WO2022103043A1 - 유전 공액디엔계 중합체 및 이를 포함하는 고무 조성물 - Google Patents
유전 공액디엔계 중합체 및 이를 포함하는 고무 조성물 Download PDFInfo
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- WO2022103043A1 WO2022103043A1 PCT/KR2021/015618 KR2021015618W WO2022103043A1 WO 2022103043 A1 WO2022103043 A1 WO 2022103043A1 KR 2021015618 W KR2021015618 W KR 2021015618W WO 2022103043 A1 WO2022103043 A1 WO 2022103043A1
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- WIPO (PCT)
- Prior art keywords
- conjugated diene
- polymer
- based polymer
- oil
- bis
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 291
- 150000001993 dienes Chemical class 0.000 title claims abstract description 168
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- 238000004458 analytical method Methods 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims description 88
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- 238000000034 method Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 125000000524 functional group Chemical group 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 18
- 238000000518 rheometry Methods 0.000 claims description 10
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- 235000012424 soybean oil Nutrition 0.000 claims description 9
- 235000019482 Palm oil Nutrition 0.000 claims description 4
- 235000012343 cottonseed oil Nutrition 0.000 claims description 4
- 239000002385 cottonseed oil Substances 0.000 claims description 4
- 239000002540 palm oil Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019774 Rice Bran oil Nutrition 0.000 claims description 2
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- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 239000008165 rice bran oil Substances 0.000 claims description 2
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- 238000005299 abrasion Methods 0.000 abstract description 34
- 230000001976 improved effect Effects 0.000 abstract description 18
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- 125000004432 carbon atom Chemical group C* 0.000 description 80
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- 239000000243 solution Substances 0.000 description 50
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 46
- 150000001875 compounds Chemical class 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000000654 additive Substances 0.000 description 37
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- 238000004519 manufacturing process Methods 0.000 description 23
- -1 methylene, ethylene, propylene Chemical group 0.000 description 23
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- 239000002174 Styrene-butadiene Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 241001441571 Hiodontidae Species 0.000 description 8
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
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- 125000005370 alkoxysilyl group Chemical group 0.000 description 6
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- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 6
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- 229910052717 sulfur Inorganic materials 0.000 description 6
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
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- 125000000753 cycloalkyl group Chemical group 0.000 description 3
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- 125000005842 heteroatom Chemical group 0.000 description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- UVBMZKBIZUWTLV-UHFFFAOYSA-N n-methyl-n-propylpropan-1-amine Chemical compound CCCN(C)CCC UVBMZKBIZUWTLV-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
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- 239000011591 potassium Substances 0.000 description 3
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
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- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 2
- DTGZORBDGLEVNY-UHFFFAOYSA-N 2-propyloxolane Chemical compound CCCC1CCCO1 DTGZORBDGLEVNY-UHFFFAOYSA-N 0.000 description 2
- OKJPJYXEDILLNA-UHFFFAOYSA-N 3-[[3-[bis(trimethylsilyl)amino]propyl-diethoxysilyl]oxy-diethoxysilyl]-N,N-bis(trimethylsilyl)propan-1-amine Chemical compound C(C)O[Si](O[Si](OCC)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C OKJPJYXEDILLNA-UHFFFAOYSA-N 0.000 description 2
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 description 2
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
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- HTMDLQGFGSQOLM-YMQJAAJZSA-N sodium (1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexan-1-olate Chemical compound [Na+].CC(C)[C@@H]1CC[C@@H](C)C[C@H]1[O-] HTMDLQGFGSQOLM-YMQJAAJZSA-N 0.000 description 2
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- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- OIEANVCCDIRIDJ-UHFFFAOYSA-N 1-ethenyl-5-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1C=C OIEANVCCDIRIDJ-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C08C19/25—Incorporating silicon atoms into the molecule
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- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
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- 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
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- 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
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- C08K5/548—Silicon-containing compounds containing sulfur
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- 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
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- 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 dielectric conjugated diene-based polymer having excellent balance in tensile properties, running resistance and workability, and having improved abrasion resistance and wet road resistance, and a rubber composition comprising 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) have been 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 content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends, and to increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for
- the solution polymerization SBR is prepared by using an anionic polymerization initiator, and a technique for introducing a functional group at the end by binding or modifying the chain end of the formed polymer using various modifiers is used.
- U.S. Patent No. 4,397,994 discloses a technique in which an 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 combined using a binder such as a tin compound. did
- the required physical properties of the tire such as running resistance can be adjusted by increasing the vinyl content in the SBR.
- the vinyl content is high, braking performance and abrasion resistance are disadvantageous, thus Although the styrene content in SBR should be maintained above a certain level, there is a problem in that the effect expressed from the high vinyl content does not appear in this case.
- Patent Document 1 US 4,397,994 A (1983. 08. 09.)
- the present invention has been devised to solve the problems of the prior art, and a tire having excellent properties such as wet road resistance and abrasion resistance while maintaining excellent tensile properties and running resistance (fuel efficiency), and improved processability
- An object of the present invention is to provide a dielectric conjugated diene-based polymer including vegetable oil and having a characteristic viscoelastic tan ⁇ peak through control of the microstructure of the polymer.
- Another object of the present invention is to provide a dielectrically modified conjugated diene-based polymer with improved abrasion resistance and wet road resistance through controlling the microstructure of the polymer itself, as well as additional driving resistance and processability through the introduction of a modifier.
- Another object of the present invention is to provide a rubber composition comprising the conjugated diene-based polymer and/or a modified conjugated diene-based polymer.
- the present invention provides a polymer unit comprising a repeating unit derived from a conjugated diene-based monomer; and vegetable oil, and in the tan ⁇ graph according to the temperature derived from the dynamic viscoelasticity analysis by the rheometric system (Advanced Rheometric Expansion System, ARES), the full width at half maximum of the tan ⁇ peak appearing in the temperature range of -100°C to 100°C (Full width at half maximum, FWHM) value is 20°C or higher, and the rheology system is a torsion mode using a dynamic mechanical analyzer under the conditions of a frequency of 10 Hz, a strain of 0.5%, and a temperature increase rate of 5°C/min. It provides a dielectric conjugated diene-based polymer that is measured under.
- ARES Advanced Rheometric Expansion System
- the present invention provides a modified polymer unit comprising a repeating unit derived from a conjugated diene-based monomer, and a functional group derived from a modifier; and vegetable oil, and in the tan ⁇ graph according to the temperature derived from the dynamic viscoelasticity analysis by the rheometric system (Advanced Rheometric Expansion System, ARES), the full width at half maximum of the tan ⁇ peak appearing in the temperature range of -100°C to 100°C (Full width at half maximum, FWHM) value is 20°C or higher, and the rheology system is a torsion mode using a dynamic mechanical analyzer under the conditions of a frequency of 10 Hz, a strain of 0.5%, and a temperature increase rate of 5°C/min. It provides a dielectrically modified conjugated diene-based polymer to be measured under.
- ARES Advanced Rheometric Expansion System
- the present invention provides a rubber composition
- a rubber composition comprising a polymer and a filler, wherein the polymer is a dielectric conjugated diene-based polymer or a dielectrically modified conjugated diene-based polymer.
- the present invention includes a conjugated diene-based polymer and a filler, and in a tan ⁇ graph according to temperature derived from dynamic viscoelasticity analysis by a rheometric system (Advanced Rheometric Expansion System, ARES), -100°C to 100°C
- ARES Advanced Rheometric Expansion System
- the full width at half maximum (FWHM) value of the tan ⁇ peak appearing in the temperature range is 31° C. or more
- the rheometry system uses a dynamic mechanical analyzer in torsional mode, with a frequency of 10 Hz and a strain of 0.5% And it is measured under the conditions of a temperature increase rate of 5 °C / min, the conjugated diene-based polymer provides a rubber composition comprising vegetable oil.
- the dielectric conjugated diene-based polymer according to the present invention has an effect of having excellent tensile properties and running resistance while remarkably improving wet road resistance and abrasion resistance, and also has excellent processability including vegetable oil.
