WO2019172185A1 - 変性液状ジエン系重合体およびゴム組成物 - Google Patents
変性液状ジエン系重合体およびゴム組成物 Download PDFInfo
- Publication number
- WO2019172185A1 WO2019172185A1 PCT/JP2019/008405 JP2019008405W WO2019172185A1 WO 2019172185 A1 WO2019172185 A1 WO 2019172185A1 JP 2019008405 W JP2019008405 W JP 2019008405W WO 2019172185 A1 WO2019172185 A1 WO 2019172185A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid diene
- polymer
- modified liquid
- diene polymer
- rubber
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 433
- 150000001993 dienes Chemical class 0.000 title claims abstract description 288
- 239000007788 liquid Substances 0.000 title claims abstract description 282
- 229920001971 elastomer Polymers 0.000 title claims abstract description 159
- 239000005060 rubber Substances 0.000 title claims abstract description 159
- 239000000203 mixture Substances 0.000 title claims abstract description 122
- -1 silane compound Chemical class 0.000 claims abstract description 168
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229920001400 block copolymer Polymers 0.000 claims abstract description 105
- 125000000524 functional group Chemical group 0.000 claims abstract description 95
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 33
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 31
- 125000002897 diene group Chemical group 0.000 claims description 25
- 239000006229 carbon black Substances 0.000 claims description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims description 15
- 229920003052 natural elastomer Polymers 0.000 claims description 15
- 229920001194 natural rubber Polymers 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 239000005062 Polybutadiene Substances 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 229920003049 isoprene rubber Polymers 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000000704 physical effect Effects 0.000 abstract description 22
- 230000006872 improvement Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 71
- 238000006116 polymerization reaction Methods 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 47
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 40
- 238000004519 manufacturing process Methods 0.000 description 39
- 238000003756 stirring Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 25
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 230000009257 reactivity Effects 0.000 description 24
- 230000000694 effects Effects 0.000 description 22
- 239000002174 Styrene-butadiene Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 18
- 229920000359 diblock copolymer Polymers 0.000 description 17
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
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- 239000002904 solvent Substances 0.000 description 14
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- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052783 alkali metal Inorganic materials 0.000 description 13
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- 229920001519 homopolymer Polymers 0.000 description 12
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
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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 7
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- 238000012360 testing method Methods 0.000 description 7
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- 229910052717 sulfur Inorganic materials 0.000 description 6
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- 150000003464 sulfur compounds Chemical class 0.000 description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 5
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 5
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- 238000007342 radical addition reaction Methods 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
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- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
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- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- YOEYNURYLFDCEV-UHFFFAOYSA-N tert-butyl hydroxy carbonate Chemical compound CC(C)(C)OC(=O)OO YOEYNURYLFDCEV-UHFFFAOYSA-N 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- FPBXRRDHCADTAL-UHFFFAOYSA-N triethoxy(3-nitropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]([O-])=O FPBXRRDHCADTAL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- KOFGNZOFJYBHIN-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSCCC[Si](OC)(OC)OC KOFGNZOFJYBHIN-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/20—Incorporating sulfur atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a modified liquid diene polymer and a rubber composition.
- a rubber composition in which mechanical strength is improved by blending a filler such as silica or carbon black with a rubber component such as natural rubber or styrene butadiene rubber is a tire that requires wear resistance and mechanical strength.
- a filler such as silica or carbon black
- a rubber component such as natural rubber or styrene butadiene rubber
- the dispersion state of the filler in the crosslinked product of the rubber composition containing the filler may affect the physical properties of the crosslinked product (for example, wet grip, wear resistance, etc.).
- the rubber composition containing this filler does not necessarily have high affinity between the rubber and the filler, and interaction between the fillers occurs, if the dispersibility of the filler is not sufficient, the physical properties of the crosslinked product are improved. May not be the ideal distributed state for.
- the present invention has been made in view of the above circumstances, and the dispersion state of the filler in the cross-linked product obtained from the rubber composition is ideal for improving physical properties, and further, wet grip, wear resistance, etc.
- a modified liquid diene polymer, a rubber composition containing the modified liquid diene polymer, and the crosslinked product, and a tire partially using the composition or the crosslinked product are provided. To do.
- the rubber composition contains a specific modified liquid diene polymer containing two types of polymer blocks having different reactivities to specific silane compounds.
- the dispersed state of the filler is ideal for improving the physical properties, and furthermore, it has been found that the wet grip and the wear resistance are excellent, and the present invention has been completed. That is, the present invention relates to the following [1] to [15].
- a silane in which a liquid diene block copolymer (B′1) containing a polymer block (b′1) containing a butadiene unit and a polymer block (b′2) is represented by the following formula (1)
- a modified liquid diene which is a modified liquid diene polymer (B1) having a functional group derived from the silane compound represented by the formula (1), which is modified by a compound, and satisfies the following (i) to (iv): -Based polymer (B1).
- the weight average molecular weight (Mw) of the modified liquid diene rubber is 1,000 to 120,000.
- the vinyl content of butadiene units in the polymer block (b′1) is 40 to 100 mol%.
- the polymer block (b′2) contains butadiene units having a vinyl content of 0 to 25 mol%.
- Modified liquid diene polymer (B1) The average number of functional groups per molecule is 1-20.
- R 1 is a divalent alkylene group having 1 to 6 carbon atoms
- R 2 , R 3 and R 4 are each independently methoxy, ethoxy, phenoxy, methyl, ethyl, A group or a phenyl group, provided that at least one of R 2 , R 3 and R 4 is a methoxy group, an ethoxy group or a phenoxy group.
- the modified liquid diene polymer (B1) is a linear polymer, and the polymer block (b′1) is attached to one end or both ends of the liquid diene block copolymer (B′1).
- a modified liquid diene which is a modified liquid diene polymer (B2) having a functional group derived from the silane compound represented by the formula (1), which is modified by a compound, and satisfies the following (v) to (vii): -Based polymer (B2).
- the weight average molecular weight (Mw) of the modified liquid diene polymer (B2) is 1,000 to 120,000.
- the polymer block (b "2) contains at least one monomer unit selected from the group consisting of conjugated diene units other than butadiene and aromatic vinyl compound units.
- Modified liquid diene polymer (B2) The average number of functional groups per molecule is 1-20. [4]
- the modified liquid diene polymer (B2) is a linear polymer, and the polymer block (b "1) of the liquid diene block copolymer (B'2) is at one or both ends.
- the modified liquid diene polymer (B1) or (B2) is a linear polymer, and among functional groups derived from the silane compound in the modified liquid diene polymer (B1) or (B2)
- the modified liquid diene polymer (B1) according to any one of [1] to [4], wherein 65% or more thereof is present in the range of 45% in total of the total chain length from one end or both ends, or ( B2).
- the filler (C) is at least one selected from carbon black having an average particle diameter of 5 to 100 nm and silica having an average particle diameter of 0.5 to 200 nm.
- the solid rubber (A) is a styrene butadiene rubber having a weight average molecular weight of 100,000 to 2,500,000.
- the dispersion state of the filler is ideal for improving the physical properties, and further excellent in wet grip, wear resistance, etc. .
- this composition or crosslinked material is useful for a tire, for example.
- the modified liquid diene polymer of the present invention is a silane in which a polymer block containing a butadiene unit and an unmodified liquid diene block copolymer containing a polymer block different from this are represented by the above formula (1). It is a polymer modified with a compound, and the polymer has a functional group derived from the silane compound represented by the formula (1), and further needs to satisfy a specific condition.
- modified liquid diene polymer of the present invention is generically referred to as a modified liquid diene polymer (B), and the unmodified liquid diene block copolymer as a raw material is generically referred to as unmodified.
- a liquid diene block copolymer (B ′) the silane compound represented by the formula (1) is referred to as a silane compound (1).
- the modified liquid diene polymer (B) of the present invention obtained from a specific unmodified liquid diene block copolymer (B ′) has desired physical properties because the unmodified liquid diene block copolymer It is considered that there is a difference in reactivity of the silane compound (1) between the two polymer blocks contained in the polymer (B ′).
- Unmodified liquid diene block copolymer (B ′) As a raw material of the modified liquid diene polymer (B) will be described.
- Examples of the unmodified liquid diene block copolymer (B ′) include the following unmodified liquid diene block copolymer (B′1) and unmodified liquid diene block copolymer (B′2). Can be mentioned.
- the modified liquid diene polymer (B1) which is the first embodiment of the modified liquid diene polymer (B) of the present invention comprises a polymer block (b′1) and a polymer block (b′2) containing butadiene units.
- the unmodified liquid diene block copolymer (B′1) containing silane is modified with the silane compound (1) and has a functional group derived from the silane compound (1). iv) is satisfied.
- the weight average molecular weight (Mw) of the modified liquid diene rubber (B1) is 1,000 to 120,000.
- the vinyl content of butadiene units in the polymer block (b′1) is 40 to 100 mol%.
- the polymer block (b′2) contains butadiene units having a vinyl content of 0 to 25 mol%.
- Modified liquid diene polymer (B1) The average number of functional groups per molecule is 1-20.
- the raw material of the modified liquid diene polymer (B1) is an unmodified liquid diene block copolymer (B′1) and contains a polymer block (b′1) and a polymer block (b′2). .
- the polymer block (b′1) contains butadiene units having a vinyl content of 40 to 100 mol%.
- a butadiene unit having a vinyl content in a specific range is excellent in reactivity with the silane compound (1).
- the “vinyl content” refers to a total of 100 mol% of butadiene units and conjugated diene units other than butadiene units contained in a target portion (for example, the entire polymer block and liquid diene rubber). , 2-bond, and 3,4-bond conjugated diene units (conjugated diene units bonded other than 1,4-bond).
- a target portion for example, the entire polymer block and liquid diene rubber.
- 2-bond, and 3,4-bond conjugated diene units conjugated diene units bonded other than 1,4-bond.
- the vinyl content is determined based on the peaks derived from conjugated diene units bonded by 1,2-bonds and 3,4-bonds and conjugated diene units bonded by 1,4-bonds. It can be calculated from the area ratio of the peak derived.
- the vinyl content of the butadiene unit contained in the polymer block (b′1) is 40 to 100 mol%.
- the reactivity with the silane compound represented by the formula (1) is high, and it becomes easy to introduce a plurality of functional groups into the polymer block (b′1).
- it is preferably 50 to 100 mol%, and 55 to 100 mol%. More preferably, it is more preferably 60 to 100 mol%.
- the vinyl content of the conjugated diene unit such as a butadiene unit of the polymer block (b′1) is, for example, the type of solvent used in preparing the polymer block (b′1), and the polarity used as necessary.
- the desired value can be obtained by controlling the compound, the polymerization temperature and the like.
- the content of the butadiene unit in the polymer block (b′1) is high in reactivity with the silane compound represented by the formula (1), and a plurality of functional groups are easily added to the polymer block (b′1). From the viewpoint of introduction, it is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and more preferably 70 to 100% by mass with respect to all monomer units of the polymer block (b′1). % Is more preferable, and it may be substantially 100% by mass.
- the polymer block (b′1) may contain other monomer units.
- examples of other monomers include conjugated dienes other than butadiene, aromatic vinyl compounds, and the like.
- conjugated dienes other than butadiene examples include isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Examples include octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, and chloroprene. Of the conjugated dienes other than butadiene, isoprene is preferred.
- the vinyl content of the conjugated diene units other than butadiene is 40 to 100 mol%. It is preferably 50 to 100 mol%, more preferably 55 to 100 mol%, and particularly preferably 60 to 100 mol%.
- aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Examples thereof include vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzen
- the content of monomer units other than butadiene units in the polymer block (b′1) is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. More preferably, it may be 0% by mass.
- the unmodified liquid diene block copolymer (B′1) may contain one polymer block (b′1) or two or more polymer blocks (b′1). Further, when a plurality of polymer blocks (b′1) are contained, the properties of the polymer block (b′1) (for example, the type of monomer unit, the monomer unit composition, the polymer block Length etc.) may be the same or different.
- the polymer block (b′2) contains butadiene units having a vinyl content of 0 to 25 mol%.
- the reactivity of the butadiene unit (b′2) having a vinyl content within a specific range is suppressed with respect to the silane compound (1) as compared with the polymer block (b′1).
- the vinyl content of the butadiene unit contained in the polymer block (b′2) is preferably 0 to 20 mol% from the viewpoint of suppressing reactivity with the silane compound represented by the formula (1). It is more preferably ⁇ 15 mol%, further preferably 0 to 10 mol%.
- the vinyl content of the conjugated diene unit such as a butadiene unit in the polymer block (b′2) is, for example, the type of solvent used in preparing the polymer block (b′2), and the polarity used as necessary.
