WO2021049916A1 - 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 - Google Patents
변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 Download PDFInfo
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- WO2021049916A1 WO2021049916A1 PCT/KR2020/012333 KR2020012333W WO2021049916A1 WO 2021049916 A1 WO2021049916 A1 WO 2021049916A1 KR 2020012333 W KR2020012333 W KR 2020012333W WO 2021049916 A1 WO2021049916 A1 WO 2021049916A1
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- Prior art keywords
- carbon atoms
- group
- conjugated diene
- chain
- formula
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- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- PUJYFNMXCFLEDM-UHFFFAOYSA-N cyclopentane Chemical compound C1CC[CH+]C1 PUJYFNMXCFLEDM-UHFFFAOYSA-N 0.000 description 1
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- GSYVJAOBRKCNOT-UHFFFAOYSA-N diethoxymethyl-[3-[3-(diethoxymethylsilyl)propyltetrasulfanyl]propyl]silane Chemical compound CCOC(OCC)[SiH2]CCCSSSSCCC[SiH2]C(OCC)OCC GSYVJAOBRKCNOT-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- NRUBUZBAZRTHHX-UHFFFAOYSA-N lithium;propan-2-ylazanide Chemical compound [Li+].CC(C)[NH-] NRUBUZBAZRTHHX-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- UZJHQHKROPYURE-UHFFFAOYSA-N n-propyl-3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCN(CCC)CCC[Si](OCC)(OCC)OCC UZJHQHKROPYURE-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- QKJGTZOWMVHEHS-UHFFFAOYSA-N triethoxy-[3-(phenyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSC1=CC=CC=C1 QKJGTZOWMVHEHS-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- UMKAXYIUADSMOD-UHFFFAOYSA-N trimethoxy-[3-trimethoxysilyl-2,2-bis(trimethoxysilylmethyl)propyl]silane Chemical compound CO[Si](OC)(OC)CC(C[Si](OC)(OC)OC)(C[Si](OC)(OC)OC)C[Si](OC)(OC)OC UMKAXYIUADSMOD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- 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
- C08F236/14—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 containing elements other than carbon and hydrogen
-
- 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
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C08F236/06—Butadiene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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
- the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. Is that it can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, reduce the movement of the chain ends by bonding or denaturation of the chain ends, and increase the bonding strength with fillers such as silica or carbon black. It is widely used as a rubber material.
- the glass transition temperature of the rubber can be increased by increasing the vinyl content in the SBR, so that the required properties of the tire such as rolling resistance and braking force can be adjusted, as well as the glass transition temperature. Fuel consumption can be reduced by appropriate control.
- the solution polymerization SBR is prepared using an anionic polymerization initiator, and a technique of introducing a functional group at the terminal by bonding or denaturing the chain ends of the formed polymer using various modifiers is used. For example, U.S. Patent No.
- 4,397,994 proposes a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is bound using a binder such as a tin compound. I did.
- a technique of applying an aminoalkoxysilane modifier including an alkoxysilane group and an amine group in the molecule at the same time in order to maximize the dispersibility and reactivity of the filler is widely known.
- the solubility in the hydrocarbon solvent used for polymer production decreases, and thus it is difficult to easily perform the modification reaction.
- Patent Document 1 US4397994 A
- the present invention was conceived to solve the problems of the prior art, and a modified conjugate having excellent affinity with a filler including a second chain containing a repeating unit derived from a compound represented by Formula 1 and a unit derived from an alkoxysilane modifier It is an object of the present invention to provide a diene polymer.
- the present invention includes the step of reacting a macromonomer containing a repeating unit derived from a compound represented by Formula 1 after the denaturation reaction, thereby including a first chain of an active polymer and a second chain derived from a macromonomer, wherein the first
- An object of the present invention is to provide a method for producing the above-described modified conjugated diene-based polymer in which the chain and the second chain are coupled by a unit derived from a modifier.
- an object of the present invention is to provide a rubber composition comprising the modified conjugated diene-based polymer.
- the present invention includes a first chain comprising a repeating unit derived from a conjugated diene-based monomer; A second chain comprising a repeating unit derived from a compound represented by the following formula (1); And a unit derived from an alkoxysilane modifier, wherein the first chain and the second chain are coupled by a unit derived from the modifier to provide a modified conjugated diene-based intermediate:
- R 11a and R 11b are each independently a single bond or an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
- R 11c is an alkyl group having 1 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; Or a heterocyclic group having 3 to 20 carbon atoms,
- R 11d to R 11g 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 mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.
- the present invention comprises the steps of preparing an active first chain by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator (S1); Preparing a modified active first chain by reacting the active first chain with an alkoxysilane-based modifier (S2); And it provides a method for preparing the conjugated diene-based polymer comprising reacting (S3) a macromonomer including a repeating unit derived from a compound represented by the following formula (1) with the modified active first chain:
- R 11a and R 11b are each independently a single bond or an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
- R 11c is an alkyl group having 1 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; Or a heterocyclic group having 3 to 20 carbon atoms,
- R 11d to R 11g 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 mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.
- the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a filler.
- the modified conjugated diene-based polymer according to the present invention is derived from a denaturing agent by reacting with a macromonomer containing a repeating unit derived from a compound represented by Formula 1 and an active first chain modified after the denaturation reaction.
- a functional group derived from the compound represented by Formula 1 may be included in the polymer molecular chain, and thus, affinity with the filler may be excellent.
- the method for preparing a modified conjugated diene-based polymer according to the present invention comprises the step of reacting a macromonomer containing a repeating unit derived from a compound represented by Formula 1 after the denaturation reaction.
- a compound-derived functional group such as an amine group
- a highly modified modified conjugated diene polymer can be prepared.
- the rubber composition according to the present invention has excellent tensile properties and viscoelastic properties by including the modified conjugated diene-based polymer.
- the term'macromonomer' refers to a unit in which two or more units derived from a polymerization-reactive monomer are repeated, and may be bonded to another polymer chain or a reactive compound through an end group.
- the term'polymer' refers to a polymer compound prepared by polymerizing monomers.
- the generic term polymer encompasses the term homopolymer and the term copolymer, which are commonly used to refer to polymers made from only one monomer.
- the term'main chain' may refer to a molecular chain of a main skeleton constituting a polymer, and a chain mainly including a conjugated diene-based monomer or a repeating unit of a conjugated diene-based monomer and an aromatic vinyl-based monomer
- The'second chain' may refer to a chain having a smaller number of repeating units than the first chain, and mainly including repeating units derived from a compound represented by Formula 1.
- the term'vinyl content' refers to the mass (or weight) of butadiene contained at positions 1 and 2 in the polymer chain based on the conjugated diene monomer (butadiene, etc.) part (total amount of polymerized butadiene) in the polymer. ) Refers to the percent.