- the conjugated diene-based polymer according to the present invention can implement excellent abrasion resistance and wet road resistance through microstructure control, and has excellent processability including vegetable oil, and in addition, excellent running resistance (fuel efficiency characteristics) and tensile properties by introducing a modifier can be implemented
- ARES Advanced Rheometric Expansion System
- polymer refers to a polymer compound prepared by polymerizing monomers, whether of the same or different type.
- generic term polymer encompasses the term homopolymer, which is usually used to refer to a polymer prepared from one kind of monomer, and the term copolymer as defined below.
- the term '1,2-vinyl bond content' refers to the 1,2-position in the polymer chain of the polymer based on the portion (total amount of polymerized butadiene) derived from the conjugated diene-based monomer (butadiene, etc.) in the polymer. Refers to the mass (or weight) percentage of butadiene contained.
- 'styrene bond content' refers to a percentage by mass (or weight) of styrene contained in the polymer chain of the polymer derived from an aromatic vinylic monomer (styrene, etc.) in the polymer.
- room temperature' refers to a natural temperature without heating or cooling, and is a temperature of 20 ⁇ 5°C.
- substitution' may mean that hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, within the functional group, atomic group or compound
- One or two or more plural substituents may be present depending on the number of hydrogens present, and when plural substituents are present, each substituent may be the same or different from each other.
- the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and may include a linear alkyl group such as methyl, ethyl, propyl, and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl and neo-pentyl; and cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbons including one or two or more unsaturated bonds.
- 'alkylene group' may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.
- 'cycloalkyl group' may mean a cyclic saturated hydrocarbon.
- '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. may be meant to include all of them.
- 'aralkyl' is also referred to as aralkyl, and may refer to a combination group of an alkyl group and an aryl group formed by substituting an aryl group for a hydrogen atom bonded to a carbon constituting the alkyl group.
- the term 'single bond' may refer to a single covalent bond itself 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 material itself derived from a certain material.
- the term 'polymer unit' refers to a polymer chain formed by polymerizing one kind of monomer or multiple kinds of monomers.
- the term 'modified polymer unit' refers to a modified polymer chain that further includes a functional group derived from a modifier in a polymer chain formed by polymerizing a kind of monomer or multiple kinds of monomers.
- '1,2-vinyl bond content' and 'styrene bond content' are measured and analyzed by using Varian VNMRS 500 MHz NMR to measure and analyze the vinyl (Vinyl) content and styrene content in the polymer unit.
- 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 6.0 ppm, 7.2 ⁇ 6.9 ppm random styrene, 6.9 ⁇ 6.2 ppm block styrene, and 5.8 ⁇ 5.1 ppm 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm are measured by calculating the 1,2-vinyl bond content and the styrene bond content in the entire polymer, respectively, using the peak of 1,2-vinyl.
- 'weight average molecular weight (Mw)', 'molecular weight distribution (MWD)' and 'unimodal characteristic' are GPC (Gel permeation chromatograph) (PL GPC220, Agilent Technologies), and the weight average molecular weight (Mw) under the following conditions , number average molecular weight (Mn) was measured, a molecular weight distribution curve was obtained, and molecular weight distribution (PDI, MWD, Mw/Mn) was obtained by calculating from each of the measured molecular weights.
- GPC Gel permeation chromatograph
- the 'glass transition temperature (Tg)' is a differential scanning calorimetry (Differential Scanning Calorimetry, DSCQ100, TA company) in accordance with ISO 22768: 2006, from -100 °C to 10 °C / under the circulation of nitrogen 50 ml / min.
- the differential scanning calorimetry curve (DSC curve) is recorded while the temperature is raised to min, and the peak top (Inflection point) of the DSC differential curve is taken as the glass transition temperature.
- TA company ARES-G2
- the 'Si content' is measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) as an ICP analysis method.
- ICP-OES inductively coupled plasma emission analyzer
- crucible add about 1 mL of concentrated sulfuric acid (98% by weight, Electronic grade), and heat at 300° C. for 3 hours, and heat the sample in an electric furnace (Thermo Scientific, Lindberg Blue M) in step 1 After conducting the conversation in the program of to 3,
- 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);
- 'N content' may be measured through an NSX analysis method, and the NSX analysis method may be measured using a trace nitrogen quantitative analyzer (NSX-2100H).
- a 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 the ozonizer, and heater
- the temperature to 800°C, wait for about 3 hours to stabilize the analyzer.
- a calibration curve in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was prepared using Nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration was obtained. Then, draw a straight line using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample was placed on the auto sampler of the analyzer and measured to obtain an area. Calculate the nitrogen atom content using the area of the obtained sample and the calibration curve.
- the sample used in the NSX analysis method is a modified conjugated diene-based polymer sample obtained by removing the solvent by putting it in hot water heated with steam and stirring, and may be a sample from which residual monomers and residual denaturants are removed.
- oil if oil is added to the above sample, it may be a sample after oil is extracted (removed).
- the present invention by controlling the microstructure that can be realized in a tire having characteristics of improved wet road resistance and abrasion resistance while maintaining superiority in tensile properties and running resistance (fuel efficiency), in addition to improved processability, to provide a dielectric conjugated diene-based polymer having a viscoelastic tan ⁇ peak of
- the dielectric conjugated diene-based polymer according to the present invention includes a polymer unit including a repeating unit derived from a conjugated diene-based monomer; and vegetable oil, and in the tan ⁇ graph according to the temperature derived from the dynamic viscoelasticity analysis by the rheometric system (Advanced Rheometric Expansion System, ARES), the full width at half maximum of the tan ⁇ peak appearing in the temperature range of -100°C to 100°C (Full width at half maximum, FWHM) value is 20°C or higher, and the rheology system is a torsion mode using a dynamic mechanical analyzer under the conditions of a frequency of 10 Hz, a strain of 0.5%, and a temperature increase rate of 5°C/min. It is characterized in that it is measured under
- the dielectric conjugated diene-based polymer realizes a polymer having a specific microstructure through application of a characteristic manufacturing method described later, thereby controlling the dynamic viscoelastic behavior of the polymer to have a unique tan ⁇ peak. , through which the tensile properties and running resistance are excellent, and the wet road resistance and wear resistance can be improved.
- the conjugated diene-based polymer contains vegetable oil through the application of the manufacturing method described later, thereby having the above excellent properties and improving processability.
- the conjugated diene-based polymer is a rheometric system (Advanced Rheometric Expansion System, ARES) in the tan ⁇ graph according to the temperature derived from the dynamic viscoelasticity analysis, -100 °C to 100 °C It is characterized in that the full width at half maximum (FWHM) value of the tan ⁇ peak appearing in the temperature range is 20°C or more.
- ARES Advanced Rheometric Expansion System
- the peak width is not formed widely, such as two or more tan ⁇ peaks or a very narrow peak width. This may also be related to the glass transition temperature, and when units within a polymer are partitioned like a block copolymer and the glass transition temperature difference between blocks is large, the tan ⁇ peak is narrow and two or more peaks may appear.
- the peak width is generally very narrow.
- the glass transition temperature may be the same for both the block copolymer and the random copolymer, but there is a large difference in wet road resistance.
- the glass transition temperature is changed, there is still a problem to implement a polymer having improved performance in that a change in abrasion resistance occurs and the physical properties of the basic polymer are changed. That is, it is difficult to balance abrasion resistance and wet road resistance, and these two characteristics remain a more difficult task in that they tend not to be improved at the same time through the modification process.
- the conjugated diene-based polymer according to an embodiment of the present invention is prepared by a manufacturing method that controls the microstructure of the polymer, even if it has the same glass transition temperature as that of the conventional modified conjugated diene-based polymer, the characteristic It has a tan ⁇ peak of , so it is possible to realize the effect of simultaneously increasing wet road resistance and abrasion resistance.
- the tan ⁇ peak appears in the temperature range of -100°C to 100°C, and the half value of the tan ⁇ peak It is characterized in that the full width is 20°C or more.
- the number of tan ⁇ peaks appearing in the above temperature range may be usually one, but may be two or more.
