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WO2021049909A1 - Polymère à base de diène conjugué modifié, son procédé de production et composition de caoutchouc le comprenant - Google Patents

Polymère à base de diène conjugué modifié, son procédé de production et composition de caoutchouc le comprenant Download PDF

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Publication number
WO2021049909A1
WO2021049909A1 PCT/KR2020/012316 KR2020012316W WO2021049909A1 WO 2021049909 A1 WO2021049909 A1 WO 2021049909A1 KR 2020012316 W KR2020012316 W KR 2020012316W WO 2021049909 A1 WO2021049909 A1 WO 2021049909A1
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WO
WIPO (PCT)
Prior art keywords
conjugated diene
polymer
modified conjugated
group
based polymer
Prior art date
Application number
PCT/KR2020/012316
Other languages
English (en)
Korean (ko)
Inventor
오정환
유석준
이희승
최재선
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020200116392A external-priority patent/KR102604539B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to BR112021014723A priority Critical patent/BR112021014723A2/pt
Priority to US17/420,235 priority patent/US12110353B2/en
Priority to EP20863524.3A priority patent/EP3889193B1/fr
Priority to SG11202107480YA priority patent/SG11202107480YA/en
Priority to JP2021543236A priority patent/JP7225418B2/ja
Priority to CN202080008076.2A priority patent/CN113316596B/zh
Publication of WO2021049909A1 publication Critical patent/WO2021049909A1/fr
Priority to US18/815,403 priority patent/US20240417500A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/08—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen

Definitions

  • the present invention relates to a modified conjugated diene polymer having excellent processability and excellent tensile strength and viscoelastic properties, a method for preparing the same, and a rubber composition including the same.
  • conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization, and are used as rubber for tires. .
  • SBR styrene-butadiene rubber
  • BR butadiene rubber
  • MV R [(MV f -MV i ) / MV i ] x 100
  • the modified conjugated diene-based polymer according to the present invention contains Si atoms and N atoms in the molecule, the content of the N atoms is 150 ppm or more based on the total weight of the polymer, and the Mooney viscosity change rate according to Equation 1 is 20% or less. By satisfying the conditions at the same time, it is possible to have excellent filler affinity and excellent mechanical properties.
  • the Mooney viscosity change rate may be an index indicating that the increase in Mooney viscosity occurring during storage after production is small as well as processability.
  • the polymer according to the present invention includes a second chain containing an N-functional group-containing monomer and Due to the structural characteristics in which the alkoxysilane-based compound and the first chain of the polymer are bonded to a specific structure, processability is improved, and even when stored for a long time, the change in Mooney viscosity is low, and storage stability may be excellent.
  • R 11a and R 11b are each independently an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms; Or a functional group represented by the following formula 3a,
  • R 11c is an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms; Vinyl group; Or a functional group represented by the following formula 3a,
  • the living end of the macromonomer reacts with the Si-OR group of the modifier to form a Si-C bond, and this bond is hydrolyzed like a condensation bond. Since it is a bond in which a reaction does not occur, there is no fear of separation, and accordingly, storage stability is improved and there is no problem of loss of the initially introduced functional group.
  • Example 1 in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent, 3,3,7,7-tetra Methoxy-5,5-bis((trimethoxysilyl)methyl)-2,8-dioxa-3,7-disilanonane (3,3,7,7-tetramethoxy-5,5-bis(( trimethoxysilyl)methyl)-2,8-dioxa-3,7-disilanonane) was added ([denaturant]:[act.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through GPC (Gel permeation Chromatography) analysis, and a molecular weight distribution curve was obtained.
  • the molecular weight distribution (PDI, MWD, Mw/Mn) was obtained by calculating from the measured molecular weights.
  • the GPC is used by combining two columns of PLgel Olexis (Polymer Laboratories) and one column of PLgel mixed-C (Polymer Laboratories), and when calculating the molecular weight, the GPC standard material is PS (polystyrene). It was carried out using.
  • the GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran.
  • Each modified or unmodified conjugated diene-based polymer of Examples, Comparative Examples and Reference Examples was used as a raw material rubber and was blended under the blending conditions shown in Table 2 below.
  • the content of the raw materials in Table 2 is each part by weight based on 100 parts by weight of the raw rubber.
  • the tan ⁇ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60°C ⁇ 60°C) in Film Tension mode using a dynamic mechanical analyzer (GABO).
  • GBO dynamic mechanical analyzer
  • MV-2000 (ALPHA Technologies, Inc.) was used at 100°C with a Rotor Speed of 2 ⁇ 0.02 rpm, and a Large Rotor was used, and each of the primary formulations was left at room temperature (23 ⁇ 3°C) for 30 minutes or more, and then 27 ⁇ 3 g was collected, filled inside the die cavity, and measured for 4 minutes by operating the platen.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un polymère à base de diène conjugué modifié qui présente une excellente résistance à la traction et des caractéristiques viscoélastiques ainsi qu'une excellente aptitude au traitement, et une composition de caoutchouc la comprenant, le polymère à base de diène conjugué modifié contenant des atomes Si et des atomes N et ayant une teneur en atomes N de 150 ppm ou plus en termes de poids et un changement de viscosité Mooney (MVR) de 20 % ou moins.
PCT/KR2020/012316 2019-09-11 2020-09-11 Polymère à base de diène conjugué modifié, son procédé de production et composition de caoutchouc le comprenant WO2021049909A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BR112021014723A BR112021014723A2 (pt) 2019-09-11 2020-09-11 Polímero à base de dieno conjugado modificado, método para preparar o mesmo e composição de borracha incluindo o mesmo
US17/420,235 US12110353B2 (en) 2019-09-11 2020-09-11 Modified conjugated diene-based polymer, method for preparing the same and rubber composition including the same
EP20863524.3A EP3889193B1 (fr) 2019-09-11 2020-09-11 Polymère à base de diène conjugué modifié, son procédé de production et composition de caoutchouc le comprenant
SG11202107480YA SG11202107480YA (en) 2019-09-11 2020-09-11 Modified conjugated diene-based polymer, method for preparing the same and rubber composition including the same
JP2021543236A JP7225418B2 (ja) 2019-09-11 2020-09-11 変性共役ジエン系重合体、その製造方法、およびそれを含むゴム組成物
CN202080008076.2A CN113316596B (zh) 2019-09-11 2020-09-11 改性共轭二烯类聚合物、其制备方法和包含其的橡胶组合物
US18/815,403 US20240417500A1 (en) 2019-09-11 2024-08-26 Modified Conjugated Diene-Based Polymer, Method for Preparing the Same and Rubber Composition Including the Same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2019-0113004 2019-09-11
KR20190113004 2019-09-11
KR10-2020-0116392 2020-09-10
KR1020200116392A KR102604539B1 (ko) 2019-09-11 2020-09-10 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US17/420,235 A-371-Of-International US12110353B2 (en) 2019-09-11 2020-09-11 Modified conjugated diene-based polymer, method for preparing the same and rubber composition including the same
US18/815,403 Continuation US20240417500A1 (en) 2019-09-11 2024-08-26 Modified Conjugated Diene-Based Polymer, Method for Preparing the Same and Rubber Composition Including the Same