- the term'monovalent hydrocarbon group' means a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group.
- the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined according to the type of each substituent.
- the term'divalent hydrocarbon group' refers to 2 in which carbon and hydrogen are bonded, such as a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group containing one or more unsaturated bonds, and an arylene group. It may mean a valence group of atoms, and the minimum number of carbon atoms of a substituent represented by a divalent hydrocarbon may be determined according to the type of each substituent.
- alkyl group' may mean a monovalent saturated aliphatic hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl, and butyl, and isopropyl, sec-butyl, and tertiary It may mean including all branched alkyl groups such as tert-butyl and neo-pentyl.
- alkenyl group' may mean a monovalent aliphatic unsaturated hydrocarbon containing one or two or more double bonds.
- alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.
- alkylene group' may mean a divalent saturated aliphatic hydrocarbon such as methylene, ethylene, propylene, and butylene.
- the term'aryl group' may mean an aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. It may mean including all of.
- heterocyclic group' refers to a cycloalkyl group or an aryl group in which a carbon atom is substituted with one or more heteroatoms, and may mean including all of a heterocycloalkyl group or a heteroaryl group.
- substitution' may mean that a functional group, an atomic group, or hydrogen of a compound is substituted with a specific substituent.
- a functional group, an atomic group, or hydrogen of a compound is substituted with a specific substituent
- the functional group, atomic group, or compound Depending on the number of hydrogens present, one or two or more of a plurality of substituents may be present, and when a plurality of substituents are present, each of the substituents may be the same or different from each other.
- the term'single bond' may refer to a single covalent bond that does not include a separate atom or molecular group.
- the terms'derived unit','derived repeating unit', and'derived functional group' may refer to a component, structure, or the substance itself derived from a substance.
- compositions claimed through the use of the term'comprising', whether polymer or otherwise, may contain any additional additives, adjuvants, or compounds, unless stated to the contrary.
- the term'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except that it is not essential to operability.
- the term'consisting of' excludes any component, step or procedure not specifically described or listed.
- the'vinyl content' was measured and analyzed using Varian VNMRS 500 MHz NMR, and 1,1,2,2-tetrachloroethane was used as the solvent in the NMR measurement.
- Solvent peak is calculated as 6.0 ppm, 7.2 to 6.9 ppm is random styrene, 6.9 to 6.2 ppm is block styrene, 5.8 to 5.1 ppm is 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm is 1, It was measured by calculating the 1,2-vinyl bond content in the entire polymer using the peak of 2-vinyl.
- Mw weight average molecular weight
- Mn number average molecular weight
- Mw/Mn molecular weight distribution
- PDI molecular weight distribution
- 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 is carried out using, and the GPC measurement solvent is prepared by mixing 2 wt% of an amine compound in tetrahydrofuran.
- the'N atomic content' may be measured through an NSX analysis method as an example, and the NSX analysis method is measured using a trace nitrogen quantitative analyzer (NSX-2100H).
- a trace nitrogen quantitative analyzer NSX-2100H
- the trace nitrogen quantitative analyzer turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar 250 ml/min, O 2 350 ml/min, ozonizer 300 ml/ Set the carrier gas flow rate in min, set the heater to 800°C, and wait for about 3 hours to stabilize the analyzer.
- the analyzer After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to prepare calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and obtain the area corresponding to each concentration. After that, create a straight line using the ratio of the density to the area. Thereafter, a ceramic boat containing 20 mg of a sample is placed in the auto sampler of the analyzer to obtain an area, and the N content is calculated using the area of the obtained sample and the calibration curve. At this time, the sample is a modified conjugated diene-based polymer from which the solvent is removed by placing it in hot water heated by steam and stirring. The residual monomer, residual denaturant, and oil have been removed.
- Nitrogen standard AcuStandard S-22750-01-5 ml
- the'Si atomic content' was measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) as an ICP analysis method. Specifically, about 0.7 g of a sample was put into a platinum crucible (Pt crucible), about 1 mL of concentrated sulfuric acid (98% by weight, Electronic grade) was added, heated at 300° C. for 3 hours, and the sample was heated in an electric furnace (Thermo Scientific, Lindberg Blue M), after conducting conversation with the program of steps 1 to 3 below,
- step 1 initial temp 0°C, rate (temp/hr) 180 °C/hr, temp(holdtime) 180°C (1hr)
- step 2 initial temp 180°C, rate (temp/hr) 85 °C/hr, temp(holdtime) 370°C (2hr)
- step 3 initial temp 370°C, rate (temp/hr) 47 °C/hr, temp(holdtime) 510°C (3hr)
- the present invention provides a modified conjugated diene polymer capable of providing a rubber composition having excellent affinity with a filler and, as a result, excellent processability, tensile properties, and viscoelastic properties.
- the modified conjugated diene-based polymer includes a first chain including a repeating unit derived from a conjugated diene-based monomer; A second chain comprising a repeating unit derived from a compound represented by the following formula (1); And a unit derived from an amine-containing alkoxysilane modifier, wherein the first chain and the second chain are coupled to each other by a unit derived from the modifier.
- R 11a and R 11b are each independently a single bond or an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
- R 11c is an alkyl group having 1 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; Or a heterocyclic group having 3 to 20 carbon atoms,
- R 11d to R 11g 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 mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.
- the modified conjugated diene-based polymer comprises the step of reacting a macromonomer containing a repeating unit derived from a compound represented by Formula 1 with a modified active first chain after a modification reaction.
- the first chain containing the repeating unit derived from the conjugated diene-based monomer and the amine-containing alkoxysilane-containing modifier-derived unit bonded to at least one end of the first chain through this may be prepared by, and are derived from the macromonomer. It may have the same structure as the graft copolymer to which the second chain is bonded. That is, the modified conjugated diene-based polymer may be one in which the first chain and the second chain are coupled by a unit derived from a denaturant.
- the modified conjugated diene-based polymer according to an embodiment of the present invention will be described later comprising reacting a macromonomer containing a repeating unit derived from a compound represented by Formula 1 with a first chain having a modified activity after a modification reaction. From the macromonomer to a first chain containing a repeating unit derived from a conjugated diene-based monomer and an amine-containing alkoxysilane-containing modifier-derived unit bonded to at least one end of the first chain. It may have the same structure as the graft copolymer to which the derived second chain is bonded. That is, the modified conjugated diene-based polymer may be one in which the first chain and the second chain are coupled by a unit derived from a denaturant.
- the modified conjugated diene-based polymer when all of the functional groups are intensively distributed at one end of the modified conjugated diene-based polymer, only one end of the polymer may be bonded to silica and the other end may be free when interacting with silica. Similar to that, processability can be remarkably improved by showing an excellent effect on the dispersibility of the filler and preventing aggregation.