- the full width at half maximum of the tan ⁇ peak may be at least 20°C, and preferably at least 30°C. In addition, the full width at half maximum may be at most 80 °C, preferably 70 °C or less. As another example, the full width at half maximum of the tan ⁇ peak may be 30°C or more and 80°C or less, or 35°C or more and 60°C or less. If the full width at half maximum is less than 20 °C, there is a problem that the wet road resistance is significantly lowered at the same glass transition temperature, and when the full width at half maximum of the peak becomes greater than 80 ° C. The problem of increased hysteresis is inevitably accompanied, and accordingly, a problem of poor fuel efficiency may occur.
- the tan ⁇ peak may be a peak that appears at -100°C to 100°C, preferably at -80°C to 20°C, and more preferably at -70°C to 0°C.
- a peak appears in the above range, a more advantageous effect in abrasion resistance can be expected.
- Dynamic viscoelasticity analysis by the rheometry system was performed using a dynamic mechanical analyzer (TA company, ARES-G2) in torsional mode at a frequency of 10 Hz, strain 0.5%, and a temperature increase rate of 5 °C/min. , is to measure tan ⁇ according to temperature in a temperature range of -100° C. to 100° C., and the graph derived at this time is the tan ⁇ value with respect to temperature.
- TA company ARES-G2
- the conjugated diene-based polymer comprises a polymer unit including a repeating unit derived from a conjugated diene-based monomer; And it may be an oil-extended polymer containing vegetable oil.
- oil-extended rubber is a rubber manufactured by mixing petroleum-based oil with synthetic rubber to improve flexibility, elasticity, and compounding properties of synthetic rubber such as a conjugated diene-based polymer.
- the conjugated diene-based polymer according to the present invention is manufactured using vegetable oil derived from plants, which is an eco-friendly material, and contains vegetable oil in the polymer, and thus, it is eco-friendly and can be expected to improve flexibility, elasticity, and compounding properties.
- 'vegetable oil' is an oil component derived from a plant, that is, extracted from a plant, and is generally a triglyceride molecule represented by the following Chemical Formula 14.
- R 14a to R 14c are each a radical of an ester derived from a fatty acid, and are each an unsaturated or saturated hydrocarbon group.
- R 14a to R 14c may vary depending on the type of vegetable oil, and may be illustratively shown in Table 1 below.
- the vegetable oil may have an iodine number of 70 to 150, specifically, 110 to 140.
- the vegetable oil may have a glass transition temperature of -110°C to -100°C, and when it is within this range, the abrasion resistance of the rubber composition may be further improved.
- the vegetable oil is not particularly limited and may be included in the present invention as long as it is an oil derived from a plant, but specifically, the vegetable oil is soybean oil, rapeseed oil, canola oil, sunflower oil, linseed oil, rice bran oil, palm oil, olive oil, peanut oil , may be at least one selected from the group consisting of palm oil, cottonseed oil and coconut oil. More specifically, in terms of more advantageously achieving the desired effect, the vegetable oil may be soybean oil.
- the conjugated diene-based polymer may include 10 parts by weight to 60 parts by weight, or 20 parts by weight to 37.5 parts by weight of vegetable oil based on 100 parts by weight of the polymer unit. In this case, there is an effect that the flexibility, elasticity, and processability of the conjugated diene-based polymer are more excellent.
- the conjugated diene-based polymer includes a polymer unit including a repeating unit derived from a conjugated diene-based monomer
- the conjugated diene-based monomer is, for example, 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 means a halogen atom) ) may be at least one selected from the group consisting of.
- the polymer unit further includes a repeating unit derived from an aromatic vinyl-based monomer
- the aromatic vinyl-based monomer is, for example, 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- 1-methyl eth,
- the polymer unit may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with the repeating unit derived from the conjugated diene-based monomer.
- the repeating unit derived from the diene-based monomer 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 conjugated diene-based polymer is a copolymer further comprising a diene-based monomer
- the conjugated diene-based polymer contains more than 0 wt% to 1 wt%, more than 0 wt% to 0.1 wt%, more than 0 wt% of the repeating unit derived from the diene-based monomer Weight% to 0.01% by weight, or more than 0% by weight to 0.001% by weight may be included, and there is an effect of preventing gel formation within this range.
- the polymer unit of the conjugated diene-based polymer when two or more monomers are included in the polymer unit of the conjugated diene-based polymer, it may have a chain structure intermediate between a random copolymer and a block copolymer, and in this case, control of the microstructure is It can be easy, and there is an effect of excellent balance between the respective physical properties.
- the random copolymer may mean that the repeating units constituting the copolymer are disorderly arranged.
- the conjugated diene-based polymer may have a glass transition temperature of -100°C to 20°C.
- the glass transition temperature is a value that varies depending on the microstructure of the polymer, but in order to improve abrasion resistance, it is preferable to prepare the polymer to satisfy the above range, more preferably -100°C to 0°C, more preferably -90°C to -10°C, even more preferably -80°C to -20°C.
- the glass transition temperature is the bonding method (1,2-bond or 1,4-bond) of the conjugated diene-based monomer in the polymer unit, the presence or absence of an aromatic vinyl-based repeating unit, the content of the repeating unit derived from the aromatic vinyl-based monomer, the polymerization method, and It can be flexibly controlled by the microstructure (1,2-vinyl bond content and styrene bond content) in each unit according to polymerization conditions.
- the conjugated diene-based polymer may have a 1,2-vinyl bond content of 10 to 80 parts by weight, preferably 20 to 60 parts by weight, more preferably 20 to 50 parts by weight, based on 100 parts by weight of the polymer.
- a balanced improvement in abrasion resistance and wet road resistance can be expected while excellent in tensile properties and driving resistance.
- a modified polymer unit comprising a repeating unit derived from a conjugated diene-based monomer, and a functional group derived from a modifier; and vegetable oil, and in the tan ⁇ graph according to the temperature derived from the dynamic viscoelasticity analysis by the rheometric system (Advanced Rheometric Expansion System, ARES), the full width at half maximum of the tan ⁇ peak appearing in the temperature range of -100°C to 100°C (Full width at half maximum, FWHM) value is 20°C or higher, and the rheology system is a torsion mode using a dynamic mechanical analyzer under the conditions of a frequency of 10 Hz, a strain of 0.5%, and a temperature increase rate of 5°C/min.
- a dielectrically modified conjugated diene-based polymer that is measured under is provided.
- Si and N content may be 50 ppm or more, or 50 ppm to 1000 ppm, respectively, based on the total weight of the polymer, and in the case of the lower limit, preferably 100 It may be ppm or more, it may be 150 ppm or more, and in the case of the upper limit, it may be preferably 700 ppm or less, preferably 500 ppm or less. Within this range, there is an effect excellent in mechanical properties such as tensile properties and viscoelastic properties of the rubber composition containing the modified conjugated diene-based polymer.
- Si and N may be derived from compounds having a modifying functional group, such as a modifying agent, a modification initiator, or a modifying monomer, which will be described later.
- the modified conjugated diene-based polymer includes a functional group derived from a modifier, and the modifier is for modifying the ends of the polymer.
- the modified conjugated diene-based polymer may be a silica affinity modifier, an alkoxysilane-based 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, and thus a silica-based filler and It may mean a functional group capable of interaction between functional groups derived from the denaturant.
- the modifier may be an alkoxysilane-based modifier, and a specific example may be an alkoxysilane-based compound containing at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
- a specific example may be an alkoxysilane-based compound containing at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
- the affinity of the modified conjugated diene-based polymer with an inorganic filler and the like can be improved from the modifier-derived functional group present at one end of the polymer unit, and thus the viscoelasticity of the rubber composition comprising the modified conjugated diene-based polymer There is an effect that the characteristic is further improved.
- the alkoxysilane-based compound contains a nitrogen atom, in addition to the effect derived from the silyl group, an additional synergistic effect derived from the nitrogen atom can be expected. In order to optimally realize this effect, it is preferable to apply a compound including an N-containing functional group.
- the modifier may include a compound represented by the following formula (1).
- 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 is hydrogen, or an alkylene group having 1 to 10 carbon atoms.
- R 21 is a single bond, an alkyl having 1 to 10 carbon atoms Rene group, or -[R 42 O] j - may be, R 42 may be an alkylene group having 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, n is 0, 1 , or may be an integer of 2, and j may be an integer selected from 1 to 30.