- the desired value can be obtained by controlling the compound, the polymerization temperature and the like.
- the content of the butadiene unit in the polymer block (b′2) is selected from the viewpoint of improving the wear resistance in the DIN abrasion test of the crosslinked product of the rubber composition containing the modified liquid diene polymer (B1).
- the amount is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 70 to 100% by mass with respect to the total monomer units of the block (b′2).
- the amount may be substantially 100% by mass.
- the polymer block (b′2) may contain other monomer units.
- examples of other monomers include conjugated dienes other than butadiene, aromatic vinyl compounds, and the like.
- conjugated dienes other than butadiene are the same as conjugated dienes other than butadiene that can be other monomer units of the polymer block (b′1). Of the conjugated dienes other than butadiene, isoprene is preferred.
- the vinyl content of the conjugated diene unit other than butadiene is 0 to 25 mol%. It is preferably 0 to 20 mol%, more preferably 0 to 15 mol%, and particularly preferably 0 to 10 mol%.
- aromatic vinyl compound examples are the same as those of the aromatic vinyl compound that can be another monomer unit of the polymer block (b′1). Of these aromatic vinyl compounds, styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable.
- the content of monomer units other than butadiene units in the polymer block (b′2) is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. More preferably, it may be 0% by mass.
- the unmodified liquid diene block copolymer (B′1) may contain one polymer block (b′2) or two or more polymer blocks (b′2).
- the properties of the polymer block (b′2) for example, the type of monomer unit, the monomer unit composition, the polymer block Length etc. may be the same or different.
- the unmodified liquid diene block copolymer (B′1) may have a polymer block (b′3) other than the polymer blocks (b′1) and (b′2).
- the monomer that can be a monomer unit contained in the polymer block (b′3) include conjugated dienes other than butadiene and aromatic vinyl compounds. Specific examples of these compounds are the same as those of conjugated dienes other than butadiene and aromatic vinyl compounds which can be other monomer units of the polymer block (b′1).
- the properties of the polymer block (b′3) (for example, the type of monomer unit, the monomer unit composition, the length of the polymer block, etc.) ) May be the same or different.
- the resulting modified liquid diene polymer is a linear polymer.
- the unmodified block copolymer (B′1) is preferably a linear block copolymer.
- the polymer block (b′1) is preferably present at one or both ends of the liquid diene block copolymer (B′1). Derived from the silane compound (1) contained in the resulting modified liquid diene polymer (B1) by the presence of the polymer block (b′1) at the end of the unmodified block copolymer (B′1).
- the functional group is unevenly distributed in the polymer block at the terminal portion. For example, when the modified liquid diene polymer (B1) is used as one component of the rubber composition described later, the affinity with the filler And the wear resistance of the crosslinked product of the rubber composition containing the modified liquid diene polymer (B1) tends to be improved.
- the length occupied by the polymer block (b′1) is preferably 45% or less of the total chain length of the unmodified liquid diene block copolymer (B′1), and preferably 40% or less. More preferably, the total is further preferably 30% or less, and particularly preferably 25% or less.
- a modified liquid diene polymer (B1) obtained using such an unmodified liquid block copolymer (B′1) as a raw material is, for example, a modified liquid diene polymer (as a component of a rubber composition described later).
- the range of total X% of the total chain length means that when a plurality of polymer blocks (b′1) are included in the entire polymer, the chain length of the total polymer blocks Means X%.
- the length occupied by the polymer block in the block copolymer is calculated from the number of each monomer unit contained in each block copolymer by 1 H-NMR measurement, and the carbon in the main chain of the block copolymer is calculated. It can be determined by calculating assuming that the bond length of the carbon single bond is 150 pm, the bond length of the carbon-carbon double bond is 135 pm, and the bond angle is 120 °.
- the bonding form of the unmodified block copolymer (B′1) the polymer block (b′1) is “b′1” and the polymer block (b′2) is “b′2”.
- a linear diblock copolymer and a linear triblock copolymer represented by the following general formula are preferred.
- the resulting crosslinked product has better wear resistance.
- the polymer chain length extending from the bonding point between the silanol group on the silica surface and the modified liquid diene rubber (B1) becomes longer when the diblock copolymer is used, and the modified liquid diene This is considered to be because stress concentration at the bonding point when the entire rubber, which is a crosslinked product of the rubber composition containing the polymer (B1), is strained can be prevented.
- the rolling resistance performance of the crosslinked material of the rubber composition containing the modified liquid diene polymer (B1) becomes better.
- the polymer chain length extending from the bonding point between the silanol group on the silica surface and the modified liquid diene rubber (B1) is shortened by using a triblock copolymer, and the resulting crosslinking This is probably because the energy loss of the object is reduced and tan ⁇ is reduced.
- the content of the polymer block (b′1) in the unmodified linear block copolymer (B′1) is from the standpoint that the properties of the resulting modified liquid diene rubber are more excellent.
- the content of the polymer block (b'2) is preferably from 55% by mass to 45% by mass, and preferably from 55% by mass to 99.95% by mass.
- the content of the polymer block (b′2) is more preferably 60% by mass to 40% by mass, and more preferably 60% by mass to 99.95% by mass.
- the contents of the polymer blocks (b′1) and (b′2) in the unmodified linear block copolymer (B′1) can be determined by 1 H-NMR measurement or the like.
- the content of the polymer block (b′1) is as follows: This means the total amount of all polymer blocks (b′1) contained in the unmodified linear block copolymer (B′1) (the same applies to the content of the polymer block (b′2)). .)
- the modified liquid diene polymer (B2) which is the second embodiment of the modified liquid diene polymer (B) of the present invention includes a polymer block (b "1) and a polymer block (b" 2) containing butadiene units.
- the unmodified liquid diene block copolymer (B′2) containing silane is modified with the silane compound (1) and has a functional group derived from the silane compound (1). vii) is satisfied.
- the weight average molecular weight (Mw) of the modified liquid diene polymer (B2) is 1,000 to 120,000.
- the polymer block (b "2) contains at least one monomer unit selected from the group consisting of conjugated diene units other than butadiene and aromatic vinyl compound units.
- Modified liquid diene polymer (B2) The average number of functional groups per molecule is 1-20.
- the raw material of the modified liquid diene polymer (B2) is an unmodified liquid diene block copolymer (B′2), which contains a polymer block (b ′′ 1) and a polymer block (b ′′ 2). .
- the polymer block (b ′′ 1) contains a butadiene unit.
- the polymer block (b ′′ 1) is superior in reactivity to the silane compound (1) compared to the polymer block (b ′′ 2).
- the content of the butadiene unit in the polymer block (b "1) is high in reactivity with the silane compound represented by the formula (1), and a plurality of functional groups are easily added to the polymer block (b" 1). From the viewpoint of introduction, it is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and more preferably 70 to 100% by mass with respect to all monomer units of the polymer block (b ′′ 1). % Is more preferable, and it may be substantially 100% by mass.
- the vinyl content of the butadiene unit contained in the polymer block (b "1) is high in reactivity with the silane compound represented by the formula (1), and a plurality of functional groups are added to the polymer block (b" 1). From the viewpoint of easy introduction, it is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, further preferably 25 to 80 mol%, more preferably 30 to 80 mol%. Is particularly preferred.
- the vinyl content of the conjugated diene unit such as a butadiene unit in the polymer block (b "1) is, for example, the type of solvent used in preparing the polymer block (b" 1), and the polarity used as necessary.
- the desired value can be obtained by controlling the compound, the polymerization temperature and the like.
- the polymer block (b ′′ 1) may contain other monomer units.
- the other monomer include conjugated dienes other than butadiene, aromatic vinyl compounds, and the like.
- conjugated dienes other than butadiene are the same as conjugated dienes other than butadiene which can be other monomer units of the polymer block (b′1) of the unmodified liquid diene block copolymer (B′1). is there.
- isoprene is preferred.
- the vinyl content of the conjugated diene units other than butadiene is 1 to 80 mol%. It is preferably 10 to 80 mol%, more preferably 25 to 80 mol%, particularly preferably 30 to 80 mol%.
- aromatic vinyl compound examples are the same as those of the aromatic vinyl compound that can be another monomer unit of the polymer block (b′1) of the unmodified liquid diene block copolymer (B′1).
- aromatic vinyl compounds styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable.
- the content of monomer units other than the butadiene unit in the polymer block (b "1) is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. More preferably, it may be 0% by mass.
- the unmodified liquid diene block copolymer (B′2) may contain one polymer block (b ′′ 1) or two or more polymer blocks.
- the properties of the polymer block (b ′′ 1) for example, the type of monomer unit, the monomer unit composition, the length of the polymer block, etc. are May be the same or different.
- the polymer block (b ′′ 2) contains at least one monomer unit selected from the group consisting of conjugated diene units other than butadiene and aromatic vinyl compound units.
- the polymer block (b ′′ 2) is a polymer. Compared with the block (b "1), the reactivity with respect to the silane compound (1) is suppressed.
- conjugated dienes other than butadiene are the same as conjugated dienes other than butadiene that can be other monomer units of the polymer block (b "1). Of the conjugated dienes other than butadiene, isoprene is preferred.
- the polymer block (b ′′ 2) contains conjugated diene units as other monomer units, the vinyl content is preferably 0 to 60 mol%, and 0 to 50 mol%. More preferably, it is 0 to 45 mol%, further preferably 0 to 40 mol%.
- aromatic vinyl compound examples are the same as those of the aromatic vinyl compound that can be another monomer unit of the polymer block (b "1).
- aromatic vinyl compounds styrene, ⁇ -methylstyrene, And 4-methylstyrene are preferred.
- the content of at least one monomer unit selected from the group consisting of conjugated diene units other than butadiene and aromatic vinyl compound units in the polymer block (b ′′ 2) is the silane compound represented by the formula (1): From the standpoint of suppressing reactivity, the amount is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on all monomer units of the polymer block (b ′′ 2). More preferably, it is 70 to 100% by mass, and it may be substantially 100% by mass.
- the unmodified liquid diene block copolymer (B′2) may contain one polymer block (b ′′ 2) or two or more polymer blocks (b).
- the properties of the polymer block (b ′′ 2) (for example, the type of monomer unit, the monomer unit composition, the length of the polymer block, etc.) are May be the same or different.
- the resulting modified liquid diene polymer is a linear polymer.
- the unmodified block copolymer (B′2) is preferably a linear block copolymer.
- the polymer block (b ′′ 1) is preferably present at one or both ends of the liquid diene block copolymer (B′2).
- the functional group derived from the silane compound (1) contained in the modified liquid diene polymer (B2) obtained by the presence of (b "1) at the terminal of the unmodified block copolymer (B'2).
- the affinity with the filler is further increased.
- the rubber composition tends to improve the wear resistance of the crosslinked product.
- the length occupied by the polymer block (b ′′ 1) is preferably 45% or less in total of the total chain length of the unmodified liquid diene block copolymer (B′2), and preferably 30% or less in total. More preferably, the total is not more than 20%, and particularly preferably not more than 15%
- the modified liquid diene rubber obtained from such an unmodified liquid block copolymer (B′2) as a raw material (B2) is, for example, a portion having a high affinity for solid rubber and a portion having a high affinity for filler when the modified liquid diene polymer (B2) is used as one component of a rubber composition described later.
- the resulting crosslinked product has better wear resistance.
- the polymer chain length extending from the bonding point between the silanol group on the silica surface and the modified liquid diene rubber (B2) becomes longer when the diblock copolymer is used. This is thought to be because stress concentration at the bonding point when the entire rubber, which is a crosslinked product of the rubber composition containing the polymer (B2), is strained can be prevented.
- the rolling resistance performance of the crosslinked material of the rubber composition containing the modified liquid diene polymer (B2) becomes better.
- the polymer chain length extending from the bonding point between the silanol group on the silica surface and the modified liquid diene rubber (B2) is shortened when a triblock copolymer is used, and the resulting crosslinks are obtained. This is probably because the energy loss of the object is reduced and tan ⁇ is reduced.
- the content of the polymer block (b "1) in the unmodified linear block copolymer (B'2) is from the standpoint that the properties of the resulting modified liquid diene rubber are more excellent.
- the content of the polymer block (b ′′ 2) is preferably from 55% by mass to 45% by mass, and the content of the polymer block (b ′′ 1) is preferably from 0.5% by mass to 99.95% by mass.
- the content of the polymer block (b ′′ 2) is more preferably from 0.05% by mass to 30% by mass, and more preferably from 70% by mass to 99.95% by mass, and the content of the polymer block (b ′′ 1) is 0%.
- the content of the polymer block (b ′′ 2) is more preferably 80% by mass to 99.95% by mass.