- the second chain derived from the macromonomer and the unit derived from the denaturant are included at one end to which the functional group is bonded, so that the effect of the interaction with the filler can be achieved at a level equal to or higher than that of the existing modified polymer at both ends. Tensile properties and viscoelastic properties can be excellent.
- the modified conjugated diene-based polymer has a residue derived from a denaturant, such as an alkoxy group (-OR, where R is a hydrocarbon group) or a hydroxyl group (-OH), and condensation reaction or
- a denaturant such as an alkoxy group (-OR, where R is a hydrocarbon group) or a hydroxyl group (-OH)
- the storage stability decreases due to hydrolysis reaction, etc., resulting in an increase in Mooney viscosity and an increase in molecular weight distribution. Accordingly, the excellent properties of the blended properties of the modified conjugated diene-based polymer are not maintained. There is a problem that cannot be obtained.
- the modified conjugated diene-based polymer according to an embodiment of the present invention has a structure in which a second chain derived from the macromonomer is bonded to an alkoxy group, which is a moiety derived from a modifier present in the polymer, by being prepared by the method described below. And, as a result, there is no moiety derived from the denaturant in the polymer, or it is reduced compared to the existing manufacturing method.
- the modified conjugated diene-based polymer according to an embodiment of the present invention has the advantage of being able to introduce more functional groups than when only a modifier having a large number of functional groups is used by being prepared by a manufacturing method described below.
- the alkoxy group of the active polymer and the modifier is difficult to bind two or more polymer chains to one molecule of the modifier due to steric hindrance of the polymer, and although three or more chains may be bonded, a modified polymer in which three or more chains are coupled. Is bound to be a trace amount.
- the second chain derived from the macromonomer can bind the functional group to the alkoxy moiety of the modifier to which the polymer chain is bonded, regardless of the steric hindrance as described above, so that the functional group in the polymer chain is further You can introduce a lot.
- the introduction of a functional group in one molecule of the modifier is clearly limited, and no matter how many are introduced, the absolute functional group in the polymer is compared with the case of bonding a chain containing a functional group to an alkoxy moiety without the effect of steric hindrance as in the present invention. There must be a difference in quantity.
- the modified conjugated diene-based polymer according to the present invention has excellent storage stability over time, so that the blending properties can maintain consistently excellent properties even at the beginning of manufacture or after time elapses, and tensile properties compared to the existing end-end modified polymer. And viscoelastic properties may be excellent.
- the first chain serving as the main skeleton of the modified conjugated diene-based polymer includes a repeating unit derived from a conjugated diene-based monomer, and the conjugated diene-based monomer is 1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo has a halogen atom It may be one or more selected from the group consisting of).
- the first chain may further include a repeating unit derived from an aromatic vinyl-based monomer, and the aromatic vinyl-based monomer is styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1 -Vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidino ethyl)styrene (3-(2-pyrrolidino ethyl)styrene) , 4-(2-pyrrolidino ethyl) styrene (4-(2-pyrrolidino ethyl) styrene) and 3-(2-pyrrolidino-1-methyl ethyl)- ⁇ -methylstyrene (3-(2-pyrrolidino)
- the first chain of the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with a repeating unit derived from the conjugated diene-based monomer.
- the diene-based monomer-derived repeating unit may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. .
- the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer
- the modified conjugated diene-based polymer contains a diene-based monomer-derived repeating unit in excess of 0% to 1% by weight, more than 0% to 0.1% by weight, It may be included in an amount exceeding 0% by weight to 0.01% by weight, or exceeding 0% by weight to 0.001% by weight, and there is an effect of preventing gel formation within this range.
- the first chain constituting the skeleton of the modified conjugated diene-based polymer includes two or more repeating units derived from monomers
- the first chain may be a random copolymer chain, in which case each There is an excellent effect of having an excellent balance between physical properties.
- the random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.
- the modified conjugated diene-based polymer according to an embodiment of the present invention further includes a second chain in addition to the first chain, and the second chain is from a macromonomer containing a repeating unit derived from a compound represented by Formula 1 As derived, the main unit may be a repeating unit derived from a compound represented by Formula 1.
- R 11a and R 11b are each independently a single bond or an unsubstituted alkylene group having 1 to 10 carbon atoms
- R 11c is an alkyl group having 1 to 10 carbon atoms
- R 11d to R 11g are each Independently an alkyl group having 1 to 10 carbon atoms; Or it may be a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.
- R 11a and R 11b are each independently a single bond or an unsubstituted alkylene group having 1 to 6 carbon atoms
- R 11c is an alkyl group having 1 to 6 carbon atoms
- R 11d to R 11g are each Independently an alkyl group having 1 to 6 carbon atoms; Or it may be a trialkylsilyl group substituted with an alkyl group having 1 to 6 carbon atoms.
- the compound represented by Formula 1 may be one or more selected from compounds represented by the following Formulas 1-1 to 1-3.
- Me is a methyl group.
- the modified conjugated diene-based polymer may be in a form in which a first chain and a second chain are coupled by a unit derived from an alkoxysilane-based modifier, and the second chain may be a form in which the modifier becomes a hub.
- the modifier may be a silica affinity modifier.
- the silica-affinity modifier may mean a modifier containing a silica-affinity functional group in a compound used as a modifier, and the silica-affinity functional group has excellent affinity with a filler, particularly a silica-based filler, It may mean a functional group capable of interaction between the functional groups derived from the denaturant.
- alkoxysilane group modifier according to the present invention may be an amine-containing alkoxysilane-based modifier or an amine-free alkoxysilane-based modifier.
- the amine-containing alkoxysilane modifier may be a compound represented by the following formula (2).
- R 1 may be a single bond or an alkylene group having 1 to 10 carbon atoms
- R 2 and R 3 may each independently be an alkyl group having 1 to 10 carbon atoms
- R 4 may be hydrogen, an epoxy group, or a carbon number It may be a 1 to 10 alkyl group, a C 2 to C 10 allyl group, a mono-, di- or tri-substituted alkylsilyl group substituted with a C 1 to C 10 alkyl group, or a C 2 to C 10 heterocyclic group
- R 21 May be a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j -, and R 42 may be an alkylene group having 1 to 10 carbon atoms
- a and m are each independently 1 to 3 It may be a selected integer, n may be an integer of 0 to 2, j may be an integer selected from 1 to 30.
- the compound represented by Formula 2 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(dimethoxy(methyl)silyl) )propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine(N,N-bis(3-(diethoxy(methyl)silyl) )propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(trimethoxysilyl)propyl)-methyl- 1-amine), N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine), tri (Tri(trimethoxysilyl)
- the compound represented by Formula 2 may be one or more selected from compounds represented by the following Formulas 2-1 to 2-6.