- R 1 may be a single bond or an alkylene group having 1 to 5 carbon atoms
- R 2 and R 3 may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 4 is It may be hydrogen, an alkyl group having 1 to 5 carbon atoms, a trialkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms
- R 21 is a single bond, or an alkylene group having 1 to 5 carbon atoms, or -[R 42 O] j -
- R 42 may be an alkylene group having 1 to 5 carbon atoms
- a may be an integer of 2 or 3
- m may be an integer selected from 1 to 3
- the heterocyclic group when R 4 is a heterocyclic group, the heterocyclic group may be unsubstituted or substituted with a trisubstituted alkoxy silyl group, and when the heterocyclic group is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group It may be substituted by being connected to the heterocyclic group by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxy silyl group may mean an alkoxy silyl group substituted with an alkoxy group having 1 to 10 carbon atoms.
- the compound represented by Formula 1 may include 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), N,N-diethyl-3-(trime
- the modifier may include a compound represented by the following formula (2).
- 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 are each independently 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 are each independently 0, 1, 2 or 3, b+c ⁇ 1, and A is or may be, and in this case, 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 2 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-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine) may be one selected from the group consisting of.
- the modifier may include a compound represented by the following formula (3).
- a 1 and A 2 may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms including or not including an oxygen atom
- R 17 to R 20 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- L 1 to L 4 are each independently a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms
- 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
- a ring formed may include 1 to 3 at least one hetero atom selected from the group consisting of N, O and S.
- a 1 and A 2 may each independently be an alkylene group having 1 to 10
- R 17 to R 20 may each independently be an alkyl group having 1 to 10 carbon atoms
- L 1 to L 4 is each independently a trialkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L 1 and L 2 and L 3 and L 4 are connected to each other to form a ring having 1 to 3 carbon atoms may be formed, 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 May include dogs.
- the compound represented by Formula 3 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 -Tetraethoxydisiloxane-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) amine) (3,3''-(1,1,3,
- the modifier may include a compound represented by the following formula (4).
- R 22 and R 23 are each independently an alkylene group having 1 to 20 carbon atoms, or -R 28 [OR 29 ] f -, and R 24 to R 27 are each independently an alkyl group having 1 to 20 carbon atoms, or It may be an aryl group having 6 to 20 carbon atoms, R 28 and R 29 may each independently be an alkylene group having 1 to 20 carbon atoms, R 47 and R 48 may each independently be a divalent hydrocarbon group having 1 to 6 carbon atoms, , d and e are each independently 0, or an integer selected from 1 to 3, d+e may be an integer of 1 or more, and f may be an integer of 1 to 30.
- R 22 and R 23 may each independently be an alkylene group having 1 to 10 carbon atoms, or -R 28 [OR 29 ] f -, and R 24 to R 27 are each independently C 1 It may be an alkyl group of to 10, R 28 and R 29 may each independently be an alkylene group having 1 to 10 carbon atoms, d and e are each independently 0, or an integer selected from 1 to 3, d + e is It may be an integer of 1 or more, and f may be an integer selected from 1 to 30.
- the compound represented by Formula 4 may be a compound represented by Formula 4a, Formula 4b, or Formula 4c.
- R 22 to R 27 , d and e are the same as described above.
- the compound represented by Formula 4 is 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine (1,4-bis(3-(3-(triethoxysilyl) ) propoxy) propyl) piperazine, 1,4-bis (3- (triethoxysilyl) propyl) piperazine (1,4-bis (3- (triethoxysilyl) propyl) piperazine), 1,4-bis (3- (trimethoxysilyl) propyl) piperazine (1,4-bis (3- (trimethoxysilyl) propyl) piperazine), 1,4-bis (3- (dimethoxymethylsilyl) propyl) piperazine (1,4- bis(3-(dimethoxymethylsilyl)propyl)piperazine), 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1-(3
- the modifier may include a compound represented by the following Chemical Formula 5.
- R 30 may be a monovalent hydrocarbon group having 1 to 30 carbon atoms
- R 31 to R 33 may each independently be an alkylene group having 1 to 10 carbon atoms
- R 34 to R 37 are each independently a carbon number It may be an alkyl group of 1 to 10, g and h are each independently 0, or an integer selected from 1 to 3, g+h may be an integer of 1 or more.
- the modifier may include a compound represented by the following formula (6).
- a 3 and A 4 may each independently be an alkylene group of 1 to 10
- R 38 to R 41 may each independently be an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms
- i may be an integer selected from 1 to 30.
- the denaturant is 3,4-bis(2-methoxyethoxy)-N-(4-(triethoxysilyl)butyl)aniline (3,4-bis(2-methoxyethoxy)-N-( 4-(trimethylsilyl)butyl)aniline), N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine (N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine), 2,4-bis(2-methoxy oxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine (2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine) and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,
- the modifier may include a compound represented by the following formula (7).
- R 43 , R 45 and R 46 may each independently be an alkyl group having 1 to 10 carbon atoms, R 44 may be an alkylene group having 1 to 10 carbon atoms, and k may be an integer selected from 1 to 4 there is.
- the compound represented by Formula 7 is 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13- disila-8-stanpentadecane (8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane); 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8,8- dimetyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane), 8,8-dibutyl-3,13-dimeth
- the modifier may include a compound represented by the following formula (8).
- 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 each independently a carbon number 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 modifier may include a compound represented by the following Chemical Formula 9.
- R e1 and R e2 are each independently an alkylene group having 1 to 10 carbon atoms
- Re3 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 Re3 to Re6 is —R e7 SiR e8 Re9 Re9 Re10 , wherein Re7 is a single bond or an alkylene group having 1 to 10 carbon atoms
- Re8 to Re10 are independently of each other 1 carbon number an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein at least one of R e8 to R e10 is an alkoxy group having 1 to 10 carbon atoms.
- the modifier may include a compound represented by the following Chemical Formula 10.
- 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 a hydrogen atom, 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 and p is 0 or an integer of 1, and when p is 0, R f1 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
- the modifier may include a compound represented by the following Chemical Formula 11.
- R g1 to R g4 are each independently a hydrogen atom, 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 SiOR g6 , but R g1 to At least one of R g4 is -R g5 SiOR g6 , wherein R g5 is a single bond or an alkylene group having 1 to 10 carbon atoms, R g6 is an alkyl group having 1 to 10 carbon atoms, and Y is C or N, wherein Y When is N, R g4 is absent.
- the modifier may include a compound represented by the following Chemical Formula 12.
- 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.
- the modifier may include a compound represented by the following Chemical Formula 13.
- 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 from 2 to 100 .
- the dielectrically modified conjugated diene-based polymer according to an embodiment of the present invention has a shrinkage factor (g') of 0.1 or more, preferably 0.1 or more and 1.0 or less, obtained by gel permeation chromatography-light scattering method measurement with a viscosity detector. Specifically, it may be 0.3 or more and 0.9 or less.
- the shrinkage factor (g') obtained by the gel permeation chromatography-light scattering method measurement is the ratio of the intrinsic viscosity of the branched polymer to the intrinsic viscosity of the linear polymer having the same absolute molecular weight. It can be used as an indicator of the branching structure of a polymer, that is, as an indicator of the proportion occupied by branches, for example, as the shrinkage factor decreases, the branching index of the polymer tends to increase, so comparing polymers with equal absolute molecular weights In this case, the more branching, the smaller the shrinkage factor, so it can be used as an index of the degree of branching.
- the shrinkage factor was calculated based on the solution viscosity and light scattering method by measuring the chromatogram using a gel chromatography-light scattering measuring device equipped with a viscosity detector, specifically, a column using a polystyrene-based gel as a filler.
- the absolute molecular weight and the intrinsic viscosity corresponding to each absolute molecular weight were obtained using a GPC-light scattering measuring device equipped with two connected light scattering detectors and a viscosity detector.
- the shrinkage factor was calculated as the ratio of the intrinsic viscosity corresponding to each absolute molecular weight.
- the shrinkage factor is obtained by injecting a sample into a GPC-light scattering measuring device (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector and a viscosity detector to obtain an absolute molecular weight from the light scattering detector, and to the absolute molecular weight from the light scattering detector and the viscosity detector After obtaining the intrinsic viscosity [ ⁇ ] for ⁇ ] 0 ) was expressed as a shrinkage factor.