- the contents of the polymer blocks (b ′′ 1) and (b ′′ 2) in the unmodified linear block copolymer (B′2) can be determined by 1 H-NMR measurement or the like.
- the content of the polymer block (b ′′ 1) is as follows: This means the total amount of all polymer blocks (b ′′ 1) contained in the unmodified linear block copolymer (B′2) (the same applies to the content of the polymer block (b ′′ 2)). .
- the production method of the unmodified liquid diene block copolymer (B′1) or (B′2) is not particularly limited. However, other monomers other than the conjugated diene and the conjugated diene contained as necessary may be used. It is preferable to produce by a solution polymerization method. According to the solution polymerization method, the unmodified block copolymer (B′1) or (B′2) can be easily produced by sequentially polymerizing each polymer block.
- a known method or a method according to a known method can be applied.
- a Ziegler catalyst a metallocene catalyst, an anion-polymerizable active metal or an active metal compound in a solvent
- a monomer containing a conjugated diene is polymerized in the presence of a polar compound as necessary.
- the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Aromatic hydrocarbons such as toluene and xylene are exemplified.
- aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane
- alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane
- benzene Aromatic hydrocarbons such as toluene and xylene are exemplified.
- anion-polymerizable active metal examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium .
- alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
- an organic alkali metal compound As the active metal compound capable of anion polymerization, an organic alkali metal compound is preferable.
- the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, dilithionaphthalene Polyfunctional organolithium compounds such as 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like.
- organic alkali metal compounds organic lithium compounds are preferable, and organic monolithium compounds are more preferable.
- the amount of the organic alkali metal compound used is appropriately determined according to the melt viscosity, molecular weight, etc. of the unmodified block copolymer (B′1) or (B′2) and the modified liquid diene polymer (B1) or (B2). Although it can be set, it is usually used in an amount of 0.01 to 3 parts by mass with respect to 100 parts by mass of all monomers including the conjugated diene.
- the organic alkali metal compound can be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, dibenzylamine and the like.
- Polar compounds are usually used in anionic polymerization to adjust the microstructure of the conjugated diene moiety (eg, vinyl content) without deactivating the reaction.
- the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
- the polar compound is usually used in an amount of 0.01 to 1000 mol with respect to 1 mol of the organic alkali metal compound.
- the temperature of solution polymerization is usually in the range of ⁇ 80 to 150 ° C., preferably in the range of 0 to 100 ° C., more preferably in the range of 10 to 90 ° C.
- the polymerization mode may be either batch or continuous.
- the polymerization reaction can be stopped by adding a polymerization terminator.
- the polymerization terminator include alcohols such as methanol and isopropanol.
- the obtained polymerization reaction liquid is poured into a poor solvent such as methanol to precipitate the unmodified liquid diene block copolymer (B′1) or (B′2), or the polymerization reaction liquid is washed with water, After separation, the unmodified liquid diene block copolymer (B′1) or (B′2) can be isolated by drying.
- the unmodified liquid diene block copolymer (B′1) or (B′2) obtained in this way is converted into a silane compound represented by the formula (1) described below as it is (without hydrogenation). Modification by the derived functional group may be performed, but modification may be performed after hydrogenation of at least a part of unsaturated bonds contained in the liquid diene rubber.
- the unmodified unmodified liquid diene block copolymer (B′1) or (B′2) more preferably has the characteristics of a functional group derived from a silane compound represented by the formula (1) described later. From the point of exhibiting in a state, it is preferable that the functional group (for example, a hydroxyl group) is not modified.
- the stability of the modified liquid diene polymer (B1) or (B2) obtained by not modifying the unmodified liquid diene block copolymer (B′1) or (B′2) with other functional groups Tend to be more excellent.
- the interaction (for example, reactivity) to the filler (for example, silica) of the functional group derived from the silane compound represented by the formula (1) included in the modified liquid diene polymer (B1) or (B2) is more. It tends to be excellent.
- the unmodified liquid diene block copolymer (B′1) or (B′2) is a functional group derived from a silane compound represented by the following formula (1) (hereinafter also referred to as silane compound (1)). And is used as a modified liquid diene polymer (B1) or (B2).
- R ⁇ 1 > is a C1-C6 bivalent alkylene group.
- the divalent alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
- R 2 , R 3 and R 4 each independently represents a methoxy group, an ethoxy group, a phenoxy group, a methyl group, an ethyl group or a phenyl group. However, at least one of R 2 , R 3 and R 4 is a methoxy group, an ethoxy group or a phenoxy group.
- silane compound (1) examples include mercaptomethylenemethyldiethoxysilane, mercaptomethylenetriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethoxydimethylsilane, 2- Mercaptoethylethoxydimethylsilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxyethylsilane, 3-mercapto Examples thereof include propyldiethoxyethylsilane, 3-mercaptopropylmethoxydimethylsilane, and 3-mercaptopropylethoxydimethylsilane. These silane compounds may be used alone or in combination of two or more.
- the mercapto group (—SH) of the silane compound (1) undergoes a radical addition reaction to the carbon-carbon unsaturated bond contained in the unmodified liquid diene block copolymer (B′1) or (B′2).
- a modified liquid diene polymer (B1) or (B2) having a functional group derived from the silane compound (1), specifically, a partial structure represented by the following formula (2) as a functional group is obtained.
- R 1, R 2, R 3 and R 4 in the formula (2) is defined and specific examples of R 1, R 2, R 3 and R 4 in the formula (1) or the like and Are the same.
- Functional group derived from silane compound (1) modified liquid diene polymer (B1) or (B2) The average number of functional groups per molecule is 1 to 20, preferably 1 to 15 and 1 to 10 Is more preferable, 1 to 9 is more preferable, and 1 to 4 is particularly preferable.
- the average number of functional groups is less than 1, when the modified liquid diene polymer (B1) or (B2) is used as one component of the rubber composition described later, the affinity with the filler (C) is low, When the filler dispersibility in the rubber composition cannot be improved, and the crosslinked product obtained from the rubber composition does not have the desired physical property improvement, for example, the pain effect may not be sufficiently reduced. .
- the modified liquid diene polymer is introduced in the vicinity of the filler (C) by introducing an appropriate amount of functional groups into the modified liquid diene polymer (B1) or (B2). It is presumed that the reinforcing effect of the filler (C) is increased and the resulting crosslinked product is improved in wear resistance.
- the affinity between the solid rubber (A) and the filler (C) is improved, and a dispersed state of the filler (C) in the rubber composition is obtained. It is ideal for the physical properties of the resulting crosslinked product, for example, it is estimated that the dispersibility is improved.
- the filler in the rubber composition is caused by the interaction between the modified liquid diene polymer (B1) or (B2) adsorbed on the filler (C).
- the filler (C) may be agglomerated, and the modified liquid diene polymer may be a solid rubber.
- the modified liquid diene polymer (B1) or (B2) of a functional group derived from the silane compound (1) per molecule The average number of functional groups is preferably 1 to 9.
- the average number of functional groups per molecule of the modified liquid diene polymer (B1) or (B2) is equivalent to the functional group equivalent (g / eq) of the modified liquid diene polymer (B1) or (B2) and the number in terms of styrene. It can be determined from the average molecular weight Mn.
- Average number of functional groups per molecule [(Number average molecular weight Mn) / (Molecular weight of styrene unit) ⁇ (Average molecular weight of conjugated diene and other monomer units other than conjugated diene if necessary)] / (Equivalent functional group)
- the equivalent of the functional group of the modified liquid diene polymer (B1) or (B2) is a conjugated diene bonded per functional group and other monomers other than the conjugated diene contained as necessary.
- Means the mass of The equivalent of the functional group can be calculated from the area ratio of the peak derived from the functional group and the peak derived from the polymer main chain using 1 H-NMR or 13 C-NMR.
- the peak derived from a functional group refers to the peak derived from an alkoxy group.
- the addition amount of the silane compound (1) in the modified liquid diene polymer (B1) or (B2) is 1 with respect to 100 parts by mass of the unmodified liquid diene block copolymer (B′1) or (B′2). -60 parts by mass is preferable, 1-50 parts by mass is more preferable, and 1-40 parts by mass is more preferable.
- the amount of the modifying compound added is more than 60 parts by mass, the dispersibility effect of the filler (C) is poor and the desired physical properties of the resulting crosslinked product are not improved, for example, the Payne effect is not sufficiently reduced. Also, the wear resistance tends to decrease.
- the addition amount of the silane compound (1) added in the modified liquid diene polymer (B1) or (B2) can be determined using various analytical instruments such as nuclear magnetic resonance spectroscopy.
- the method for adding the silane compound (1) to the unmodified liquid diene block copolymer (B′1) or (B′2) is not particularly limited.
- the unmodified liquid diene block copolymer (B A method of heating in the presence or absence of an organic solvent by adding the silane compound (1) and, if necessary, a radical catalyst in '1) or (B'2) can be employed.
- a radical catalyst in '1) or (B'2) can be employed.
- organic peroxide examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy).
- Examples of the azo compound include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), and 2,2′-azobis (2-methylbutyronitrile).
- the organic solvent used in the above method includes a hydrocarbon solvent and a halogenated hydrocarbon solvent.
- hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene and xylene are preferable.
- Preferred anti-aging agents used at this time include, for example, 2,6-di-t-butyl-4-methylphenol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4 '-Thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) (AO-40), 3,9-bis [1,1-dimethyl- 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (AO-80), 2,4-bis [(octylthio) methyl] -6-methylphenol (Irganox 1520L), 2,4-bis [
- the said anti-aging agent may be used individually by 1 type, and may use 2 or more types together.
- the addition amount of the antioxidant is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the unmodified liquid diene block copolymer (B′1) or (B′2). .
- the position at which the functional group is introduced may be a polymerization terminal or a side chain of the polymer chain. From the viewpoint that can be easily introduced, it is preferably a side chain of a polymer chain.
- the said functional group may be contained individually by 1 type, and may be contained 2 or more types. Therefore, the modified liquid diene polymer (B1) or (B2) may be modified with one modified compound, or may be modified with two or more modified compounds.
- the mixing ratio of the unmodified liquid diene block copolymer (B′1) or (B′2) and the silane compound (1) is, for example, per modified liquid diene polymer (B1) or (B2) per molecule. May be appropriately set so that the average number of functional groups is a desired value.
- the mass ratio of the unmodified liquid diene block copolymer (B′1) or (B′2) and the silane compound (1) What is necessary is just to mix so that (B'1) / (1) (or (B'2) / (1)) may become 0.3-50.
- the reaction of radical addition of the silane compound (1) is allowed to react at an appropriate reaction temperature for a sufficient reaction time.
- the temperature in the reaction of adding the silane compound (1) to the unmodified liquid diene block copolymer (B′1) or (B′2) is preferably 10 to 200 ° C., more preferably 50 to 180 ° C.
- the reaction time is preferably 1 to 200 hours, more preferably 1 to 100 hours, and further preferably 1 to 50 hours.
- the melt viscosity of the modified liquid diene polymer (B1) or (B2) measured at 38 ° C. is preferably 0.1 to 4,000 Pa ⁇ s, more preferably 0.1 to 3,500 Pa ⁇ s, and 0 More preferably, it is 1 to 3,000 Pa ⁇ s. If the melt viscosity of the modified liquid diene polymer (B1) or (B2) is within the above range, it becomes easy to handle because it is in a liquid form at room temperature, and the flexibility of the resulting rubber composition is improved. Workability is improved.
- the melt viscosity of the liquid diene polymer (B1) or (B2) is a value measured with a Brookfield viscometer at 38 ° C.
- the weight average molecular weight (Mw) of the modified liquid diene polymer (B1) or (B2) is 1,000 to 120,000, preferably 2,000 to 100,000, and preferably 3,000 to 80,000. The following is more preferable.
- Mw of the liquid diene polymer (B1) or (B2) is a weight average molecular weight in terms of polystyrene determined from measurement by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the processability of the rubber composition of the present invention is improved, and the affinity of the filler (C) described later in the resulting rubber composition is improved. It becomes ideal for the manifestation of the physical properties of the crosslinked product that tends to be present in the vicinity, and as a result the dispersion state of the filler (C) in the rubber composition is obtained (for example, to improve the dispersibility of the filler (C)) To contribute). Therefore, in some cases, the pane effect of the cross-linked product becomes sufficiently small, and the dispersibility of the filler (C) in the cross-linked product is excellent.
- modified liquid polymer (B1) or (B2) is likely to be present in the vicinity of the filler (C)
- a crosslinked product having excellent wear resistance is obtained.
- a tire made of the crosslinked product has good wet grip and the like.
- two or more kinds of modified liquid diene polymers (B1) or (B2) having different Mw may be used in combination.
- Two or more liquid diene polymers (B1) and (B2) may be used in combination.