- Me is a methyl group
- Et is an ethyl group
- the amine-containing alkoxysilane modifier may be a compound represented by the following formula (3).
- R 5 , R 6 and R 9 may each independently be an alkylene group having 1 to 10 carbon atoms
- R 7 , R 8 , R 10 and R 11 may each independently be an alkyl group having 1 to 10 carbon atoms
- R 12 may be hydrogen or an alkyl group having 1 to 10 carbon atoms
- b and c may each independently be 1, 2 or 3, b+c ⁇ 4, and A is or
- R 13 , R 14 , R 15 and R 16 may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.
- the compound represented by Formula 3 is N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl Propan-1-amine (N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) and 3-(4 ,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine (3-(4,5-dihydro-1H-imidazol) It may be one selected from the group consisting of -1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).
- the amine-containing alkoxysilane modifier may be a compound represented by the following formula (4).
- a 1 and A 2 may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms containing or not including an oxygen atom, and R 17 to R 20 are each independently monovalent having 1 to 20 carbon atoms. It may be a hydrocarbon group, and L 1 to L 4 are each independently a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L 1 And L 2 and L 3 and L 4 may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L 1 and L 2 and L 3 and L 4 are connected to each other to form a ring, the formed ring May contain 1 to 3 heteroatoms selected from the group consisting of N, O and S.
- the compound represented by Formula 4 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N ,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)( 3,3'-(1,1,3,3-tetraprop
- the compound represented by Formula 4 may be a compound represented by Formula 4-1 below.
- Me is a methyl group.
- the amine-containing alkoxysilane modifier may be a compound represented by the following formula (5).
- R b2 to R b4 are each independently an alkylene group having 1 to 10 carbon atoms
- R b5 to R b8 are each independently an alkyl group having 1 to 10 carbon atoms
- R b13 and R b14 are independently of each other It is an alkylene group of 1 to 10
- R b15 to R b18 are each independently an alkyl group having 1 to 10 carbon atoms
- m 1, m 2 , m 3 and m 4 are each independently an integer of 1 to 3.
- the compound represented by Formula 5 may be a compound represented by Formula 5-1 below.
- Et is an ethyl group.
- the amine-containing alkoxysilane modifier may be a compound represented by the following formula (6).
- R e1 and R e2 are each independently an alkylene group having 1 to 10 carbon atoms
- R e3 to R e6 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or -R e7 SiR e8 R e9 R e10
- at least one of R e3 to R e6 is -R e7 SiR e8 R e9 R e10
- R e7 is a single bond or an alkylene group having 1 to 10 carbon atoms
- R e8 to R e10 are independently of each other 1
- at least one of R e8 to R e10 is an alkoxy group having 1 to 10 carbon atoms.
- the compound represented by Formula 6 may be a compound represented by Formula 6-1 below.
- Me is a methyl group.
- the amine-containing alkoxysilane modifier may be a compound represented by the following formula (7).
- R h1 and R h2 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
- R h3 is a single bond or an alkylene group having 1 to 10 carbon atoms
- a 3 is -Si (R h4 R h5 R h6 ) or -N[Si(R h7 R h8 R h9 )] 2 , wherein R h4 to R h9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms to be.
- the compound represented by Formula 7 may be a compound represented by Formula 7-1 or Formula 7-2 below.
- Me is a methyl group.
- the amine-free alkoxysilane modifier may be a compound represented by Formula 8 below.
- X is O or S
- R f1 and R f2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms
- R f3 to R f8 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms.
- p is an integer of 0 or 1
- R f1 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
- the compound represented by Formula 9 may be a compound represented by Formula 9-1 or Formula 9-2 below.
- the amine-free alkoxysilane modifier may be a compound represented by Formula 10 below.
- R g1 to R g4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R g5 Si(OR g6)r (R g7 ) 3-r , but at least one of R g1 to R g4 is -R g5 Si(OR g6)r (R g7 ) 3-r , wherein R g5 is a single bond or an alkylene group having 1 to 10 carbon atoms And R g6 and R g7 are each independently an alkyl group having 1 to 10 carbon atoms, r is 1 to 3, Y is C or N, but when Y is N, R g4 does not exist.
- the compound represented by Formula 10 may be a compound represented by Formula 10-1 below.
- Me is a methyl group.
- the amine-free alkoxysilane modifier may be a compound represented by the following formula (11).
- R g1 to R g3 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
- R g4 is an alkoxy group having 1 to 10 carbon atoms
- q is an integer of 2 to 100 .
- R g1 to R g3 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms
- R g4 is an alkoxy group having 1 to 6 carbon atoms
- q is 2 to 50 Is the integer of
- the content of N atoms in the polymer according to NSX analysis is 150 ppm or more by weight, and the content of Si atoms in the polymer according to ICP analysis is based on weight. It may be more than 180 ppm.
- the content of Si atoms in the polymer according to ICP analysis may be 180 ppm or more, preferably 190 ppm or more, more preferably 200 ppm or more.
- the content of the Si atom may be derived from a denaturant, and in some cases, may be derived from a compound represented by Formula 1 and a denaturant, and the content of the Si atom is a functional group present in the modified conjugated diene-based polymer, that is, a filler and It can be a major factor in addition to improving processability as it is expected to improve the affinity of.
- the modified conjugated diene-based polymer may have a content of N atoms in the polymer according to NSX analysis of 150 ppm or more, preferably 160 ppm or more, and more preferably 170 ppm or more.
- the modified conjugated diene-based polymer may have a relatively high content of N atoms by a method in which a functional group derived from the compound represented by Formula 1, such as an amine group, is repeatedly present, and the functional group derived from the compound represented by Formula 1 is a polymer agent.
- the affinity with a filler, such as silica, and the dispersibility of silica are remarkably improved during the blending process, thereby having excellent viscoelastic properties and at the same time. Processability can be greatly improved.
- the modified conjugated diene-based polymer according to an embodiment of the present invention may have a molar ratio (N/Si) of N atoms and Si atoms of 0.75 or more.
- a polymer modified by a modifier it may contain Si atoms and N atoms due to a modified polymerization initiator, a modified monomer, etc., but as described above, the polymer according to an embodiment of the present invention is represented by Formula 1
- the content of the N atom may be relatively large due to the inclusion of the repeating unit derived from the indicated compound, and the molar ratio of the N atom and the Si atom may be 0.75 or more, and preferably 0.77 or more, or 0.78 or more as a symbolic meaning. , More preferably 0.8 or more, and most optimally 0.9 or more. Through this, it is possible to optimize the effect of improving processability by improving dispersibility during compounding.