- a GPC-light scattering measuring device Viscotek TDAmax, Malvern Co.
- the eluent is a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (20 mL of N,N,N',N'-tetramethylethylenediamine is mixed with 1L of tetrahydrofuran adjusted), and the column was used for PL Olexix (Agilent), and was measured at an oven temperature of 40° C. and a THF flow rate of 1.0 mL/min. The sample was prepared by dissolving 15 mg of polymer in 10 mL of THF. .
- Equation 1 M is an absolute molecular weight.
- the dielectrically modified conjugated diene-based polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, or 10 wt% to 60 wt%.
- the vinyl content may mean the content of a 1,2-added conjugated diene-based monomer rather than 1,4-added based on 100% by weight of a conjugated diene-based polymer composed of a monomer having a vinyl group and an aromatic vinyl-based monomer. there is.
- the dielectrically modified conjugated diene-based polymer may have a Mooney stress relaxation rate measured at 100° C. of less than 0.7, and may be 0.7 to 3.0.
- the Mooney stress relaxation rate may be less than 0.7, preferably 0.6 or less, more preferably 0.5 or less, and optimally 0.4 or less in the case of a branched polymer with a high degree of branching, and in the case of a linear polymer with a small degree of branching
- it may be 0.7 to 2.5, more preferably 0.7 to 2.0.
- the Mooney stress relaxation rate represents a change in stress that appears in response to the same amount of strain, and may be measured using a Mooney viscometer. Specifically, the Mooney stress relaxation rate was 27 ⁇ 3 g after leaving the polymer at room temperature (23 ⁇ 5°C) for more than 30 minutes at 100°C and a rotor speed of 2 ⁇ 0.02 rpm using a Monsanto MV2000E Large Rotor. was collected and filled in the die cavity, and a platen was operated to measure the Mooney viscosity while applying a torque, and then measure the slope value of the Mooney viscosity change that appears as the torque is released.
- the Mooney stress relaxation rate can be used as an index of the branching structure of the polymer.
- the Mooney stress relaxation rate can be used as an index of the branching degree.
- the dielectric (modified) conjugated diene-based polymer according to an embodiment of the present invention may include a functional group derived from a denaturation initiator at the other end in addition to one end including a functional group derived from a denaturant, wherein the denaturation initiator is N- It may be a reaction product of a functional group-containing compound and an organometallic compound.
- the N-functional group-containing compound may be an aromatic hydrocarbon compound containing an N-functional group including an amino group, an amide group, an amino group, an imidazole group, a pyrimidyl group or a cyclic amino group substituted or unsubstituted with a substituent
- the substituent is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or alkoxysilyl having 1 to 10 carbon atoms. it can be a gimmick
- the dielectric (modified) conjugated diene-based polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 300,000 g/mol to 3,000,000 g/mol , 400,000 g/mol to 2,500,000 g/mol, or 500,000 g/mol to 2,000,000 g/mol, within this range, driving resistance and wet road resistance are more balanced and excellent.
- Mw weight average molecular weight measured by gel permeation chromatography
- the dielectric (modified) conjugated diene-based polymer according to an embodiment of the present invention may be a high molecular weight polymer having a weight average molecular weight of 800,000 g/mol or more, preferably 1,000,000 g/mol or more, and thus a polymer having excellent tensile properties can be implemented, and this can be achieved by realizing the effect of lengthening the chain of the polymer along with the control of the microstructure when manufactured according to the above-described manufacturing method.
- the dielectric (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 1,500,000 g/mol, or 100,000 g/mol to 1,200,000 g/mol, and the number average molecular weight may be preferably 400,000 g/mol or more, more preferably 500,000 g/mol or more.
- the peak top 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. Within this range, there is an excellent effect of rolling resistance and wet road resistance.
- the molecular weight distribution curve by gel permeation chromatography is unimodal, and the molecular weight distribution may be 1.0 to 3.0, preferably 1.0 to 2.5, more preferably 1.0 to 2.0, even more preferably 1.0 or more and less than 1.7, wherein the unimodal curve shape and molecular weight distribution can be simultaneously satisfied by continuous polymerization to be described later.
- the dielectric (modified) conjugated diene-based polymer according to an embodiment of the present invention must satisfy that the Mooney viscosity measured under ASTM D1646 is 40 to 120, preferably 45 to 100. . There may be various scales for evaluating the processability, but when the Mooney viscosity satisfies the above range, the processability may be quite excellent.
- the difference between the glass transition initiation temperature and the termination temperature is through the control of the polymer microstructure such as the styrene bond content and the 1,2-vinyl bond content.
- the present invention provides a method for producing a conjugated diene-based polymer as follows in order to prepare the dielectric conjugated diene-based polymer.
- the dielectric conjugated diene-based polymer production method is a continuous production method, comprising the steps of polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of a hydrocarbon solvent, a polymerization initiator and a polar additive (S1); and a step (S2) of mixing vegetable oil after step (S1), wherein step (S1) is continuously performed in two or more polymerization reactors, and when the polymerization conversion of the first reactor is 70% to 85% It is transferred to the second reactor, and a polar additive or a polar additive and a conjugated diene-based monomer are additionally added to the second reactor.
- the hydrocarbon solvent is not particularly limited, but may be, for example, at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
- the polymerization initiator may be used in an amount of 0.1 to 3.0 equivalents based on 1.0 equivalent of the monomer, preferably 0.1 to 2.0 equivalents, and more preferably 0.5 to 1.5 equivalents. In another example, the polymerization initiator may be used in an amount of 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 100 g of the total monomer.
- 100 g of the total of the monomers may represent the total amount of the conjugated diene-based monomer and the aromatic vinyl-based monomer.
- the polymerization initiator may be an organometallic compound, for example, at least one selected from an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.
- the organometallic compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1- Naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl It may be at least one selected from the group consisting of potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropyl
- the polymerization initiator may be a modification initiator
- the modification initiator may be a reaction product of an N-functional group-containing compound and the organometallic compound.
- step (S1) is, for example, a step in which a polymerization reaction of a conjugated diene-based monomer and an aromatic vinyl-based monomer is performed by anionic polymerization.
- 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 (adiabatic polymerization), and the constant temperature polymerization includes the step of polymerizing by its own heat of reaction without optionally applying heat after the polymerization initiator is added.
- the elevated temperature polymerization may refer to a polymerization method
- the elevated temperature polymerization may refer to a polymerization method in which the temperature is increased by arbitrarily applying heat after the polymerization initiator is added, and the isothermal polymerization is heat by adding heat after the polymerization initiator is added It may refer to a polymerization method in which the temperature of the polymer is kept constant by increasing the temperature or taking heat away.
- the polymerization in step (S1) may be carried out by further including 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 may be, for example, 1,2-butadiene.
- the polymerization of step (S1) is carried out in two or more polymerization reactors, and the polymerization conversion rate in the first polymerization reactor among the polymerization reactors is 70% or more and 85% or less, or 70 % to 80%. That is, the polymerization in step (S1) is characterized in that the polymerization is performed only until the polymerization conversion rate in the first polymerization reactor is 70% or more, 70% or more and 85% or less, or 70% or more and 80% or less.
- the polymerization in the first reactor may be carried out, for example, 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, 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, within this range.
- the step (S1) is performed in two or more reactors, and after polymerization to the above-mentioned polymerization conversion rate in the first reactor is made, it is transferred to the second reactor, and the polar additive is added to the second reactor.
- additional input of a conjugated diene-based monomer is performed.
- the additionally added polar additive, or polar additive or conjugated diene-based monomer may be added simultaneously or sequentially, and may be added at one point in the polymerization conversion range described above, or divided at several points in the range. It may be added or continuously added within the time point of the above range.
- Additional input of a polar additive or a polar additive and a conjugated diene-based monomer can be a means for realizing the glass transition temperature characteristics of the polymer to be prepared in addition to controlling the polymerization conversion rate in the first reactor. After a certain polymerization conversion rate, further energization of the polymerization reaction can cause a deformation of the microstructure.
- the polar additive has an effect of inducing easy formation of a random copolymer by correcting a difference in reaction rate between the conjugated diene-based monomers and the aromatic vinyl-based monomers when copolymerizing them.