- the molecular weight distribution (Mw / Mn) of the modified liquid diene polymer (B1) or (B2) is preferably 1.0 to 20.0, more preferably 1.0 to 15.0, and more preferably 1.0 to 10.0. Is more preferable, 1.0 to 5.0 is more preferable, and 1.0 to 2.0 is particularly preferable. It is more preferable that Mw / Mn is within the above range because the resulting modified liquid diene polymer (B1) or (B2) has a small variation in viscosity.
- a radical catalyst is added during the modification reaction, and the reaction temperature is low and the reaction time is short. Is effective.
- molecular weight distribution (Mw / Mn) means the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) in terms of standard polystyrene determined by GPC measurement.
- the modified liquid diene polymer (B1) or (B2) of the present invention has a functional group derived from the silane compound represented by the formula (1), and the modified liquid diene polymer (B) of the functional group.
- the average number of functional groups per molecule is in the range of 1 to 20, but the modified liquid diene polymer (B) is a linear polymer, and the silane compound in the modified liquid diene polymer (B) It is preferable that 65% or more of the functional groups derived from is present in a total range of 45% from one end or both ends.
- the length occupied by the polymer block in the block copolymer is calculated from the number of each monomer unit contained in each block copolymer by 1 H-NMR measurement, and the carbon in the main chain of the block copolymer is calculated. It can be determined by calculating assuming that the bond length of the carbon single bond is 150 pm, the bond length of the carbon-carbon double bond is 135 pm, and the bond angle is 120 °.
- the functional groups derived from the silane compound in the modified liquid diene polymer (B) the proportion existing in a range of 45% of the total chain length from one end or both ends is highly reactive with the silane compound.
- the ratio of the number of 1,2-bonded butadiene units existing in the above range can be determined by calculating from 1 H-NMR measurement.
- the modified liquid diene polymer (B1) or (B2) has high affinity with the filler (C) described later and is concentrated in the vicinity of the filler (C) and is excellent in the reinforcing property of the filler (C). Moreover, it is estimated that it contributes also to the compatibility improvement of a filler (C) and solid rubber (A). Therefore, the dispersion state of the filler (C) in the rubber composition is ideal for expressing the physical properties of the crosslinked product obtained from the rubber composition. For example, the dispersibility of the filler (C) in the rubber composition is improved. In some cases, the pain effect of the crosslinked product obtained from the rubber composition is sufficiently reduced. Further, the cross-linked product is excellent in mechanical strength such as wear resistance and wet grip. Therefore, for example, when the crosslinked product is used as a tire or the like, these physical properties are excellent.
- the modified liquid diene polymer (B1) or (B2) may be used alone or in combination of two or more.
- the modified liquid diene polymers (B1) and (B2) may be used in combination.
- the amount of catalyst residue derived from the polymerization catalyst used for the production thereof is preferably in the range of 0 to 200 ppm in terms of metal.
- an organic alkali metal such as an organic lithium compound
- the metal used as the standard of the catalyst residue amount is an alkali metal such as lithium.
- the amount of catalyst residue derived from the polymerization catalyst used in the production of the modified liquid diene polymer (B) is more preferably 0 to 150 ppm, and still more preferably 0 to 100 ppm in terms of metal.
- the amount of catalyst residue can be measured by using, for example, a polarized Zeeman atomic absorption spectrophotometer.
- the modified liquid diene polymer (B1) or (B2) or the unmodified liquid diene polymer (B ′) as a raw material is used.
- examples thereof include a method of purifying 1) or (B′2) and sufficiently removing catalyst residues.
- a purification method washing with water or warm water, an organic solvent typified by methanol, acetone or the like or supercritical fluid carbon dioxide is preferable.
- the number of washings is preferably 1 to 20 times and more preferably 1 to 10 times from the economical viewpoint.
- the washing temperature is preferably 20 to 100 ° C., more preferably 40 to 90 ° C.
- the amount of polymerization catalyst required can be reduced, The amount of catalyst residue can be reduced.
- the amount of catalyst residue in the rubber composition containing the solid rubber (A), the modified liquid diene polymer (B1) or (B2) and the filler (C) of the present invention is a metal. It is preferably 0 to 200 ppm in terms of conversion, more preferably 0 to 150 ppm, and even more preferably 0 to 100 ppm.
- the catalyst residue amount in this case is a catalyst derived from the polymerization catalyst used for the production of the solid rubber (A), the modified liquid diene polymer (B1) or (B2) and / or other optional components contained in the rubber composition.
- the amount of residue may be sufficient.
- the rubber composition of the present invention contains 100 parts by mass of the solid rubber (A), 0.1 to 50 parts by mass of the modified liquid diene polymer (B), and 20 to 200 parts by mass of the filler (C).
- Solid rubber (A) used in the rubber composition of the present invention means a rubber that can be handled in a solid state at 20 ° C., and the Mooney viscosity ML 1 + 4 at 100 ° C. of the solid rubber (A) is usually 20 to 200. It is in the range.
- the solid rubber (A) include natural rubber, styrene butadiene rubber (hereinafter also referred to as “SBR”), butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber, and butadiene acrylonitrile copolymer.
- SBR styrene butadiene rubber
- Examples thereof include rubber, chloroprene rubber, acrylic rubber, fluorine rubber, and urethane rubber.
- solid rubbers (A) natural rubber, SBR, butadiene rubber, and isoprene rubber are preferable, and natural rubber and SBR are more preferable.
- These solid rubbers (A) may be used alone or in combination of two or more.
- the number average molecular weight (Mn) of the solid rubber (A) is preferably 80,000 or more from the viewpoint of sufficiently exhibiting the characteristics of the obtained rubber composition and crosslinked product, and is 100,000 to 3,000. More preferably, it is within the range of 1,000.
- the number average molecular weight in this specification is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
- the natural rubber is generally used in the tire industry such as SMR (Malaysia TSR), SIR (Indonesian TSR), STR (Thailand TSR), and other TSR (Technically Specialized Rubber) and RSS (Ribbed Smoked Sheet).
- SMR Melia TSR
- SIR Indonesian TSR
- STR Thailand TSR
- RSS Rabbed Smoked Sheet
- modified natural rubber such as natural rubber, high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, and grafted natural rubber.
- SMR20, STR20, and RSS # 3 are preferable from the viewpoint of little variation in quality and easy availability.
- These natural rubbers may be used alone or in combination of two or more.
- the SBR those commonly used for tire applications can be used. Specifically, those having a styrene content of 0.1 to 70% by mass are preferred, those having a styrene content of 5 to 50% by mass are more preferred, and 15 More preferable is 35% by mass.
- the vinyl content is preferably 0.1 to 60% by mass, more preferably 0.1 to 55% by mass.
- the weight average molecular weight (Mw) of SBR is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and 200,000 to 1,500,000. More preferably it is. When it is in the above range, both workability and mechanical strength can be achieved.
- the weight average molecular weight in this specification is the weight average molecular weight of polystyrene conversion calculated
- the glass transition temperature obtained by differential thermal analysis of SBR used in the present invention is preferably ⁇ 95 to 0 ° C., more preferably ⁇ 95 to ⁇ 5 ° C. By setting the glass transition temperature in the above range, the viscosity of the SBR can be set in a range that is easy to handle.
- SBR that can be used in the present invention is obtained by copolymerizing styrene and butadiene.
- SBR there is no particular limitation on the production method of SBR, and any of an emulsion polymerization method, a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method can be used. Among these production methods, an emulsion polymerization method and a solution polymerization method are preferable. .
- Emulsion-polymerized styrene butadiene rubber (hereinafter also referred to as E-SBR) can be produced by a conventional emulsion polymerization method known in the art or in accordance with a known method. For example, it can be obtained by emulsifying and dispersing a predetermined amount of styrene and butadiene monomer in the presence of an emulsifier, and emulsion polymerization with a radical polymerization initiator.
- a solution-polymerized styrene butadiene rubber (hereinafter also referred to as S-SBR) can be produced by an ordinary solution polymerization method.
- S-SBR styrene butadiene rubber
- an active metal capable of anion polymerization in a solvent is used, and optionally in the presence of a polar compound. Polymerizes styrene and butadiene.
- the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, And aromatic hydrocarbons such as toluene.
- aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane
- alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane
- benzene And aromatic hydrocarbons such as toluene.
- These solvents are usually preferably used in a range where the monomer concentration is 1 to 50% by mass.
- anion-polymerizable active metal examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium .
- alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
- organic alkali metal compounds are more preferably used.
- organic alkali metal compound examples include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4 -Polyfunctional organolithium compounds such as dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like.
- organic lithium compound is preferable, and an organic monolithium compound is more preferable.
- the amount of the organic alkali metal compound used is appropriately determined depending on the required molecular weight of S-SBR.
- the organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, and dibenzylamine.
- the polar compound is not particularly limited as long as it is usually used for adjusting the microstructure of the butadiene site and the distribution in the copolymer chain of styrene without deactivating the reaction in anionic polymerization.
- examples include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
- the temperature of the polymerization reaction is usually in the range of ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., more preferably 30 to 90 ° C.
- the polymerization mode may be either a batch type or a continuous type.
- styrene and butadiene are continuously or intermittently supplied into the reaction solution so that the composition ratio of styrene and butadiene in the polymerization system falls within a specific range. Is preferred.
- the polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator.
- the target S-SBR can be recovered by separating the solvent by direct drying, steam stripping or the like.
- the polymerization solution and the extending oil may be mixed in advance and recovered as an oil-extended rubber.
- a modified SBR in which a functional group is introduced into the SBR may be used as long as the effects of the present invention are not impaired.
- the functional group include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group, and a carboxyl group.
- the modified SBR for example, before adding a polymerization terminator, tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, which can react with a polymerization active terminal, Coupling agents such as 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate, 4,4′-bis (diethylamino) benzophenone, N-vinylpyrrolidone, etc. And a method of adding other modifiers described in JP2011-132298A.
- the position of the polymer into which the functional group is introduced may be a polymerization terminal or a side chain of the polymer chain.
- butadiene rubber examples include Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel;
- Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel
- a lanthanoid rare earth metal catalyst such as an aluminum-organic acid neodymium-Lewis acid type or the like, or an organic alkali metal compound in the same manner as S-SBR can be used.
- Butadiene rubber polymerized with a Ziegler catalyst is preferred because of its high cis isomer content.
- the vinyl content of the butadiene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. When the vinyl content exceeds 50% by mass, the rolling resistance performance tends to deteriorate.
- the lower limit of the vinyl content is not particularly limited.
- the glass transition temperature varies depending on the vinyl content, but is preferably ⁇ 40 ° C. or lower, and more preferably ⁇ 50 ° C. or lower.
- the weight average molecular weight (Mw) of the butadiene rubber is preferably 90,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When Mw is in the above range, workability and mechanical strength are good.
- the butadiene rubber has a polyfunctional modifier, for example, tin tetrachloride, silicon tetrachloride, alkoxysilane having an epoxy group in the molecule, or amino group, as long as the effects of the present invention are not impaired.
- a modifier such as alkoxysilane, it may have a branched structure or a polar functional group.
- isoprene rubber examples include Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel;
- Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel
- a commercially available isoprene rubber polymerized with an lanthanoid rare earth metal catalyst such as an aluminum-organic acid neodymium-Lewis acid system or an organic alkali metal compound in the same manner as S-SBR can be used.
- Isoprene rubber polymerized with a Ziegler catalyst is preferred because of its high cis isomer content.
- the vinyl content of the isoprene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. When the vinyl content exceeds 50% by mass, the rolling resistance performance tends to deteriorate.
- the lower limit of the vinyl content is not particularly limited.
- the glass transition temperature varies depending on the vinyl content, but is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower.
- the weight average molecular weight (Mw) of the isoprene rubber is preferably 90,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When Mw is in the above range, workability and mechanical strength are good.
- a part thereof is a polyfunctional modifier, such as tin tetrachloride, silicon tetrachloride, alkoxysilane having an epoxy group in the molecule, or amino group-containing
- a modifier such as alkoxysilane, it may have a branched structure or a polar functional group.
- the content of the modified liquid diene polymer (B) with respect to 100 parts by mass of the solid rubber (A) is 0.1 to 50 parts by mass, and 0.1 to 45 parts by mass. Preferably, it is 0.5 to 40 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 2 to 40 parts by mass.
- the dispersion state of the filler (C) in the rubber composition becomes ideal (for example, reduction of the Pain effect in the resulting crosslinked product). Effect), wear resistance is improved, and for example, steering stability and rolling resistance performance of tires and the like are improved.
- filler (C) for example, carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, fibrous filler, examples thereof include inorganic fillers such as glass balloons; organic fillers such as resin particles, wood powder, and cork powder.