- the modified conjugated diene-based polymer has a Mooney viscosity change rate (MV R ) of 20% or less according to Equation 1 below.
- MV R [(MV f -MV i ) / MV i ] x 100
- Equation 1 MV R is the Mooney viscosity change rate, MV f is the 100°C Mooney viscosity after leaving the polymer at 25°C for 30 days, and MV i is the initial 100°C Mooney viscosity of the polymer.
- the Mooney viscosity change rate may be an indicator that not only processability but also the increase in Mooney viscosity occurring during storage after manufacture is small.
- the polymer according to the present invention includes a repeating unit derived from a compound represented by Formula 1 Due to the structural characteristics in which the second chain, the denaturant-derived unit, and the first chain of the polymer are bonded to each other in a specific structure, the processability is improved, and even when stored for a long time, the change rate of Mooney viscosity is low, so storage stability can be excellent.
- the Mooney viscosity change rate is the initial Mooney viscosity of the polymer and the rate of change in the Mooney viscosity after storing the polymer at room temperature for 30 days.
- a polymer having 20% or less is provided, and preferably 15% or less.
- the Mooney viscosity is 100° C. Mooney viscosity, and can be measured by a conventional method applied in this technical field.
- the modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 100,000 g/mol. mol to 800,000 g/mol, and a weight average molecular weight (Mw) of 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol, and ,
- the peak average molecular weight (Mp) may be 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol.
- the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more and 3.0 or less, or 1.1 or more and 2.5 or less, or 1.1 or more and 2.0 or less, and tensile properties within this range And viscoelastic properties are excellent, and there is an effect of excellent balance between physical properties.
- PDI molecular weight distribution
- the modified conjugated diene-based polymer may have a Mooney viscosity at 100° C., 30 or more, 40 to 150, or 40 to 140, and has excellent processability and productivity within this range.
- the Mooney viscosity may be measured using a Mooney viscometer. Specifically, using a large rotor of Monsanto's MV2000E, under the conditions of 100°C and a rotor speed of 2 ⁇ 0.02 rpm, leave the polymer at room temperature (23 ⁇ 5°C) for 30 minutes or more, and then collect 27 ⁇ 3 g to the inside of the die cavity. It was measured while filling in and applying torque by operating a platen.
- the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight.
- the vinyl content refers to the content of 1,2-added conjugated diene-based monomer, not 1,4-added, based on 100% by weight of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl-based monomer. I can.
- the present invention provides a method for preparing the modified conjugated diene-based polymer.
- the method for preparing the modified conjugated diene-based polymer comprises polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator to prepare an active first chain.
- R 11a to R 11g are as described above.
- the modifier, the conjugated diene-based monomer, and the aromatic vinyl-based monomer are as described above.
- the hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.
- the polymerization initiator is not particularly limited, for example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyl Lithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium , Naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium is
- the polymerization initiator is 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on a total of 100 g of monomers.
- the total of 100 g of the monomers may represent the total amount of a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer.
- the polymerization in step (S1) may be an anionic polymerization as an example, and a specific example may be a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion.
- the polymerization in step (S1) may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (insulation polymerization), and the constant temperature polymerization includes polymerization by self-reaction heat without optionally applying heat after the polymerization initiator is added.
- the elevated-temperature polymerization may mean a polymerization method in which heat is arbitrarily applied after the polymerization initiator is added to increase the temperature, and the isothermal polymerization is heated by applying heat after the polymerization initiator is added. It may mean a polymerization method in which the temperature of the polymerized product is kept constant by increasing or taking away heat.
- the polymerization in step (S1) may further include a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer.
- a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer.
- the diene-based compound it may be 1,2-butadiene.
- step (S1) may be carried out in a temperature range of 80°C or less, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C, or 10°C to 70°C, for example, within this range.
- a temperature range of 80°C or less 80°C or less, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C, or 10°C to 70°C, for example, within this range.
- the active polymer chain prepared by the step (S1) may mean a polymer in which a polymer anion and an organic metal cation are bonded.
- the polymerization of step (S1) may be carried out including a polar additive, and the polar additive is 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on a total of 100 g of monomers. It can be added in proportion. As another example, the polar additive may be added in a ratio of 0.001 g to 10 g, 0.005 g to 5 g, and 0.005 g to 4 g based on a total of 1 mmol of the polymerization initiator.
- the polar additives include, for example, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether.
- Tertiary-butoxyethoxyethane bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetra It may be one or more selected from the group consisting of methylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di(2-tetra) Hydrofuryl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and when the polar additive is included, conjugated diene
- the polar additive is included, conjugated diene
- the step (S2) is a step for preparing a modified active first chain by reacting the active first chain with an amine-containing alkoxysilane modifier, wherein the reaction may be a modification or a coupling reaction, wherein the The denaturant may be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers.
- the modifier may be used in a molar ratio of 1:0.1 to 10, 1: 0.1 to 5, or 1:0.1 to 1:3, based on 1 mole of the polymerization initiator in step (S1).
- step (S3) is a step for preparing a modified conjugated diene-based polymer by reacting a macromonomer including an active first chain and a repeating unit derived from the compound represented by Chemical Formula 1.
- the manufacturing method according to an embodiment of the present invention may further include the step of preparing a macromonomer prior to the step (S3), and the step of preparing the macromonomer is a chemical formula in the presence of an organolithium compound in a hydrocarbon solvent.
- the polymerization reaction may be a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion, and thus, the macromonomer may be a living anionic end in which one end can act as a monomer.
- the organolithium compound may be an alkyllithium compound, specifically methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n -Decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyl It may be lithium or 4-cyclopentylium, more specifically n-butyllithium.
- the macromonomer may be prepared through Reaction Scheme 1 below, and thus may be a compound having a structure represented by Formula M below.
- R 11a to R 11g are as defined in Formula 1, R-Li is an alkyllithium compound, and R is an alkyl group derived from the alkyllithium.
- the macromonomer includes 1 to 80, 1 to 60, or 1 to 50 repeating units derived from the compound represented by Formula 1, exemplarily, in the formula M, r is 1 to 80, 1 to 60 or 1 It may be to 50.
- r is 1 to 80, 1 to 60 or 1 It may be to 50.
- the processability, tensile properties, and viscoelastic properties of the modified conjugated diene-based polymer including the second chain derived from the macromonomer may be excellent in balance.
- the (S3) step may be to prepare a modified conjugated diene-based polymer by reacting a functional group derived from a denaturant in the modified active polymer with a macromonomer and a living anion end of the macromonomer.
