zinc halides and complex compounds thereof with Lewis acids; and (C4) Ionic compounds comprising a non-coordinating anion and a counter cation; the element shown in (C) being not essential when element (A) comprises a halogen or a non-coordinating anion or element (B) comprises an aluminoxane. 10. A process for producing a conjugated diene-based polymer according to any one of claims 2 and 9, wherein the rare earth element is at least one element selected from a group consisting of lanthanum, neodymium, praseodymium, samarium and gadolinium. 11. A process for producing a conjugated diene-based polymer according to any one of claims 1 to 3 and 4, wherein the conjugated diene-based polymer is at least one polymer selected from the group consisting of polybutadiene, polyisoprene and copolymers of butadiene with other conjugated dienes.
연구과제 타임라인
LOADING...
LOADING...
LOADING...
LOADING...
LOADING...
이 특허에 인용된 특허 (4)
Takeichi Hideo,JPX ; Graves Daniel F. ; Sarkar Sunil B. ; Lawson David F. ; Hergenrother William L. ; Cole William M. ; Oziomek James, Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds.
Krumbe, Wolfgang; Feller, Rolf; Wagner, Paul; Paul, Hanns-Ingolf; Siebuerger, Martin; Kloppenburg, Heike; Le-Sattler, Alicia; Lovegrove, John, Process for the production of water and solvent-free polymers.
※ AI-Helper는 부적절한 답변을 할 수 있습니다.