Publications (1)

Publication Number Publication Date
WO2021049909A1 true WO2021049909A1 (fr) 2021-03-18

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397994A (en) 1980-09-20 1983-08-09 Japan Synthetic Rubber Co., Ltd. High vinyl polybutadiene or styrene-butadiene copolymer
US20030100683A1 (en) * 2001-03-26 2003-05-29 Jsr Corporation Hydrogenated modified polymer, process for producing the same and composition containing the same
KR20120083387A (ko) * 2009-09-09 2012-07-25 가부시키가이샤 브리지스톤 변성제, 변성제를 사용한 변성 공액 디엔계 중합체의 제조 방법 및 그 변성 공액 디엔계 중합체
KR20170121694A (ko) * 2016-04-25 2017-11-02 주식회사 엘지화학 변성 공액디엔계 중합체 및 이의 제조방법
WO2017216344A1 (fr) 2016-06-17 2017-12-21 Trinseo Europe Gmbh Stabilité au stockage du caoutchouc améliorée par le silane
KR20180080639A (ko) * 2017-01-04 2018-07-12 주식회사 엘지화학 변성 공액디엔계 중합체 및 이의 제조방법
KR101926619B1 (ko) * 2018-03-29 2018-12-11 금호석유화학 주식회사 기능성 단량체를 포함하는 공중합체 및 그 제조방법
KR20190030216A (ko) * 2016-08-19 2019-03-21 아사히 가세이 가부시키가이샤 변성 공액 디엔계 중합체, 그의 제조 방법, 고무 조성물, 타이어

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397994A (en) 1980-09-20 1983-08-09 Japan Synthetic Rubber Co., Ltd. High vinyl polybutadiene or styrene-butadiene copolymer
US20030100683A1 (en) * 2001-03-26 2003-05-29 Jsr Corporation Hydrogenated modified polymer, process for producing the same and composition containing the same
KR20120083387A (ko) * 2009-09-09 2012-07-25 가부시키가이샤 브리지스톤 변성제, 변성제를 사용한 변성 공액 디엔계 중합체의 제조 방법 및 그 변성 공액 디엔계 중합체
KR20170121694A (ko) * 2016-04-25 2017-11-02 주식회사 엘지화학 변성 공액디엔계 중합체 및 이의 제조방법
WO2017216344A1 (fr) 2016-06-17 2017-12-21 Trinseo Europe Gmbh Stabilité au stockage du caoutchouc améliorée par le silane
KR20190030216A (ko) * 2016-08-19 2019-03-21 아사히 가세이 가부시키가이샤 변성 공액 디엔계 중합체, 그의 제조 방법, 고무 조성물, 타이어
KR20180080639A (ko) * 2017-01-04 2018-07-12 주식회사 엘지화학 변성 공액디엔계 중합체 및 이의 제조방법
KR101926619B1 (ko) * 2018-03-29 2018-12-11 금호석유화학 주식회사 기능성 단량체를 포함하는 공중합체 및 그 제조방법

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* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "2550 WeConnectScience", LG CHEM, 15 February 2022 (2022-02-15), pages 1, XP055965905
ANONYMOUS: "2550H WeConnectScience", LG CHEM, 15 February 2022 (2022-02-15), pages 1, XP055965857
ANONYMOUS: "F3438 WeConnectScience", LG CHEM, 15 February 2022 (2022-02-15), pages 1, XP055965910
ANONYMOUS: "F3626E WeConnectScience", LG CHEM, 15 February 2022 (2022-02-15), pages 1, XP055965914
ANONYMOUS: "SLF 30H41 TECHNICAL DATA SHEET", GOODYEAR INTERNATIONAL CORPORATION, 8 July 2019 (2019-07-08), pages 1, XP055965847, ISBN: 1-800-548-8107
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See also references of EP3889193A4

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