- the modified active polymer chain prepared in step (S2) contains a functional group derived from a denaturant, and the functional group derived from the denaturant contains an alkoxy group remaining without reacting with the polymer chain, and thus the living anion of the macromonomer It may be that the terminal and the alkoxy group react to prepare the modified conjugated diene-based polymer.
- the macromonomer may be used in an amount of 0.1 to 4.0 moles, 0.1 to 2.0 moles, or 0.5 to 1.5 moles relative to 1 mole of the polymerization initiator.
- condensation reaction in which the active polymer is modified with a modifier and a compound capable of condensation with the Si-O bond of the modifier has been applied as a way to additionally introduce a functional group into the polymer.
- the condensation reaction is used in this way, the bond between the substance having an additional functional group and the modified active polymer is formed into -Si-O-Si-, and hydrolysis may occur during the subsequent steam stripping step, washing step, or storage. Is present, and thus there is a problem in that the bond is separated at the condensation bonding site, resulting in a problem in which a functional group is lost.
- 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.
- the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
- the rubber composition may contain the modified conjugated diene-based polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight, and within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and excellent balance between properties.
- the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, and in this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition.
- the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.
- the rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc.
- NR natural rubber
- EMR epoxidized natural rubber
- DPNR deproteinized natural rubber
- hydrogenated natural rubber etc.
- Styrene-butadiene copolymer SBR
- polybutadiene BR
- polyisoprene IR
- butyl rubber IIR
- ethylene-propylene copolymer polyisobutylene-co-isoprene, poly(ethylene-co- Propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene -Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and the like, and any one or a mixture of two or more of them may be used.
- the rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention.
- the filler may be a silica-based filler as an example, and a specific example may be wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate, or colloidal silica, and preferably, the effect of improving fracture properties and wet It may be wet-type silica that has the best effect of both wet grip.
- the rubber composition may further include a carbon black-based filler if necessary.
- silica when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation properties may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide.
- it when considering the effect of improving reinforcing properties, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.
- the amount of the silane coupling agent is usually It may be less than the case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight based on 100 parts by weight of silica, and the effect as a coupling agent within this range is While sufficiently exerted, there is an effect of preventing the gelation of the rubber component.
- the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent.
- the vulcanizing agent may specifically be a sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, within this range, while securing the required elastic modulus and strength of the vulcanized rubber composition, and at the same time having low fuel economy. It has an excellent effect.
- the rubber composition according to an embodiment of the present invention includes various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, an antioxidant, a plasticizer, an anti-aging agent, an anti-scorch agent, and zinc. white), stearic acid, a thermosetting resin, or a thermoplastic resin.
- the vulcanization accelerator is, for example, a thiazole compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG
- a thiazole compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG
- a guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.
- the process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering tensile strength and abrasion resistance, when considering aromatic process oil price, hysteresis loss, and low-temperature characteristics Naphthenic or paraffinic process oil may be used.
- the process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.
- the antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol (2,6-bis( (dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio)methyl)phenol), It may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.
- the anti-aging agent is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensation product of diphenylamine and acetone, and the like, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.
- the rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, or an internal mixer according to the formulation, and has low heat generation and abrasion resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.
- a kneader such as a Banbury mixer, a roll, or an internal mixer according to the formulation
- the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreas, or bead coated rubber, and other tire members, anti-vibration rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products.
- the present invention provides a tire manufactured using the rubber composition.
- the tire may include a tire or a tire tread.
- N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine instead of N,N,N',N',1-pentamethyl-1-vinylsilanediamine (N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine) was added (3 mole ratio to 1 mole of [act.
- n-hexane 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and then n-butyl Lithium 3.2 g (10wt% in n-hexane) was added, and the internal temperature of the reactor was adjusted to 60°C, and an adiabatic heating reaction was performed. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene.
- Example 1 a solution containing the macromonomer prepared in Preparation Example 1 instead of n-butyllithium was added so that the n-butyllithium of Example 1 and the macromonomer became equimolar to perform an adiabatic heating reaction, and then A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the reaction was stopped after capping butadiene without performing the step of adding and reacting a denaturant and a macromonomer.
- n-hexane 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and then n-butyllithium 3.2 g (10 wt% in n-hexane) was adjusted to the internal temperature of the reactor at 60° C. and an adiabatic heating reaction was performed. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene.
- the styrene unit content, vinyl content, and weight average molecular weight (Mw, X10 3 g/mol), number average molecular weight (Mn, X10 3 g) in the polymer, respectively. /mol), molecular weight distribution (PDI, MWD), Mooney viscosity (MV), Mooney viscosity change rate, and Si and N contents were measured, respectively.
- the results are shown in Table 1 below.
- styrene units (SM) and vinyl (Vinyl) in each of the polymers were measured and analyzed using Varian VNMRS 500 MHz NMR.
- 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.
- the Mooney viscosity (MV, (ML1+4, @100°C) MU) was measured using a Rotor Speed 2 ⁇ 0.02 rpm, Large Rotor at 100°C using MV-2000 (ALPHA Technologies). Samples were left at room temperature (23 ⁇ 3°C) for at least 30 minutes, and then 27 ⁇ 3 g was collected, filled in the die cavity, and platen was operated to measure for 4 minutes.
- the Si content was measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) by an ICP analysis method. Specifically, about 0.7 g of a sample was put into a platinum crucible (Pt crucible), about 1 mL of concentrated sulfuric acid (98% by weight, Electronic grade) was added, heated at 300° C. for 3 hours, and the sample was heated in an electric furnace (Thermo Scientific, Lindberg Blue M), after conducting conversation with the program of steps 1 to 3 below,
- step 1 initial temp 0°C, rate (temp/hr) 180 °C/hr, temp(holdtime) 180°C (1hr)
- step 2 initial temp 180°C, rate (temp/hr) 85 °C/hr, temp(holdtime) 370°C (2hr)
- step 3 initial temp 370°C, rate (temp/hr) 47 °C/hr, temp(holdtime) 510°C (3hr)
- the N content was measured using an NSX analysis method, a trace nitrogen quantitative analyzer (NSX-2100H). Specifically, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), set the carrier gas flow rate to 250 ml/min for Ar, 350 ml/min for O 2 , and 300 ml/min for ozonizer, and heater After setting at 800° C., the analyzer was stabilized by waiting for about 3 hours. After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to prepare calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and obtain the area corresponding to each concentration.
- NSX-2100H a trace nitrogen quantitative analyzer
- Comparative Example 1 is a polymer prepared without using the modifier presented in the present invention
- Comparative Examples 2 to 4 are polymers prepared without using the macromonomer presented in the present invention
- the polymers of Examples 1 to 5 From the fact that the N atom and Si atom are present and the content of N atom and Si atom is significantly increased compared to Comparative Examples 1 to 4, the modified conjugated diene polymer according to the present invention comprises a repeating unit derived from the compound represented by Formula 1 in the polymer.