- inorganic fillers such as glass balloons
- organic fillers such as resin particles, wood powder, and cork powder.
- carbon black and silica are preferable from the viewpoint of improving physical properties such as improvement of mechanical strength.
- Examples of the carbon black include furnace black, channel black, thermal black, acetylene black, and ketjen black. Of these carbon blacks, furnace black is preferable from the viewpoint of improving the crosslinking speed and mechanical strength. These carbon blacks may be used alone or in combination of two or more.
- the average particle size of the carbon black is preferably 5 to 100 nm, more preferably 5 to 80 nm, and further preferably 5 to 70 nm from the viewpoint of improving dispersibility, mechanical strength, hardness and the like.
- the average particle size of carbon black can be determined by measuring the particle diameter with a transmission electron microscope and calculating the average value.
- Examples of commercially available products of the furnace black include Mitsubishi Chemical Corporation “Diamond Black” and Tokai Carbon Co., Ltd. “Seast”.
- Examples of commercially available acetylene black include “DENKA BLACK” manufactured by Denki Kagaku Kogyo Co., Ltd.
- Examples of commercially available ketjen black include “ECP600JD” manufactured by Lion Corporation.
- the above carbon black is subjected to acid treatment with nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof, or surface oxidation treatment by heat treatment in the presence of air. May be performed.
- heat treatment may be performed at 2,000 to 3,000 ° C. in the presence of a graphitization catalyst.
- Examples of the graphitization catalyst include boron, boron oxide (for example, B 2 O 2 , B 2 O 3 , B 4 O 3 , B 4 O 5 ), boron oxoacid (for example, orthoboric acid, metaboric acid, Tetraboric acid etc.) and salts thereof, boron carbide (eg B 4 C, B 6 C etc.), boron nitride (BN), and other boron compounds are preferably used.
- boron oxide for example, B 2 O 2 , B 2 O 3 , B 4 O 3 , B 4 O 5
- boron oxoacid for example, orthoboric acid, metaboric acid, Tetraboric acid etc.
- boron carbide eg B 4 C, B 6 C etc.
- BN boron nitride
- other boron compounds are preferably used.
- the carbon black can be used after adjusting the particle size by pulverization or the like.
- high-speed rotary pulverizer hammer mill, pin mill, cage mill
- various ball mills rolling mill, vibration mill, planetary mill
- stirring mill be used for carbon black pulverization.
- silica examples include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate and the like.
- wet silica is preferable from the viewpoint of further improving processability, mechanical strength, and wear resistance.
- These silicas may be used alone or in combination of two or more.
- the average particle diameter of silica is preferably 0.5 to 200 nm, more preferably 5 to 150 nm, and even more preferably 10 to 100 nm from the viewpoint of improving processability, rolling resistance performance, mechanical strength, and wear resistance.
- the average particle diameter of silica can be determined by measuring the diameter of the particles with a transmission electron microscope and calculating the average value.
- the filler (C) contains silica.
- the content of the filler (C) with respect to 100 parts by mass of the solid rubber (A) is 20 to 200 parts by mass, preferably 20 to 180 parts by mass, and more preferably 25 to 150 parts by mass.
- the content of the filler (C) is within the above range, workability, rolling resistance performance, mechanical strength and wear resistance are improved.
- the content thereof is preferably 20 to 120 parts by mass, and 20 to 90 parts by mass with respect to 100 parts by mass of the solid rubber (A). Is more preferable, and 20 to 80 parts by mass is even more preferable.
- These fillers (C) may be used alone or in combination of two or more.
- the rubber composition of the present invention may further contain a crosslinking agent (D) in order to crosslink the rubber.
- a crosslinking agent (D) include sulfur, sulfur compounds, oxygen, organic peroxides, phenol resins, amino resins, quinone and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides. And organometallic halides and silane compounds.
- the sulfur compound include morpholine disulfide and alkylphenol disulfide.
- organic peroxide examples include cyclohexanone peroxide, methyl acetoacetate peroxide, t-butyl peroxyisobutyrate, t-butyl peroxybenzoate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, and di-t-oxide. -Butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene and the like.
- These crosslinking agents (D) may be used individually by 1 type, and may use 2 or more types together.
- the crosslinking agent (D) is usually 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the solid rubber (A) from the viewpoint of mechanical properties of the crosslinked product. 0.8 to 5 parts by mass is contained.
- the rubber composition of the present invention further contains a vulcanization accelerator (E) when sulfur, a sulfur compound or the like is contained as a crosslinking agent (D) for crosslinking (vulcanizing) rubber, for example.
- a vulcanization accelerator (E) examples include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds, aldehyde-ammonia compounds. Imidazoline compounds, xanthate compounds, and the like.
- These vulcanization accelerators (E) may be used alone or in combination of two or more.
- the vulcanization accelerator (E) is usually contained in an amount of 0.1 to 15 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid rubber (A).
- the rubber composition of the present invention further contains a vulcanization aid (F), for example, when sulfur, sulfur compounds, etc. are contained as a crosslinking agent (D) for crosslinking (vulcanizing) rubber. It may be.
- a vulcanization aid (F) include fatty acids such as stearic acid, metal oxides such as zinc white, and fatty acid metal salts such as zinc stearate. These vulcanization aids (F) may be used alone or in combination of two or more.
- the vulcanization aid (F) is usually contained in an amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the solid rubber (A).
- silica when silica is contained as the filler (C), it is a preferable embodiment that a silane coupling agent is contained.
- the silane coupling agent include sulfide compounds, mercapto compounds, vinyl compounds, amino compounds, glycidoxy compounds, nitro compounds, chloro compounds, and the like.
- sulfide compounds include bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (2-trimethoxy).
- Silylethyl) tetrasulfide bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) Disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trieth
- Examples of the mercapto compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.
- Examples of vinyl compounds include vinyl triethoxysilane and vinyl trimethoxysilane.
- Examples of amino compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, and 3- (2-aminoethyl) aminopropyltrimethyl. And methoxysilane.
- glycidoxy compounds include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycidoxypropylmethyldimethoxysilane. Is mentioned.
- Examples of the nitro compound include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.
- Examples of the chloro compound include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.
- Examples of other compounds include octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, hexadecyltrimethoxysilane, and the like.
- silane coupling agents may be used alone or in combination of two or more.
- silane coupling agents bis (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) tetrasulfide, and 3-mercaptopropyltrimethoxysilane are used from the viewpoint of high addition effect and cost. Is preferred.
- the silane coupling agent is preferably contained in an amount of 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and further preferably 1 to 15 parts by mass with respect to 100 parts by mass of silica.
- content of the silane coupling agent is within the above range, dispersibility, coupling effect, reinforcing property, and wear resistance are improved.
- the rubber composition of the present invention is intended to improve processability, fluidity, etc. within a range that does not impair the effects of the present invention, and if necessary, silicone oil, aroma oil, TDAE (Treated Distilled Aromatic Extracts), MES ( Process oils such as Mild Extracted Solvates, RAE (Residual Aromatic Extracts), paraffin oil, naphthenic oil, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9 resins, rosin resins, coumarone-indene resins, phenols
- a resin component such as a resin may be contained as a softening agent.
- the content is preferably less than 50 parts by mass with respect to 100 parts by mass of the solid rubber (A).
- the rubber composition of the present invention is an anti-aging agent, a wax, an antioxidant, a lubricant, if necessary for the purpose of improving weather resistance, heat resistance, oxidation resistance, etc., as long as the effects of the present invention are not impaired.
- Light stabilizers, scorch inhibitors, processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, and antibacterial agents You may contain additives, such as a mold agent and a fragrance
- the antioxidant include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxyl compounds, and the like.
- the antiaging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds, and phosphorus compounds. These additives may be used alone or in combination of two or more.
- the manufacturing method of the rubber composition of this invention will not be specifically limited if said each component can be mixed uniformly.
- a tangential or meshing type closed kneader such as a kneader ruder, a brabender, a banbury mixer, an internal mixer, a single screw extruder, a twin screw extruder, a mixing roll, etc. , And rollers.
- the rubber composition can be produced usually in the temperature range of 70 to 270 ° C.
- a crosslinked product can be obtained by crosslinking the rubber composition of the present invention.
- the crosslinking conditions of the rubber composition can be appropriately set according to the use and the like. For example, when sulfur or a sulfur compound is used as a cross-linking agent and the rubber composition is cross-linked (vulcanized) with a mold, the cross-linking temperature is usually 120 to 200 ° C., and the pressurizing condition is usually 0.5 to 2.0 MPa. Can be crosslinked (vulcanized).
- the extraction rate of the modified liquid diene polymer (B) from the crosslinked product is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
- the extraction rate can be calculated from the amount of the modified liquid diene polymer (B) that is obtained by immersing 2 g of the crosslinked product in 400 mL of toluene and extracting it in toluene after 48 hours at 23 ° C.
- the rubber composition of the present invention and the crosslinked product of the rubber composition can also be used as at least a part of a tire.
- the tire thus obtained has an ideal dispersed state of filler (C) (for example, the Pain effect is sufficiently reduced), so that it has excellent rolling resistance performance and wear resistance. Good properties.
- Examples of the tire portion where the rubber composition and the crosslinked product of the rubber composition can be used include treads (cap treads, under treads), sidewalls, rubber reinforcing layers (liners, etc.) for run-flat tires, rim cushions, and beads.
- Examples include fillers, bead insulation, bead apex, clinch apex, belt, belt cushion, breaker, breaker cushion, chafer, chafer pad, strip apex and the like.
- Production Example 1 Production of modified liquid diene polymer (B-1, B-2) A sufficiently dried 5 L autoclave was purged with nitrogen, 1860 g of cyclohexane and 61 g of s-butyllithium (1.0 mol / L, cyclohexane solution) The mixture was heated to 50 ° C., and then 5.8 g of tetrahydrofuran was added under stirring conditions. Then, 1175 g of isoprene and 219 g of butadiene were successively added to carry out polymerization while controlling the polymerization temperature to be 50 ° C. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymer solution.
- a modified liquid diene polymer (B-2), which is a diblock copolymer composed of a linear isoprene homopolymer block and a butadiene homopolymer block, modified in step (1) was obtained.
- the butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- Production Example 2 Production of Modified Liquid Diene Polymer (B-3, B-13) A sufficiently dried 5 L autoclave was purged with nitrogen, 1860 g of cyclohexane and 57 g of s-butyllithium (1.1 mol / L, cyclohexane solution) After adding 5.8 g of tetrahydrofuran under stirring conditions, 116 g of butadiene, 1087 g of isoprene and 83 g of butadiene were successively added while controlling the polymerization temperature to be 50 ° C. did. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymer solution.
- the butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- (B-13) (3-mercaptopropyl) triethoxysilane not radically added was washed away with methanol, and the average number of functional groups per molecule calculated from 1 H-NMR was 15. I understood.
- the butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- Production Example 3 Production of Modified Liquid Diene Polymer (B-4) A well-dried 5 L autoclave was purged with nitrogen and charged with 1850 g of cyclohexane and 69 g of s-butyllithium (1.1 mol / L, cyclohexane solution). After the temperature was raised to 0 ° C., 823 g of butadiene was successively added while controlling the polymerization temperature to 50 ° C. under stirring conditions, and then 3.4 g of N, N, N ′, N′-tetramethylethylenediamine was added. Then, 550 g of butadiene was sequentially added and polymerized.
- the high vinyl content butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- Production Example 4 Production of Modified Liquid Diene Polymer (B-5) A well-dried 1 L autoclave was purged with nitrogen, and 65 g of cyclohexane, 76 g of s-butyllithium (1.1 mol / L, cyclohexane solution), and 13 g of triethylamine were added. The temperature was raised to 50 ° C. Under stirring conditions, 8.3 g of 1,3-bis (1-methylethenyl) benzene was added and stirred at 70 ° C. The resulting reaction solution was cooled to 25 ° C., 23 g of butadiene was added all at once under stirring conditions, the temperature was raised to 50 ° C. and stirred for 30 minutes, and then cooled to 25 ° C.
- a fully dried 5 L autoclave was purged with nitrogen, charged with 2060 g of cyclohexane and the total amount of the above reaction solution, heated to 50 ° C., and 352 g of butadiene was added under stirring conditions while controlling the polymerization temperature to be 50 ° C.
- 3.4 g of N, N, N ′, N′-tetramethylethylenediamine was added, and 198 g of butadiene was sequentially added for polymerization.
- methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the resulting polymer solution and stirred, and the polymer solution was washed with water.
- a modified liquid diene polymer which is a triblock copolymer composed of a linear high vinyl content butadiene homopolymer block modified with a low vinyl content butadiene homopolymer block and a high vinyl content butadiene homopolymer block ( B-5) was obtained.