- an appropriate amount of the polar additive to be added may be used in a direction in which the full width at half maximum of the tan ⁇ peak is widened.
- the additionally added polar additive may be used in a proportion of 0.001 g to 10 g, or 0.01 g to 1.0 g, more preferably 0.02 g to 0.5 g, based on 100 g of the total monomer used in the polymerization initiation.
- the optionally added conjugated diene-based monomer may be used in an amount of 5 g to 25 g, or 5 g to 20 g based on 100 g of the monomer used in the polymerization initiation.
- the additionally added polar additive or conjugated diene monomer is controlled in the same amount as above, it is easy to control the glass transition temperature of the polymer and finer adjustment is possible. There are advantages.
- the total amount of the polar additive used in the polymerization of step (S1) may be used in a ratio of 0.001 g to 50 g, or 0.002 g to 1.0 g based on 100 g of the total monomer.
- the total amount of the polar additive may be used in a ratio of greater than 0 g to 1 g, 0.01 g to 1 g, or 0.1 g to 0.9 g based on 100 g of the total polymerization initiator.
- the total amount of the polar additive used means a content including the additionally added polar additive.
- the polymerization in the second reactor may be carried out, for example, 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, 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, within this range.
- the polymerization temperature in the first reactor and the second reactor may also be affected, and in this case, the polymerization temperature of the second reactor is set to the first It is preferable that the polymerization temperature of the reactor is controlled to be lower than or equal to the polymerization temperature of the reactor, and the polymerization temperature of the second reactor is preferably 60° C. or higher.
- the polar additive is, for example, tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene glycol dimethyl ether, diethylene glycol, dimethyl Ether, tertiary-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'- It may be at least one selected from the group consisting of tetramethylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di (2- tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate
- the polymerization conversion rate may be determined by measuring the concentration of solids in a polymer solution containing a polymer during polymerization, for example.
- a positive polymer solution is filled in a cylindrical container, the cylindrical container is separated from the reactor, the weight (A) of the cylinder filled with the polymer solution is measured, and the polymer solution filled in the cylindrical container is placed in an aluminum container; For example, transfer to an aluminum dish and measure the weight (B) of the cylindrical container from which the polymer solution has been removed, the aluminum container containing the polymer solution is dried in an oven at 140° C. for 30 minutes, and the weight (C) of the dried polymer is measured After the measurement, it may be calculated according to Equation 2 below.
- the total solid content is the total solid content (monomer) content in the polymer solution separated in each reactor, and is a weight percentage of the solid content with respect to 100% of the polymer solution.
- the total solid content is 20% by weight, when this is applied to Equation 2, it may be calculated by substituting 20/100, that is, 0.2.
- the polymer polymerized in the second reactor may be sequentially transferred to the final polymerization reactor, and polymerization may proceed until the polymerization conversion ratio is 95% or more.
- the polymerization conversion rate for each reactor may be appropriately adjusted for each reactor to control the molecular weight distribution, and then a reaction terminator for inactivating the active site may be added, and modified conjugated diene
- the active polymer may be transferred to a denaturation reaction process, and the reaction terminator may be applied without limitation as long as it is a material that can be generally used in the art.
- the active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organometallic cation of a polymerization initiator are combined.
- the step (S2) may be performed by adding and mixing vegetable oil before drying the polymer after the step (S1).
- the present invention provides a method for preparing the modified conjugated diene-based polymer as follows in order to prepare the modified conjugated diene-based polymer.
- the modified conjugated diene-based polymer production method is a continuous production method, comprising the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of a hydrocarbon solvent, a polymerization initiator and a polar additive (S3); a denaturing reaction step of reacting the phase active polymer with a modifier (S4); and adding and mixing vegetable oil (S5), wherein the step (S3) is continuously performed in two or more polymerization reactors, and when the polymerization conversion of the first reactor is 70% to 85%, the second reactor It is characterized in that a polar additive or a polar additive and a conjugated diene-based monomer are additionally added to the second reactor.
- the (S3) step of preparing the active polymer and the (S5) step of mixing the vegetable oil are the same as the (S1) and (S2) steps of the conjugated diene-based polymer, respectively, so the description thereof omit
- the step (S4) is a modification step of reacting the active polymer prepared in step (S3) with a modifier, and an anionic active site of the active polymer may react with an alkoxy group bonded to the silane of the modifier.
- the modifier may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.
- 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).
- the denaturant may be introduced into the denaturation reactor, and step (S4) may be performed in the denaturation reactor.
- the modifier may be added to a transport unit for transporting the active polymer prepared in step (S3) to the modification reactor for performing step (S4), and the active polymer and modifier are mixed in the transport unit.
- the reaction may be a modification reaction in which the modifier is simply bound to the active polymer, or a coupling reaction in which the active polymer is connected based on the modifier.
- the step of reacting by additionally adding a conjugated diene-based monomer to the active polymer prepared in the step (S3) before the modification reaction of the step (S4) can be further performed.
- the conjugated diene-based monomer may be added in an amount of 1 mol to 100 mol relative to 1 mol of the active polymer.
- the method for producing the dielectric (modified) conjugated diene-based polymer according to an embodiment of the present invention is a method capable of satisfying the characteristics of the above-described dielectric (modified) conjugated diene-based polymer, and is achieved in the present invention as described above
- the desired effect can be achieved when the above characteristics are satisfied, but other polymerization conditions are controlled in various ways, so that the physical properties of the dielectric (modified) conjugated diene-based polymer according to the present invention can be realized.
- a rubber composition comprising the dielectric conjugated diene-based polymer or the dielectrically modified conjugated diene-based polymer.
- the present invention includes a conjugated diene-based polymer and a filler, and in a tan ⁇ graph according to temperature derived from dynamic viscoelasticity analysis by a rheometric system (Advanced Rheometric Expansion System, ARES) , the full width at half maximum (FWHM) value of the tan ⁇ peak appearing in the temperature range of -100°C to 100°C is 31°C or higher, and the rheometry system has a frequency of 10 in torsion mode using a dynamic mechanical analyzer It is measured under the conditions of Hz, strain 0.5% and temperature increase rate of 5 °C/min, and the conjugated diene-based polymer is provided with a rubber composition comprising vegetable oil.
- ARES Advanced Rheometric Expansion System
- the full width at half maximum of the tan ⁇ peak may be 31°C or higher, preferably 35°C or higher, and more preferably 40°C or higher.
- the full width at half maximum may be at most 100 °C, preferably 80 °C or less. If the full width at half maximum is less than 31 °C, there is a problem that the wet road resistance is significantly lowered at the same glass transition temperature. A problem of increasing hysteresis is inevitably accompanied, and accordingly, a problem of poor fuel efficiency may occur.
- the tan ⁇ peak may be a peak that appears at -100°C to 100°C, preferably at -80°C to 20°C, and more preferably at -70°C to 0°C.
- the conjugated diene-based polymer may be unmodified or modified by a modifier.
- the rubber composition may include 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 tensile strength within this range; It has excellent mechanical properties such as abrasion resistance and excellent balance between the physical properties.
- the rubber composition may further include other rubber components as needed in addition to the (modified) conjugated diene-based polymer, wherein 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 thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber that are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, 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-
- 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, for example, a silica-based filler, and specific examples thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving the breaking properties and wet It may be wet silica that has the best effect of compatibility with wet grip.
- the rubber composition may further include a carbon-based filler if necessary.
- silane coupling agent for improving reinforcing properties and low heat generation may be used together, and in a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide , bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) propyl) tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 3-trimethoxys
- it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.
- a modified conjugated diene-based polymer in which a functional group with high affinity for silica is introduced is used as a rubber component, so the compounding amount of the silane coupling agent is conventional. may be reduced 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 It has the effect of preventing the gelation of the rubber component while being sufficiently exhibited.
- the rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent.
- the vulcanizing agent may be specifically 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, and within this range, the vulcanized rubber composition has a low fuel efficiency while securing the required elasticity modulus and strength. It has an excellent effect.
- the rubber composition according to an embodiment of the present invention includes, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, an anti-scorch agent, zinc white, It may further include stearic acid, a thermosetting resin, or a thermoplastic resin.