- Second chain contains a unit derived from an amine-containing alkoxysilane modifier, and prepared by a manufacturing method in which a macromonomer containing a derived repeating unit represented by Formula 1 is reacted with the first chain of the denatured active polymer after the modification reaction.
- the polymer can contain a high content of N atoms and Si atoms.
- 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 rubber specimen is kneaded through the first stage kneading and the second stage kneading.
- first-stage kneading raw rubber, silica (filling agent), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc agent (ZnO), stearic acid are used using a Banbari mixer attached with a temperature control device.
- TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer)
- anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine)
- wax Merocrystaline Wax
- the first blend sulfur, a rubber accelerator (DPG (diphenylguanidine)) and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and at a temperature of 100°C or less.
- the mixture was mixed to obtain a second blend, and then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.
- each test piece was prepared according to the tensile test method of ASTM 412, and the tensile stress (300% modulus) at the time of 300% elongation of the test piece was measured. Specifically, tensile properties were measured at a rate of 50 cm/min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.
- 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.
- the modified styrene-butadiene copolymers of Examples 1 to 5 reacted with a macromonomer after the denaturing reaction using a denaturing agent according to an embodiment of the present invention have excellent processability characteristics compared to Comparative Examples 1 to 6. At the same time, it was confirmed that the tensile properties and viscoelastic properties were also excellent.
- Examples 1 to 5 exhibited equally superior tensile properties compared to Comparative Examples 5 and 6, while exhibiting improved viscoelastic properties and remarkably improved processability properties.
- the modified conjugated diene-based polymer of the present invention comprises a copolymer having a structure different from that of Comparative Examples 5 and 6, such as a repeating unit derived from a compound represented by Formula 1 derived from a macromonomer.
- the second chain is coupled to the first chain of the modified polymer by a unit derived from a modifier and bonded in the same structure as the graft copolymer, and the tensile properties, viscoelastic properties, and processability properties are balanced by these structural differences. It was confirmed that there is a remarkably excellent effect (see Table 1 and Table 3 above).
- N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine instead of N,N,N',N',1-pentamethyl-1-vinylsilanediamine (N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine) was added (3 mole ratio to 1 mole of [act.
- n-hexane 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and then n-butyl Lithium 3.2 g (10wt% in n-hexane) was added, and the internal temperature of the reactor was adjusted to 60°C, and an adiabatic heating reaction was performed. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene.
- Example 6 a solution containing the macromonomer prepared in Preparation Example 1 instead of n-butyllithium was added in an amount such that the n-butyllithium of Example 6 and the macromonomer became animals to proceed with an adiabatic heating reaction. Then, a modified styrene-butadiene copolymer was prepared in the same manner as in Example 6, except that the step of adding and reacting a denaturant and a macromonomer was not performed, and the reaction was stopped after capping butadiene.
- n-hexane 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and then n-butyllithium 3.2 g (10 wt% in n-hexane) was adjusted to the internal temperature of the reactor at 60° C. and an adiabatic heating reaction was performed. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene.
- Comparative Example 8 a solution containing the macromonomer prepared in Preparation Example 1 instead of n-butyllithium was added in an amount such that n-butyllithium of Comparative Example 8 and the macromonomer became equimolar to perform an adiabatic heating reaction.
- a modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 8 except for proceeding.
- the styrene unit content, vinyl content, and weight average molecular weight (Mw, X10 3 g/mol), number average molecular weight (Mn, X10 3 g) in the polymer, respectively. /mol), molecular weight distribution (PDI, MWD), Mooney viscosity (MV), Si atom and N atom content were measured in the same manner as in Experiment #1, respectively. The results are shown in Table 4 below.
- Comparative Example 7 was prepared without using a modifier
- Comparative Example 8 was prepared without using the macromonomer presented in the present invention, and the Si content and N content in the polymer were significantly compared to Comparative Examples 7 and 8.
- a second chain comprising a repeating unit derived from a compound represented by the following formula (1) in the modified conjugated diene-based polymer according to the present invention from the increase; And a unit derived from an amine-free alkoxysilane modifier.
- Example 6 exhibited improved viscoelastic properties and remarkably improved processability properties while exhibiting equally superior tensile properties compared to Comparative Example 9, except that Comparative Example 9 used the macromonomer in Example 6 as a modification initiator.
- Comparative Example 9 used the macromonomer in Example 6 as a modification initiator.
- the present invention-modified conjugated diene-based polymer through the difference in the manufacturing method of Example 6 and Comparative Example 9 and the remarkable difference in effect between Example 6 and Comparative Example 9 despite the fact that the Si atom and N atom in the polymer are contained at the same level.
- a copolymer having a structure different from that of Comparative Example 9 for example, a second chain containing a repeating unit derived from a compound represented by Formula 1 derived from a macromonomer is coupled to the first chain of a modified polymer by a unit derived from a denaturant to be grafted.
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Abstract
Description
Claims (13)
- 공액디엔계 단량체 유래 반복단위를 포함하는 제1사슬; 하기 화학식 1로 표시되는 화합물 유래 반복단위를 포함하는 제2사슬; 및 알콕시실란계 변성제 유래 단위를 포함하고,상기 제1사슬과 제2사슬은 변성제 유래 단위에 의하여 커플링 결합되어 있는 것인 변성 공액디엔계 중합체:[화학식 1]상기 화학식 1에서,R11a 및 R11b는 서로 독립적으로 단일결합 또는 치환기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기; 치환기로 치환 또는 비치환된 탄소수 5 내지 20의 시클로알킬렌기; 또는 치환기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기이고, 여기에서 상기 치환기는 탄소수 1 내지 10의 알킬기, 탄소수 5 내지 10의 시클로알킬기, 또는 탄소수 6 내지 20의 아릴기이고,R11c는 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알카이닐기; 탄소수 1 내지 20의 헤테로알킬기; 탄소수 2 내지 20의 헤테로알케닐기; 탄소수 2 내지 20의 헤테로알카이닐기; 탄소수 5 내지 20의 시클로알킬기; 탄소수 6 내지 20의 아릴기; 또는 탄소수 3 내지 20의 헤테로고리기이고,R11d 내지 R11g는 서로 독립적으로 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알카이닐기; 탄소수 1 내지 20의 헤테로알킬기; 탄소수 2 내지 20의 헤테로알케닐기; 탄소수 2 내지 20의 헤테로알카이닐기; 탄소수 5 내지 20의 시클로알킬기; 탄소수 6 내지 20의 아릴기; 탄소수 3 내지 20의 헤테로고리기; 또는 탄소수 1 내지 10의 알킬기로 치환된 1치환, 2치환 또는 3치환의 알킬실릴기이다.