- the high vinyl content butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- the high vinyl content butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- Production Example 8 Production of Modified Liquid Diene Polymer (B-9) A well-dried 5 L autoclave was purged with nitrogen and charged with 1660 g of cyclohexane and 262 g of s-butyllithium (1.2 mol / L, cyclohexane solution). After the temperature was raised to 0 ° C., 964 g of isoprene was sequentially added while controlling the polymerization temperature to 50 ° C. under stirring conditions, and then 14.7 g of N, N, N ′, N′-tetramethylethylenediamine was added Then, 275 g of butadiene was sequentially added and polymerized.
- the butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- unmodified liquid diene polymer (B′-10) was charged into a 1 L autoclave and degassed with stirring at 60 ° C. for 3 hours.
- Functional group derived from silane compound (1) by adding 4.3 g of 1,1-bis (t-hexylperoxy) cyclohexane and 56 g of (3-mercaptopropyl) triethoxysilane and reacting at 105 ° C. for 8 hours.
- An unmodified liquid diene polymer (B-11) which is a triblock copolymer composed of a linear butadiene homopolymer block, an isoprene homopolymer block, and a butadiene homopolymer block modified with 1. In such a block copolymer, the butadiene homopolymer block is preferentially modified with a functional group derived from the silane compound (1) due to a difference in reactivity with the silane compound (1).
- Production Example 11 Production of Modified Liquid Diene Rubber (B-12) A well-dried 5 L autoclave was purged with nitrogen, charged with 1150 g of hexane and 154 g of n-butyllithium (17% by mass hexane solution) and heated to 50 ° C. Thereafter, 10 g of N, N, N ′, N′-tetramethylethylenediamine was added under stirring conditions, and then 1250 g of butadiene was successively added to carry out polymerization while controlling the polymerization temperature to be 50 ° C. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymer solution.
- Mw of the modified liquid diene polymer (B) was determined by GPC (gel permeation chromatography) as a standard polystyrene equivalent molecular weight.
- the measuring apparatus and conditions are as follows. ⁇ Equipment: GPC device “HLC-8320GPC” manufactured by Tosoh Corporation Separation column: “TSKgelSuperHZ4000 ⁇ 2” manufactured by Tosoh Corporation ⁇ Eluent: Tetrahydrofuran ⁇ Eluent flow rate: 0.35 mL / min ⁇ Sample concentration: 5 mg / 10 mL -Column temperature: 40 ° C
- Glass-transition temperature 10 mg of the modified liquid diene polymer (B) is collected in an aluminum pan, and a thermogram is measured by a differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min. The peak top value of the DDSC is converted into a glass transition. It was temperature.
- melt viscosity at 38 ° C. The melt viscosity at 38 ° C. of the modified liquid diene polymer (B) was measured with a Brookfield viscometer (BROOKFIELD ENGINEERING LAB. INC.).
- the equivalent of the functional group of the modified liquid diene polymer (B) means the mass of the conjugated diene bonded per functional group and the monomer other than the conjugated diene contained if necessary. To do.
- the equivalent of the functional group can be calculated from the area ratio of the peak derived from the functional group and the peak derived from the polymer main chain using 1 H-NMR or 13 C-NMR.
- the peak derived from a functional group refers to the peak derived from an alkoxy group.
- the ratio of the length occupied by the polymer block (b′1) or (b ′′ 1) in the unmodified liquid diene block copolymer (B′1) or (B′2) is the total proportion of the block copolymer. It can be determined from the chain length and the length occupied by the polymer block in the block copolymer. The length occupied by the polymer block in the block copolymer is the amount of each monomer contained in each block copolymer.
- the number of body units is calculated from 1 H-NMR measurement, the bond length of the carbon-carbon single bond in the main chain of the block copolymer is 150 pm, the bond length of the carbon-carbon double bond is 135 pm, and the bond angle is 120 °.
- the total chain length of the block copolymer can be obtained from the total number of monomer units contained in each block copolymer obtained above. it can.
- the physical properties of the modified liquid diene polymers (B-1) to (B-13) obtained in Production Examples 1 to 11 are summarized below in Table 1.
- the bonding modes of the unmodified liquid diene block copolymers (B′-1) to (B′-11) as raw materials for the modified liquid diene polymers (B-1) to (B-13) are shown. Sum it up in two.
- Examples 1 to 18 and Comparative Examples 1 to 5 According to the blending ratio (parts by mass) described in Tables 3 to 6, solid rubber (A), modified liquid diene polymer (B), filler (C), TDAE, silane coupling agent, zinc white, stearic acid, The wax and the anti-aging agent were respectively put into a closed Banbury mixer and kneaded for 6 minutes so that the starting temperature was 60 ° C. and the resin temperature was 150 ° C., then taken out of the mixer and cooled to room temperature.
- this mixture was put into a Banbury mixer again, and a rubber composition was obtained by adding a vulcanizing agent and a vulcanization accelerator and kneading for 75 seconds such that the starting temperature was 50 ° C. and the ultimate temperature was 100 ° C.
- the obtained rubber composition was press-molded (160 ° C., 30 to 50 minutes) to produce a vulcanized rubber sheet (thickness 2 mm). Based on the following methods, the Payne effect, Mooney viscosity, rolling resistance performance, Abrasion resistance, wet grip, tensile breaking elongation, and tensile breaking strength were evaluated. The results are shown in Tables 3-6. In addition, the measuring method of each evaluation is as follows.
- Mooney viscosity According to JIS K 6300, the Mooney viscosity (ML 1 + 4 ) of the rubber composition before vulcanization was measured at 130 ° C.
- the numerical values of the examples and comparative examples in Table 3 are the values when the value of Comparative Example 2 is 100, and the numerical values of the Examples and Comparative Examples in Table 6 are the relative values when the value of Comparative Example 4 is 100. Value. It shows that the processability of a rubber composition is so favorable that a numerical value is small.
- Examples 12 to 18 using the modified liquid diene polymer of the present invention have good dispersibility of silica, rolling resistance performance, wear resistance, and fracture characteristics.
- the rubber composition of the present invention is not only excellent in processability and filler dispersibility, but also when a crosslinkable rubber composition is added by adding a crosslinking agent, the filler is dispersed in the crosslinked product obtained from the composition.
- Is ideal for improving physical properties for example, a reduction in the Payne effect is seen
- gives an excellent crosslinked product with improved wear resistance, etc. so that it is used for tires, industrial belts, industrial rubber hoses.
- It can use suitably for industrial member uses, such as.