- the vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), or DPG
- a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), 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. Naphthenic or paraffinic process oils 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, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.
- the antioxidant 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 condensate of diphenylamine and acetone, etc., 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, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.
- a kneader such as a Banbury mixer, a roll, an internal mixer, etc.
- the rubber composition may be used for each member of the tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, cheffer, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of
- the present invention provides a tire manufactured using the rubber composition.
- the tire may include a tire or a tire tread.
- a polar additive solution in which propane was dissolved in 2 wt% was continuously added at a flow rate of 2.25 g/hr. At this time, the internal temperature of the reactor was maintained at 60° C., and when the polymerization conversion reached 70%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.
- the temperature of the second reactor was maintained to be 60° C., and in the second reactor, a solution in which 1,3-butadiene was dissolved in n-hexane in an amount of 60 wt % was dissolved in 0.2 kg/hr, and di-diol in n-hexane as a polar additive.
- the polar additive solution in which tetrahydrofurylpropane was dissolved at 10 wt% was continuously added at 6 g/hr to participate in the reaction, and when the polymerization conversion reached 95% or more, the third reactor in the second reactor through the transfer pipe Transfer the polymer to the reactor, add a solution in which 5 wt% of N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine is dissolved in n-hexane as a modifier at 17.8 g/hr and 30 minutes The reaction proceeded while.
- IR1520 (BASF Corporation) dissolved in 30% by weight as an antioxidant was injected at a rate of 100 g/h and stirred.
- the resulting polymer was put into hot water heated by steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to prepare a modified conjugated diene-based polymer.
- Example 1 in the first reactor, 1.13 kg/hr of a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane, 0.28 kg/hr of a monomer solution in which 60 wt% of styrene was dissolved in n-hexane , the polar additive solution is continuously introduced at 4.0 g/hr, the polymer is transferred from the first reactor to the second reactor when the polymerization conversion rate of the first reactor is 72%, and N in n-hexane as a modifier in the third reactor, N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine ) to prepare a modified conjugated diene-based polymer in the same manner as in Example 1, except that a solution in which 5 wt% was dissolved was added at 29.0 g/hr.
- Example 1 in the first reactor, 1.08 kg/hr of a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane, 0.35 kg/hr of a monomer solution in which 60 wt% of styrene was dissolved in n-hexane , the polar additive solution was continuously introduced at 3.0 g/hr, and a solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously added to the second reactor at 0.24 kg/hr, and the denaturant was added to the third reactor.
- Example 1 when the polymerization conversion rate of the first reactor is 80%, it is transferred to the second reactor, and 2,2-dimethoxy-1-(3-(trimethoxysilyl) in n-hexane as a modifier in the third reactor )Propyl)-1,2-azasilolidine (2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azasilolidine) was dissolved in 5% by weight of a solution of 23.4 g/hr A modified conjugated diene-based polymer was prepared in the same manner as in Example 1 except that it was added.
- Example 2 As in Example 1, except that when the polymerization conversion rate in the first reactor was 75% in Example 1, the polymer was transferred from the first reactor to the second reactor, and cottonseed oil was continuously introduced at 200 g/hr instead of soybean oil. In the same manner, a modified conjugated diene-based polymer was prepared.
- Example 1 a monomer solution dissolved in 60 wt% of 1,3-butadiene in n-hexane was continuously introduced into the first reactor at 1.37 kg/hr, and the internal temperature of the first reactor was maintained at 70°C, and the first When the polymerization conversion rate in the reactor is 77%, the polymer is transferred from the first reactor to the second reactor, and a monomer solution in which 1,3-butadiene is dissolved at 60 wt% in n-hexane is not added to the second reactor. Except that, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.
- Example 1 a monomer solution in which 60 wt% of 1,3-butadiene in n-hexane was dissolved in the first reactor was 1.13 kg/hr, and a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was 0.28 kg/hr. hr, when the polymerization conversion rate of the first reactor is 78%, the polymer is transferred to the second reactor, and 1,3-butadiene and the polar additive are not added to the second reactor. A conjugated diene-based polymer was prepared.
- Example 1 a monomer solution in which 60 wt% of 1,3-butadiene in n-hexane was dissolved in the first reactor was 1.08 kg/hr, and a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was 0.35 kg/hr. hr, except that the polar additive solution was added at 3.0 g/hr, the polymer was transferred to the second reactor when the polymerization conversion rate of the first reactor was 64%, and 1,3-butadiene was not added to the second reactor Then, in the same manner as in Example 1, a modified conjugated diene-based polymer was prepared.
- Example 1 an initiator solution in which 6.6% by weight of n-butyllithium was dissolved in n-hexane in n-hexane was continuously added to the first reactor at 8.34 g/hr, and when the polymerization conversion in the first reactor was 55%, the polymer was A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that it was transferred to the second reactor.
- Example 1 when the polymerization conversion rate in the first reactor was 75%, the polymerization product was transferred from the first reactor to the second reactor, and the step of introducing and mixing soybean oil into the third reactor was not performed.
- a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.
- Example 1 when the polymerization conversion in the first reactor is 74%, the polymer is transferred from the first reactor to the second reactor, 1,3-butadiene and a polar additive are not added to the second reactor, and the third In Example 1, except that a solution in which silicon tetrachloride was dissolved at 13.5 wt% in n-hexane as a coupling agent instead of a modifier in the reactor was continuously supplied at 3.7 g/hr to proceed with the coupling reaction. In the same manner, an unmodified conjugated diene-based polymer was prepared.
- Styrene bond content (SM) and 1,2-vinyl bond content (Vinyl) in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.
- 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 6.00 ppm, 7.2 ⁇ 6.9 ppm random styrene, 6.9 ⁇ 6.2 ppm block styrene, and 5.8 ⁇ 5.1 ppm 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm were calculated as 1,2-vinyl peaks, and the styrene unit bond content and 1,2-vinyl bond content were calculated.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured by gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies) under the following conditions, and the weight average molecular weight was measured as a number average The molecular weight distribution was calculated by dividing by the molecular weight.
- the full-width at half maximum value of the tan ⁇ peak is all 20° C. or higher, but all of the comparative examples not by the manufacturing method according to the present invention are less than 20° C. It can be seen that the value of
- Each of the modified or unmodified conjugated diene-based polymers of Examples and Comparative Examples was compounded under the compounding conditions shown in Table 3 below as raw rubber.
- the content of the raw material in Table 3 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 (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid is used using a Banbari mixer with a temperature control device.
- antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) ) was kneaded.At this time, the initial temperature of the kneader was controlled to 70 ° C., and after the mixing was completed, a first blend was obtained at a discharge temperature of 145 ° C.
- the first blend was cooled to room temperature, Add the primary compound, sulfur, rubber accelerator (DPG (diphenylguanidine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) to a kneader, and mix at a temperature of 100° C. or less.
- DPG diphenylguanidine
- CZ vulcanization accelerator
- each test piece was prepared according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece was measured. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester. In Table 4 below, the results are indexed based on the measurement results of Comparative Example 5, and the higher the number, the better.
- each primary formulation was left at room temperature (23 ⁇ 3°C) for at least 30 minutes and then 27 ⁇ 3 g was collected, filled inside the die cavity, and the platen was operated for 4 minutes.
- the full width at half maximum value of tan ⁇ is controlled through fine structure control, and by including vegetable oil, the tensile properties, running resistance, and workability are excellent in a well-balanced manner, while the wet road resistance and abrasion resistance are excellent. It was confirmed that there was a remarkably improved effect.
- a polar additive solution in which propane was dissolved in 2 wt% was continuously added at a flow rate of 2.25 g/hr. At this time, the internal temperature of the reactor was maintained at 60° C., and when the polymerization conversion reached 75%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.
- the temperature of the second reactor was maintained to be 60° C., and in the second reactor, a solution in which 1,3-butadiene was dissolved in n-hexane in an amount of 60 wt % was dissolved in 0.2 kg/hr, and di-diol in n-hexane as a polar additive.
- the polar additive solution in which tetrahydrofurylpropane was dissolved at 10 wt% was continuously added at 6 g/hr to participate in the reaction, and when the polymerization conversion reached 95% or more, the third reactor in the second reactor through the transfer pipe
- the polymer was transferred to the reactor, and a solution in which 13.5 wt% of silicon tetrachloride was dissolved in n-hexane as a coupling agent was continuously supplied at 3.7 g/hr to proceed with the coupling reaction.