- 제1항에 있어서,상기 화학식 1에서,R11a 및 R11b는 서로 독립적으로 단일결합 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고,R11c는 탄소수 1 내지 10의 알킬기이고,R11d 내지 R11g는 서로 독립적으로 탄소수 1 내지 10의 알킬기; 또는 탄소수 1 내지 10의 알킬기로 치환된 1치환, 2치환 또는 3치환의 알킬실릴기인 변성 공액디엔계 중합체.
- 제1항에 있어서,상기 화학식 1에서,R11a 및 R11b는 서로 독립적으로 단일결합 또는 비치환된 탄소수 1 내지 6의 알킬렌기이고,R11c는 탄소수 1 내지 6의 알킬기이고,R11d 내지 R11g는 서로 독립적으로 탄소수 1 내지 6의 알킬기; 또는 탄소수 1 내지 6의 알킬기로 치환된 트리알킬실릴기인 변성 공액디엔계 중합체.
- 제1항에 있어서,상기 제1사슬은 방향족 비닐계 단량체 유래 반복단위를 더 포함하는 것인 변성 공액디엔계 중합체.
- 제1항에 있어서,상기 제2사슬은 공액디엔계 단량체 유래 단위를 더 포함하는 것인 변성 공액디엔계 중합체.
- 제1항에 있어서,수평균 분자량(Mn)이 1,000 g/mol 내지 2,000,000 g/mol이고, 중량평균 분자량(Mw)이 1,000 g/mol 내지 3,000,000 g/mol이고, 피크평균 분자량(Mp)이 1,000 g/mol 내지 3,000,000 g/mol인 변성 공액디엔계 중합체.
- 탄소 용매 중에서, 중합 개시제 존재 하에 공액디엔계 단량체 또는 공액디엔계 단량체와 방향족 비닐계 단량체를 중합하여 활성 제1사슬을 제조하는 단계(S1);상기 활성 제1사슬과 알콕시실란계 변성제를 반응시켜 변성된 활성 제1사슬을 제조하는 단계(S2); 및상기 변성된 활성 제1사슬과 하기 화학식 1로 표시되는 화합물 유래 반복단위를 포함하는 마크로모노머를 반응시키는 단계(S3)를 포함하는 제1항의 변성 공액디엔계 중합체의 제조방법:[화학식 1]상기 화학식 1에서,R11a 및 R11b는 서로 독립적으로 단일결합 또는 치환기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기; 치환기로 치환 또는 비치환된 탄소수 5 내지 20의 시클로알킬렌기; 또는 치환기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기이고, 여기에서 상기 치환기는 탄소수 1 내지 10의 알킬기, 탄소수 5 내지 10의 시클로알킬기, 또는 탄소수 6 내지 20의 아릴기이고,R11c는 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알카이닐기; 탄소수 1 내지 20의 헤테로알킬기; 탄소수 2 내지 20의 헤테로알케닐기; 탄소수 2 내지 20의 헤테로알카이닐기; 탄소수 5 내지 20의 시클로알킬기; 탄소수 6 내지 20의 아릴기; 또는 탄소수 3 내지 20의 헤테로고리기이고,R11d 내지 R11g는 서로 독립적으로 탄소수 1 내지 20의 알킬기; 탄소수 2 내지 20의 알케닐기; 탄소수 2 내지 20의 알카이닐기; 탄소수 1 내지 20의 헤테로알킬기; 탄소수 2 내지 20의 헤테로알케닐기; 탄소수 2 내지 20의 헤테로알카이닐기; 탄소수 5 내지 20의 시클로알킬기; 탄소수 6 내지 20의 아릴기; 탄소수 3 내지 20의 헤테로고리기; 또는 탄소수 1 내지 10의 알킬기로 치환된 1치환, 2치환 또는 3치환의 알킬실릴기이다.
- 제7항에 있어서,상기 마크로모노머는 공액디엔계 단량체 유래 단위를 더 포함하는 것인 변성 공액디엔계 중합체의 제조방법,
- 제7항에 있어서,상기 마크로모노머는 탄화수소 용매 중에서 유기리튬 화합물의 존재 하에 화학식 1로 표시되는 화합물; 또는 화학식 1로 표시되는 화합물과 공액디엔계 단량체를 저중합 반응시켜 제조하는 것인 변성 공액디엔계 중합체의 제조방법.
- 제7항에 있어서,상기 변성제는 중합 개시제 1 몰 대비 0.1 몰 내지 10 몰로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 제7항에 있어서,상기 마크로모노머는 중합 개시제 1 몰 대비 0.1 내지 4.0 몰로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 제1항의 변성 공액디엔계 중합체 및 충전제를 포함하는 고무 조성물.
- 제12항에 있어서,변성 공액디엔계 중합체 100 중량부를 기준으로 0.1 중량부 내지 200 중량부의 충전제를 포함하는 것인 고무 조성물.
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EP20863407.1A EP3925991B1 (en) | 2019-09-11 | 2020-09-11 | Modified conjugated diene-based polymer, method for preparing the same and rubber composition including the same |
CN202080020475.0A CN113574077B (zh) | 2019-09-11 | 2020-09-11 | 改性共轭二烯类聚合物、它的制备方法和包含它的橡胶组合物 |
US17/440,994 US20220162363A1 (en) | 2019-09-11 | 2020-09-11 | Modified Conjugated Diene-Based Polymer, Method for Preparing the Same and Rubber Composition Including the Same |
JP2021547721A JP7242881B2 (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 |
BR112021019924A BR112021019924A2 (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 |
SG11202110158PA SG11202110158PA (en) | 2019-09-11 | 2020-09-11 | Modified conjugated diene-based polymer, method for preparing the same and rubber composition including the same |
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KR1020200116220A KR102504655B1 (ko) | 2020-09-10 | 2020-09-10 | 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 |
KR1020200116221A KR20220033854A (ko) | 2020-09-10 | 2020-09-10 | 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 |
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- 2020-09-11 CN CN202080020475.0A patent/CN113574077B/zh active Active
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EP3925991A4 (en) | 2022-08-10 |
US20220162363A1 (en) | 2022-05-26 |
TW202122426A (zh) | 2021-06-16 |
BR112021019924A2 (pt) | 2022-04-12 |
JP7242881B2 (ja) | 2023-03-20 |
CN113574077A (zh) | 2021-10-29 |
EP3925991B1 (en) | 2023-06-28 |
SG11202110158PA (en) | 2021-10-28 |
CN113574077B (zh) | 2024-01-09 |
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