- a crosslinked product is used for a tire application or the like, it is useful because wet grip performance, wear resistance, and the like are improved.
Abstract
Description
しかし、ゴム組成物から得られる架橋物の物性(例えば、ウェットグリップ及び耐摩耗性)については、従来技術ではいまだ改善の余地があった。
また、この物性の向上にはその架橋物中のフィラーの分散状態が関与する可能性があるが、例えば、ゴム組成物中のフィラーの分散性向上の指標となるペイン効果の低減を十分に達成するという視点では、従来の技術ではいまだ改善の余地があった。
すなわち、本発明は以下〔1〕~〔15〕に関する。
(i)変性液状ジエン系ゴムの重量平均分子量(Mw)が1,000~120,000。
(ii)重合体ブロック(b'1)のブタジエン単位のビニル含量が40~100モル%。
(iii)重合体ブロック(b'2)が、ビニル含量が0~25モル%のブタジエン単位を含む。
(iv)変性液状ジエン系重合体(B1)一分子当たりの平均官能基数が1~20個。
〔3〕ブタジエン単位を含む重合体ブロック(b"1)および重合体ブロック(b"2)を含有する液状ジエン系ブロック共重合体(B'2)が前記式(1)で表されるシラン化合物により変性された、該式(1)で表されるシラン化合物に由来する官能基を有する変性液状ジエン系重合体(B2)であり、下記(v)~(vii)を満たす、変性液状ジエン系重合体(B2)。
(v)変性液状ジエン系重合体(B2)の重量平均分子量(Mw)が1,000~120,000。
(vi)重合体ブロック(b"2)がブタジエン以外の共役ジエン単位および芳香族ビニル化合物単位からなる群より選ばれる少なくとも1つの単量体単位を含む。
(vii)変性液状ジエン系重合体(B2)一分子当たりの平均官能基数が1~20個。
〔4〕変性液状ジエン系重合体(B2)が直鎖状の重合体であり、液状ジエン系ブロック共重合体(B'2)の重合体ブロック(b"1)が片末端または両末端に存在し、重合体ブロック(b"1)の占める長さが液状ジエン系ブロック共重合体(B'2)全鎖長の合計45%以下である、〔3〕に記載の変性液状ジエン系重合体(B2)。
〔5〕変性液状ジエン系重合体(B1)または(B2)が直鎖状の重合体であり、変性液状ジエン系重合体(B1)または(B2)中のシラン化合物に由来する官能基のうち、その65%以上が、片末端または両末端から全鎖長の合計45%の範囲に存在する、〔1〕~〔4〕のいずれかに記載の変性液状ジエン系重合体(B1)または(B2)。
〔6〕38℃における溶融粘度が0.1~4,000Pa・sである、〔1〕~〔5〕のいずれかに記載の変性液状ジエン系重合体(B1)または(B2)。
〔8〕前記フィラー(C)が、カーボンブラック及びシリカから選ばれる少なくとも1種である、〔7〕に記載のゴム組成物。
〔9〕前記フィラー(C)が、平均粒径5~100nmのカーボンブラック及び平均粒径が0.5~200nmのシリカから選ばれる少なくとも1種である、〔8〕に記載のゴム組成物。
〔10〕前記フィラー(C)がシリカを含み、シリカ100質量部に対し、シランカップリング剤を0.1~30質量部含有する、〔8〕又は〔9〕に記載のゴム組成物。
〔11〕前記固形ゴム(A)が、天然ゴム、スチレンブタジエンゴム、ブタジエンゴム及びイソプレンゴムから選ばれる少なくとも1種である、〔7〕~〔10〕のいずれかに記載のゴム組成物。
〔12〕前記固形ゴム(A)が、重量平均分子量が100,000~2,500,000のスチレンブタジエンゴムである、〔11〕に記載のゴム組成物。
〔13〕前記固形ゴム(A)が、スチレン含量が0.1~70質量%であるスチレンブタジエンゴムである、〔11〕又は〔12〕に記載のゴム組成物。
〔14〕〔7〕~〔13〕のいずれかに記載のゴム組成物を架橋させた架橋物。
〔15〕〔7〕~〔13〕のいずれかに記載のゴム組成物又は〔14〕に記載の架橋物を少なくとも一部に用いたタイヤ。
本発明の変性液状ジエン系重合体は、ブタジエン単位を含む重合体ブロックおよびこれとは異なる重合体ブロックを含有する未変性の液状ジエン系ブロック共重合体が前記式(1)で表されるシラン化合物により変性された重合体であり、その重合体は前記式(1)で表されるシラン化合物に由来する官能基を有し、さらに特定の条件を満たすことが必要である。
以下、変性液状ジエン系重合体(B)の原料となる未変性液状ジエン系ブロック共重合体(B')について説明をする。未変性液状ジエン系ブロック共重合体(B')としては、例えば、下記の未変性液状ジエン系ブロック共重合体(B'1)および未変性液状ジエン系ブロック共重合体(B'2)が挙げられる。
本発明の変性液状ジエン系重合体(B)の第1態様である変性液状ジエン系重合体(B1)は、ブタジエン単位を含む重合体ブロック(b'1)および重合体ブロック(b'2)を含有する未変性液状ジエン系ブロック共重合体(B'1)がシラン化合物(1)により変性され、シラン化合物(1)に由来する官能基を有しており、さらに下記(i)~(iv)を満たしている。
(i)変性液状ジエン系ゴム(B1)の重量平均分子量(Mw)が1,000~120,000。
(ii)重合体ブロック(b'1)のブタジエン単位のビニル含量が40~100モル%。
(iii)重合体ブロック(b'2)が、ビニル含量が0~25モル%のブタジエン単位を含む。
(iv)変性液状ジエン系重合体(B1)一分子当たりの平均官能基数が1~20個。
直鎖状ジブロック共重合体:b'1-b'2
直鎖状トリブロック共重合体:b'1-b'2-b'1
本発明の変性液状ジエン系重合体(B)の第2態様である変性液状ジエン系重合体(B2)は、ブタジエン単位を含む重合体ブロック(b"1)および重合体ブロック(b"2)を含有する未変性液状ジエン系ブロック共重合体(B'2)がシラン化合物(1)により変性され、シラン化合物(1)に由来する官能基を有しており、さらに下記(v)~(vii)を満たしている。
(v)変性液状ジエン系重合体(B2)の重量平均分子量(Mw)が1,000~120,000。
(vi)重合体ブロック(b"2)がブタジエン以外の共役ジエン単位および芳香族ビニル化合物単位からなる群より選ばれる少なくとも1つの単量体単位を含む。
(vii)変性液状ジエン系重合体(B2)一分子当たりの平均官能基数が1~20個。
直鎖状ジブロック共重合体:b"1-b"2
直鎖状トリブロック共重合体:b"1-b"2-b"1
このようにして得られた未変性液状ジエン系ブロック共重合体(B'1)または(B'2)は、そのまま(水素添加されない状態で)後述する式(1)で表されるシラン化合物に由来する官能基による変性が行われてもよいが、その液状ジエン系ゴム中に含まれる不飽和結合の少なくとも一部を水素添加した後に変性が行われてもよい。
(一分子当たりの平均官能基数)=[(数平均分子量Mn)/(スチレン単位の分子量)×(共役ジエン及び必要に応じて含まれる共役ジエン以外の他の単量体単位の平均分子量)]/(官能基の当量)
この時に用いる好ましい老化防止剤としては、例えば、2,6-ジt-ブチル-4-メチルフェノール(BHT)、2,2'-メチレンビス(4-メチル-6-t-ブチルフェノール)、4,4'-チオビス(3-メチル-6-t-ブチルフェノール)、4,4'-ブチリデンビス(3-メチル-6-t-ブチルフェノール)(AO-40)、3,9-ビス[1,1-ジメチル-2-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]エチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン(AO-80)、2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール(Irganox1520L)、2,4-ビス[(ドデシルチオ)メチル]-6-メチルフェノール(Irganox1726)、2-[1-(2-ヒドロキシ-3,5-ジt-ペンチルフェニル)エチル]-4,6-ジt-ペンチルフェニルアクリレート(SumilizerGS)、2-tブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェニルアクリレート(SumilizerGM)、6-t-ブチル-4-[3-(2,4,8,10-テトラ-t-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イルオキシ)プロピル]-2-メチルフェノール(SumilizerGP)、亜りん酸トリス(2,4-ジt-ブチルフェニル)(Irgafos168)、ジオクタデシル3,3'-ジチオビスプロピオネート、ヒドロキノン、p-メトキシフェノール、N-フェニル-N'-(1,3-ジメチルブチル)-p-フェニレンジアミン(ノクラック6C)、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート(LA-77Y)、N,N-ジオクタデシルヒドロキシルアミン(IrgastabFS042)、ビス(4-t-オクチルフェニル)アミン(Irganox5057)などが挙げられる。上記老化防止剤は、1種単独で用いてもよく、2種以上を併用してもよい。
老化防止剤の添加量は、未変性液状ジエン系ブロック共重合体(B'1)または(B'2)100質量部に対して0~10質量部が好ましく、0~5質量部がより好ましい。
本発明のゴム組成物は、固形ゴム(A)100質量部、上記変性液状ジエン系重合体(B)0.1~50質量部、及びフィラー(C)20~200質量部を含有する。
本発明のゴム組成物で用いる固形ゴム(A)とは、20℃において固形状で取り扱うことができるゴムをいい、固形ゴム(A)の100℃におけるムーニー粘度ML1+4は通常20~200の範囲にある。上記固形ゴム(A)としては、例えば、天然ゴム、スチレンブタジエンゴム(以下、「SBR」ともいう。)、ブタジエンゴム、イソプレンゴム、ブチルゴム、ハロゲン化ブチルゴム、エチレンプロピレンジエンゴム、ブタジエンアクリロニトリル共重合体ゴム、クロロプレンゴム、アクリルゴム、フッ素ゴム、及びウレタンゴム等が挙げられる。これら固形ゴム(A)の中でも、天然ゴム、SBR、ブタジエンゴム、及びイソプレンゴムが好ましく、天然ゴム、及びSBRがさらに好ましい。これら固形ゴム(A)は、1種単独で用いてもよく、2種以上を併用してもよい。
本発明のゴム組成物で用いるフィラー(C)としては、例えば、カーボンブラック、シリカ、クレー、マイカ、炭酸カルシウム、水酸化マグネシウム、水酸化アルミニウム、硫酸バリウム、酸化チタン、ガラス繊維、繊維状フィラー、ガラスバルーン等の無機フィラー;樹脂粒子、木粉、及びコルク粉等の有機フィラーなどが挙げられる。このようなフィラーがゴム組成物に含まれることにより、機械強度、耐熱性、又は耐候性等の物性の改善、硬度の調整、ゴムの増量をすることができる。機械強度の向上等の物性の改善などの観点からは、上記フィラー(C)の中でも、カーボンブラック及びシリカが好ましい。
本発明のゴム組成物において、固形ゴム(A)100質量部に対するフィラー(C)の含有量は20~200質量部であり、20~180質量部が好ましく、25~150質量部がより好ましい。フィラー(C)の含有量が前記範囲内であると、加工性、転がり抵抗性能、機械強度及び耐摩耗性が向上する。
これらフィラー(C)は1種単独で用いてもよく、2種以上を併用してもよい。
本発明のゴム組成物は、そのゴムを架橋するために、さらに架橋剤(D)を含有していてもよい。架橋剤(D)としては、例えば、硫黄、硫黄化合物、酸素、有機過酸化物、フェノール樹脂、アミノ樹脂、キノン及びキノンジオキシム誘導体、ハロゲン化合物、アルデヒド化合物、アルコール化合物、エポキシ化合物、金属ハロゲン化物及び有機金属ハロゲン化物、及びシラン化合物などが挙げられる。硫黄化合物としては、例えば、モルホリンジスルフィド、及びアルキルフェノールジスルフィドなどが挙げられる。有機過酸化物としては、例えば、シクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、t-ブチルパーオキシイソブチレート、t-ブチルパーオキシベンゾエート、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ジクミルパーオキサイド、ジt-ブチルパーオキサイド、及び1,3-ビス(t-ブチルパーオキシイソプロピル)ベンゼンなどが挙げられる。これら架橋剤(D)は1種単独で用いてもよく、2種以上を併用してもよい。上記架橋剤(D)は、架橋物の力学物性の観点から、固形ゴム(A)100質量部に対し、通常0.1~10質量部、好ましくは0.5~10質量部、より好ましくは0.8~5質量部含有される。
アミノ系化合物としては、例えば、3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-(2-アミノエチル)アミノプロピルトリエトキシシラン、及び3-(2-アミノエチル)アミノプロピルトリメトキシシランなどが挙げられる。
クロロ系化合物としては、例えば、3-クロロプロピルトリメトキシシラン、3-クロロプロピルトリエトキシシラン、2-クロロエチルトリメトキシシラン、及び2-クロロエチルトリエトキシシランなどが挙げられる。
その他の化合物としては、例えば、オクチルトリエトキシシラン、メチルトリエトキシシラン、メチルトリメトキシシラン、ヘキサデシルトリメトキシシランなどが挙げられる。
本発明のゴム組成物の製造方法は、上記各成分を均一に混合できれば特に限定されない。ゴム組成物の製造に用いる装置としては、例えば、ニーダールーダー、ブラベンダー、バンバリーミキサー、インターナルミキサー等の接線式又は噛合式の密閉式混練機、単軸押出機、二軸押出機、ミキシングロール、及びローラーなどが挙げられる。上記ゴム組成物を製造は、通常70~270℃の温度範囲で行うことができる。
本発明のゴム組成物を架橋することにより、架橋物を得ることができる。ゴム組成物の架橋条件は、その用途等に応じて適宜設定できる。例えば、硫黄又は硫黄化合物を架橋剤とし、ゴム組成物を金型により架橋(加硫)する場合には、架橋温度は通常120~200℃、加圧条件は通常0.5~2.0MPaとし、架橋(加硫)することができる。
なお、上記抽出率は、架橋物2gをトルエン400mL中に浸漬し、23℃で48時間後にトルエン中に抽出された変性液状ジエン系重合体(B)の量から算出することができる。
本実施例及び比較例において使用した各成分は以下のとおりである。
溶液重合スチレンブタジエンゴム:HPR355(JSR株式会社製、アルコキシシリル基を末端に導入、スチレン含量:28質量%、ビニル含量56質量%)
ブタジエンゴム:BR01(JSR株式会社製、Mw:55万、シス体含有量95質量%)
<変性液状ジエン系重合体(B)>
後述の製造例1~11で得られた変性液状ジエン系重合体
<フィラー(C)>
シリカ:ULTRASIL7000GR(エボニック デグサ ジャパン製、湿式シリカ、平均粒径14nm)
<架橋剤(D)>
硫黄(微粉硫黄200メッシュ、鶴見化学工業株式会社製)
<加硫促進剤(E)>
加硫促進剤(1):ノクセラーCZ-G (大内新興化学工業株式会社製)
加硫促進剤(2):ノクセラーD (大内新興化学工業株式会社製)
加硫促進剤(3):ノクセラーTBT-N(大内新興化学工業株式会社製)
<加硫助剤(F)>
ステアリン酸:ルナックS-20(花王株式会社製)
亜鉛華:酸化亜鉛(堺化学工業株式会社製)
<任意成分>
TDAE:VivaTec500(H&R社製)
シランカップリング剤(1):Si-75(エボニック デグサ ジャパン製)
老化防止剤(1):ノクラック6C(大内新興化学工業株式会社製)
ワックス:サンタイトS(精工化学株式会社製)