- IR1520 (BASF Corporation) dissolved in 30% by weight as an antioxidant was injected at a rate of 100 g/h and stirred.
- the resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water to prepare an unmodified conjugated diene-based polymer.
- Example 7 As in Example 7, except that when the polymerization conversion rate in the first reactor was 74% in Example 7, the polymer was transferred from the first reactor to the second reactor, and cottonseed oil was continuously introduced at 200 g/hr instead of soybean oil. In the same manner, an unmodified conjugated diene-based polymer was prepared.
- An unmodified conjugated diene-based polymer was prepared in the same manner as in Example 7, except that the polymer was transferred from the first reactor to the second reactor when the polymerization conversion rate of the first reactor was 70% in Example 7.
- An unmodified conjugated diene-based polymer was prepared in the same manner as in Example 7, except that it was transferred to the second reactor when the polymerization conversion rate of the first reactor was 80% in Example 7.
- Example 7 the internal temperature of the first reactor is maintained at 70° C., and when the polymerization conversion in the first reactor is 76%, the polymer is transferred from the first reactor to the second reactor, and the second reactor is n-hexane
- An unmodified conjugated diene-based polymer was prepared in the same manner as in Example 7, except that a monomer solution in which 1,3-butadiene was dissolved at 60 wt% was not added.
- Example 7 when the polymerization conversion rate in the first reactor was 74%, the polymer was transferred from the first reactor to the second reactor, and 1,3-butadiene and the polar additive were not added to the second reactor, except that was carried out in the same manner as in Example 7 to prepare an unmodified conjugated diene-based polymer.
- Example 7 a monomer solution in which 60 wt% of 1,3-butadiene in n-hexane was dissolved in the first reactor was 1.08 kg/hr, and a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was 0.35 kg/hr. hr, when the polymerization conversion rate of the first reactor is 64%, the polymer is transferred to the second reactor, and 1,3-butadiene is not added to the second reactor. In the same manner as in Example 7, unmodified conjugated diene A polymer was prepared.
- a modified conjugated diene-based polymer was prepared in the same manner as in Example 7, except that the polymer was transferred to the second reactor when the polymerization conversion rate of the first reactor was 55% in Example 7.
- Example 7 a monomer solution in which 60 wt% of 1,3-butadiene in n-hexane was dissolved was 1.13 kg/hr, and a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was 0.28 kg/hr in the first reactor.
- the full width at half maximum of the tan ⁇ peak is all 20° C. or higher, but all of the comparative examples not by the manufacturing method according to the present invention are less than 20° C. It can be seen that the value of
- the dielectrically modified conjugated diene-based polymer of the present invention the full width at half maximum value of tan ⁇ is controlled through fine structure control, and by including vegetable oil, it has excellent tensile properties, running resistance and workability in a balanced way, and at the same time has excellent wet road resistance and It was confirmed that there was an effect of remarkably improving the abrasion resistance.
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Abstract
Description
Claims (14)
- 공액디엔계 단량체 유래 반복단위를 포함하는 중합체 단위; 및식물유를 포함하고,레오메트리 시스템(Advanced Rheometric Expansion System, ARES)에 의한 동적 점탄성 분석으로부터 도출되는 온도에 따른 tanδ 피크 그래프에 있어서, -100℃ 내지 100℃의 온도 범위에서 나타나는 tanδ 피크의 반치전폭(Full width at half maximum, FWHM) 값이 20℃ 이상이고,상기 레오메트리 시스템은 동적 기계 분석기를 이용하여 비틀림 모드로 주파수 10 Hz, 변형률(Strain) 0.5% 및 승온속도 5 ℃/min의 조건하에 측정되는 것인 유전 공액디엔계 중합체.
- 제1항에 있어서,상기 tanδ 피크의 반치전폭 값은 30℃ 이상 80℃ 이하인 것인 유전 공액디엔계 중합체.
- 제1항에 있어서,상기 tanδ 피크의 반치전폭 값은 35℃ 이상 60℃ 이하인 것인 유전 공액디엔계 중합체.
- 제1항에 있어서,상기 식물유는 대두유, 유채유, 카놀라유, 해바라기유, 아마유, 쌀겨유, 팜유, 올리브유, 땅콩유, 야자유, 면실유 및 코코넛유로 이루어진 군에서 선택된 하나 이상인 것인 유전 공액디엔계 중합체.
- 제1항에 있어서,상기 식물유는 중합체 단위 100 중량부 대비 10 중량부 내지 60 중량부로 포함되는 것인 유전 공액디엔계 중합체.
- 제1항에 있어서,상기 tan δ 피크는 -80℃ 내지 20℃의 온도 범위에서 나타나는 것인 유전 공액디엔계 중합체.
- 제1항에 있어서,상기 중합체 단위는 방향족 비닐계 단량체 유래 반복단위를 더 포함하는 것인 유전 공액디엔계 중합체.
- 공액디엔계 단량체 유래 반복단위, 및 변성제 유래 작용기를 포함하는 변성 중합체 단위; 및식물유를 포함하고,레오메트리 시스템(Advanced Rheometric Expansion System, ARES)에 의한 동적 점탄성 분석으로부터 도출되는 온도에 따른 tanδ 그래프에 있어서, -100℃ 내지 100℃의 온도 범위에서 나타나는 tanδ 피크의 반치전폭(Full width at half maximum, FWHM) 값이 20℃ 이상이고,상기 레오메트리 시스템은 동적 기계 분석기를 이용하여 비틀림 모드로 주파수 10 Hz, 변형률(Strain) 0.5% 및 승온속도 5 ℃/min의 조건하에 측정되는 것인 유전 변성 공액디엔계 중합체.
- 제8항에 있어서,상기 변성제는 알콕시실란계 변성제이고,상기 변성 공액디엔계 중합체는 중합체 전체 중량을 기준으로 Si 및 N 함량이 각각 50 ppm 이상인 것인 유전 변성 공액디엔계 중합체.
- 중합체 및 충진제를 포함하고,상기 중합체는 제1항에 따른 유전 공액디엔계 중합체 또는 제8항에 따른 유전 변성 공액디엔계 중합체인 것인 고무 조성물.
- 제9항에 있어서,상기 중합체 100 중량부를 기준으로 0.1 중량부 내지 200 중량부의 충진제를 포함하는 것인 고무 조성물.
- 공액디엔계 중합체 및 충진제를 포함하고,레오메트리 시스템(Advanced Rheometric Expansion System, ARES)에 의한 동적 점탄성 분석으로부터 도출되는 온도에 따른 tan δ 그래프에 있어서, -100℃ 내지 100℃의 온도 범위에서 나타나는 tan δ 피크의 반치전폭(Full width at half maximum, FWHM) 값이 31℃ 이상이고,상기 레오메트리 시스템은 동적 기계 분석기를 이용하여 비틀림 모드로 주파수 10 Hz, 변형률(Strain) 0.5% 및 승온속도 5 ℃/min의 조건하에 측정되는 것이며,상기 공액디엔계 중합체는 식물유를 포함하는 것인 고무 조성물.
- 제12항에 있어서,상기 공액디엔계 중합체는 미변성 유전 공액디엔계 중합체인 것인 고무 조성물.
- 제12항에 있어서,상기 공액디엔계 중합체는 변성제 유래 작용기를 포함하는 유전 변성 공액디엔계 중합체인 것인 고무 조성물.
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CN202180028043.9A CN115397871A (zh) | 2020-11-16 | 2021-11-01 | 充油共轭二烯类聚合物和包含其的橡胶组合物 |
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JP2018178103A (ja) * | 2017-04-05 | 2018-11-15 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
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EP4112658A4 (en) | 2023-11-08 |
TW202225210A (zh) | 2022-07-01 |
JP7447306B2 (ja) | 2024-03-11 |
JP2023521131A (ja) | 2023-05-23 |
US20230146440A1 (en) | 2023-05-11 |
CN115397871A (zh) | 2022-11-25 |
EP4112658A1 (en) | 2023-01-04 |
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