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1860g及びs-ブチルリチウム(1.0mol/L、シクロヘキサン溶液)61gを仕込み、50℃に昇温した後、撹拌条件下、テトラヒドロフラン5.8gを添加した後、重合温度を50℃となるように制御しながら、イソプレン1175gとブタジエン219gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、直鎖状のイソプレン単独重合体ブロック-ブタジエン単独重合体ブロックからなるジブロック共重合体である未変性液状ジエン系重合体(B'-1)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1860g及びs-ブチルリチウム(1.1mol/L、シクロヘキサン溶液)57gを仕込み、50℃に昇温した後、撹拌条件下、テトラヒドロフラン5.8gを添加した後、重合温度を50℃となるように制御しながらブタジエン116g、イソプレン1087g、ブタジエン83gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、直鎖状のブタジエン単独重合体ブロック-イソプレン単独重合体ブロック-ブタジエン単独重合体ブロックからなるトリブロック共重合体である未変性液状ジエン系重合体(B'-2)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1850g及びs-ブチルリチウム(1.1mol/L、シクロヘキサン溶液)69gを仕込み、50℃に昇温した後、撹拌条件下、重合温度を50℃となるように制御しながら、ブタジエン823gを逐次添加した後、N,N,N',N'-テトラメチルエチレンジアミン3.4gを添加し、ブタジエン550gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、直鎖状の低ビニル含量ブタジエン単独重合体ブロック-高ビニル含量ブタジエン単独重合体ブロックからなるジブロック共重合体である未変性液状ジエン系重合体(B'-3)を得た。
十分に乾燥した1Lオートクレーブを窒素置換し、シクロヘキサン65g、s-ブチルリチウム(1.1mol/L、シクロヘキサン溶液)76g、トリエチルアミン13gを仕込み、50℃に昇温した。撹拌条件下、1,3-ビス(1-メチルエテニル)ベンゼン8.3gを添加し、70℃で撹拌した。得られた反応液を25℃まで冷却し、撹拌条件下、ブタジエン23gを一括添加し、50℃に昇温して30分撹拌した後、25℃まで冷却した。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1860g及びs-ブチルリチウム(1.0mol/L、シクロヘキサン溶液)61gを仕込み、50℃に昇温した後、撹拌条件下、テトラヒドロフラン5.8gを添加した後、重合温度を50℃となるように制御しながら予め調製したブタジエン、イソプレンの混合物(ブタジエン166gとイソプレン1120gとをボンベ内で混合)1286gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、イソプレン/ブタジエンランダム共重合体である未変性液状ジエン系重合体(B'-5)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1850g及びs-ブチルリチウム(1.1mol/L、シクロヘキサン溶液)69gを仕込み、50℃に昇温した後、撹拌条件下、テトラヒドロフラン3.8gを添加した後、重合温度を50℃となるように制御しながらブタジエン1363gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、ブタジエン単独重合体からなる未変性液状ジエン系重合体(B'-6)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1570g及びs-ブチルリチウム(0.99mol/L、シクロヘキサン溶液)347gを仕込み、50℃に昇温した後、撹拌条件下、重合温度を50℃となるように制御しながら、ブタジエン797gを逐次添加した後、N,N,N',N'-テトラメチルエチレンジアミン10.8gを添加し、ブタジエン522gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、直鎖状の低ビニル含量ブタジエン単独重合体ブロック-高ビニル含量ブタジエン単独重合体ブロックからなるジブロック共重合体である未変性液状ジエン系重合体(B'-7)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1660g及びs-ブチルリチウム(1.2mol/L、シクロヘキサン溶液)262gを仕込み、50℃に昇温した後、撹拌条件下、重合温度を50℃となるように制御しながら、イソプレン964gを逐次添加した後、N,N,N',N'-テトラメチルエチレンジアミン14.7gを添加し、ブタジエン275gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、直鎖状のイソプレン単独重合体ブロック-ブタジエン単独重合体ブロックからなるジブロック共重合体である未変性液状ジエン系重合体(B'-8)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1580g及びs-ブチルリチウム(0.99mol/L、シクロヘキサン溶液)336gを仕込み、50℃に昇温した後、撹拌条件下、テトラヒドロフラン23.4gを添加した後、重合温度を50℃となるように制御しながらブタジエン218g、イソプレン776g、ブタジエン234gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、直鎖状のブタジエン単独重合体ブロック-イソプレン単独重合体ブロック-ブタジエン単独重合体ブロックからなるトリブロック共重合体である未変性液状ジエン系重合体(B'-9)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、シクロヘキサン1570g及びs-ブチルリチウム(0.99mol/L、シクロヘキサン溶液)336gを仕込み、50℃に昇温した後、撹拌条件下、テトラヒドロフラン11.3gを添加した後、重合温度を50℃となるように制御しながらブタジエン205g、イソプレン732g、ブタジエン275gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を140℃で3時間乾燥することにより、直鎖状のブタジエン単独重合体ブロック-イソプレン単独重合体ブロック-ブタジエン単独重合体ブロックからなるトリブロック共重合体である未変性液状ジエン系重合体(B'-10)を得た。
十分に乾燥した5Lオートクレーブを窒素置換し、ヘキサン1150g及びn-ブチルリチウム(17質量%ヘキサン溶液)154gを仕込み、50℃に昇温した後、撹拌条件下、N,N,N',N'-テトラメチルエチレンジアミン10gを添加した後、重合温度を50℃となるように制御しながらブタジエン1250gを逐次添加して重合した。その後メタノールを添加して重合反応を停止させ、重合体溶液を得た。得られた重合体溶液に水を添加して撹拌し、水で重合体溶液を洗浄した。撹拌を終了し、重合体溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合体溶液を70℃で24時間真空乾燥することにより、ブタジエン単独重合体からなる未変性液状ジエン系重合体(B'-11)を得た。
なお、製造例で得られた変性液状ジエン系重合体等の各物性の測定方法及び算出方法は以下の通りである。
変性液状ジエン系重合体(B)のMwは、GPC(ゲルパーミエーションクロマトグラフィー)により標準ポリスチレン換算分子量で求めた。測定装置及び条件は、以下の通りである。
・装置 :東ソー株式会社製GPC装置「HLC-8320GPC」
・分離カラム :東ソー株式会社製「TSKgelSuperHZ4000×2」
・溶離液 :テトラヒドロフラン
・溶離液流量 :0.35mL/分
・サンプル濃度:5mg/10mL
・カラム温度 :40℃
変性液状ジエン系重合体(B)、重合体ブロック(b'1)または(b"1)、重合体ブロック(b'2)または(b"2)のビニル含量を、日本電子株式会社製1H-NMR(500MHz)を使用し、サンプル/重クロロホルム=50mg/1mLの濃度、積算回数32回で測定した。得られたスペクトルの1,2-結合、3,4-結合で結合をしている共役ジエン単位由来のピークと、1,4-結合で結合をしている共役ジエン単位に由来するピークとの面積比から、ビニル含量を算出した。
変性液状ジエン系重合体(B)10mgをアルミパンに採取し、示差走査熱量測定(DSC)により10℃/分の昇温速度条件においてサーモグラムを測定し、DDSCのピークトップの値をガラス転移温度とした。
変性液状ジエン系重合体(B)の38℃における溶融粘度をブルックフィールド型粘度計(BROOKFIELD ENGINEERING LABS.INC.製)により測定した。
変性液状ジエン系重合体(B)一分子当たりの平均官能基数は、変性液状ジエン系重合体(B)の官能基の当量(g/eq)とスチレン換算の数平均分子量Mnより求めることができる。
(一分子当たりの平均官能基数)=[(数平均分子量Mn)/(スチレン単位の分子量)×(共役ジエン及び必要に応じて含まれる共役ジエン以外の他の単量体単位の平均分子量)]/(官能基の当量)
未変性液状ジエン系ブロック共重合体(B'1)または(B'2)中の重合体ブロック(b'1)または(b"1)が占める長さの割合は、ブロック共重合体の全鎖長と、ブロック共重合体中の重合体ブロックの占める長さから求めることができる。ブロック共重合体中の重合体ブロックの占める長さは、それぞれのブロック共重合体に含まれる各単量体単位の数を1H-NMR測定より算出し、ブロック共重合体の主鎖における炭素-炭素単結合の結合長を150pm、炭素-炭素二重結合の結合長を135pm、結合角を120°と仮定し計算することで、求めることができる。また、ブロック共重合体の全鎖長は上記で得られるそれぞれのブロック共重合体に含まれる各単量体単位の数の合計から求めることができる。
表3~6に記載した配合割合(質量部)にしたがって、固形ゴム(A)、変性液状ジエン系重合体(B)、フィラー(C)、TDAE、シランカップリング剤、亜鉛華、ステアリン酸、ワックス、及び老化防止剤を、それぞれ密閉式バンバリーミキサーに投入して開始温度60℃、樹脂温度が150℃となるように6分間混練した後、ミキサー外に取り出して室温まで冷却した。次いで、この混合物を再度バンバリーミキサーに入れ、加硫剤及び加硫促進剤を加えて開始温度50℃、到達温度100℃となるように75秒混練することでゴム組成物を得た。
なお、各評価の測定方法は以下のとおりである。
実施例及び比較例で作製したゴム組成物のシートから縦40mm×横5mmの試験片を切り出し、GABO社製動的粘弾性測定装置を用いて、測定温度25℃、歪0.5%の貯蔵弾性率E'(0.5%)と、歪5.0%の貯蔵弾性率E'(5.0%)を測定し、E'(0.5%)とE'(5.0%)の差(絶対値)を算出した。表3における各実施例及び比較例の数値は、比較例2の値を100とした際の、表5における各実施例及び比較例の数値は、比較例5の値を100とした際の相対値である。数値が小さいほどペイン効果が低減され、ゴム組成物のシリカの分散性が良好であることを示す。
JIS K 6300に準拠して、加硫前のゴム組成物のムーニー粘度(ML1+4)を130℃で測定した。表3における各実施例及び比較例の数値は、比較例2の値を100とした際の、表6における各実施例及び比較例の数値は、比較例4の値を100とした際の相対値である。数値が小さいほどゴム組成物の加工性が良好であることを示す。
実施例及び比較例で作製したゴム組成物のシートから縦40mm×横5mmの試験片を切り出し、GABO社製動的粘弾性測定装置を用いて、測定温度60℃、周波数10Hz、静的歪み10%、動的歪み2%の条件で、tanδを測定し、転がり抵抗性能の指標とした。表3における各実施例及び比較例の数値は、比較例2の値を100とした際の、表5における各実施例及び比較例の数値は、比較例5の値を100とした際の相対値である。数値が小さいほどゴム組成物の転がり抵抗性能が良好であることを示す。
JIS K 6264に準拠して、10N荷重下、摩耗距離40mでのDIN摩耗量を測定した。表3における各実施例及び比較例の数値は、DIN摩耗量の逆数において比較例2の値を100とした際の、表5における各実施例及び比較例の数値は、DIN摩耗量の逆数において比較例5の値を100とした際の相対値である。数値が大きいほど摩耗量が少なく耐摩耗性が良好であることを示す。
実施例及び比較例で作製したゴム組成物から直径50mm、厚み10mmの専用芯金大の穴が開いた試験片を作製し、上島製作所製FPS摩耗試験機を用いて、摩耗路面として株式会社ノリタケコーテッドアブレーシブ社製のMETABRIT(粒度240、砥粒A)、試料速度80m/分、荷重40N、タルクフィーダ0.4rpm、設定温度35℃、スリップ率3%の条件で、FPS摩耗量を測定した。表4における各実施例及び比較例の数値は、FPS摩耗量の逆数において比較例4の値を100とした際の相対値である。数値が大きいほど摩耗量が少なく耐摩耗性が良好であることを示す。
実施例及び比較例で作製したゴム組成物のシートから縦40mm×横5mmの試験片を切り出し、GABO社製動的粘弾性測定装置を用いて、測定温度0℃、周波数10Hz、静的歪み10%、動的歪み2%の条件で、tanδを測定し、ウェットグリップの指標とした。表4及び6における各実施例及び比較例の数値は、比較例4の値を100とした際の相対値である。数値が大きいほどゴム組成物のウェットグリップが良好であることを示す。
実施例及び比較例で作製したゴム組成物をプレス成形した加硫ゴムシートからJISダンベル状3号形試験片を打ち抜き、インストロン社製引張試験機を用いて、JIS K 6251に準じて引張破断伸度を測定した。表5における各実施例及び比較例の数値は、比較例5の値を100とした際の相対値である。数値が大きいほど、破断特性が良好であることを示す。
実施例及び比較例で作製したゴム組成物をプレス成形した加硫ゴムシートからJISダンベル状3号形試験片を打ち抜き、インストロン社製引張試験機を用いて、JIS K 6251に準じて引張破断強度を測定した。表5における各実施例及び比較例の数値は、比較例5の値を100とした際の相対値である。数値が大きいほど、破断特性が良好であることを示す。
Claims (15)
- ブタジエン単位を含む重合体ブロック(b'1)および重合体ブロック(b'2)を含有する液状ジエン系ブロック共重合体(B'1)が下記式(1)で表されるシラン化合物により変性された、該式(1)で表されるシラン化合物に由来する官能基を有する変性液状ジエン系重合体(B1)であり、下記(i)~(iv)を満たす、変性液状ジエン系重合体(B1)。
(i)変性液状ジエン系重合体(B1)の重量平均分子量(Mw)が1,000~120,000。
(ii)重合体ブロック(b'1)のブタジエン単位のビニル含量が40~100モル%。
(iii)重合体ブロック(b'2)が、ビニル含量が0~25モル%のブタジエン単位を含む。
(iv)変性液状ジエン系重合体(B1)一分子当たりの平均官能基数が1~20個。
- 変性液状ジエン系重合体(B1)が直鎖状の重合体であり、重合体ブロック(b'1)が液状ジエン系ブロック共重合体(B'1)の片末端または両末端に存在し、重合体ブロック(b'1)の占める長さが液状ジエン系ブロック共重合体(B'1)全鎖長の合計45%以下である、請求項1に記載の変性液状ジエン系重合体(B1)。
- ブタジエン単位を含む重合体ブロック(b"1)および重合体ブロック(b"2)を含有する液状ジエン系ブロック共重合体(B'2)が下記式(1)で表されるシラン化合物により変性された、該式(1)で表されるシラン化合物に由来する官能基を有する変性液状ジエン系重合体(B2)であり、下記(v)~(vii)を満たす、変性液状ジエン系重合体(B2)。
(v)変性液状ジエン系重合体(B2)の重量平均分子量(Mw)が1,000~120,000。
(vi)重合体ブロック(b"2)がブタジエン以外の共役ジエン単位および芳香族ビニル化合物単位からなる群より選ばれる少なくとも1つの単量体単位を含む。
(vii)変性液状ジエン系重合体(B2)一分子当たりの平均官能基数が1~20個。
- 変性液状ジエン系重合体(B2)が直鎖状の重合体であり、液状ジエン系ブロック共重合体(B'2)の重合体ブロック(b"1)が片末端または両末端に存在し、重合体ブロック(b"1)の占める長さが液状ジエン系ブロック共重合体(B'2)全鎖長の合計45%以下である、請求項3に記載の変性液状ジエン系重合体(B2)。
- 変性液状ジエン系重合体(B1)または(B2)が直鎖状の重合体であり、変性液状ジエン系重合体(B1)または(B2)中のシラン化合物に由来する官能基のうち、その65%以上が、片末端または両末端から全鎖長の合計45%の範囲に存在する、請求項1~4のいずれか1項に記載の変性液状ジエン系重合体(B1)または(B2)。
- 38℃における溶融粘度が0.1~4,000Pa・sである、請求項1~5のいずれか1項に記載の変性液状ジエン系重合体(B1)または(B2)。
- 固形ゴム(A)100質量部、請求項1~6のいずれか1項に記載の変性液状ジエン系重合体(B1)または(B2)0.1~50質量部、及びフィラー(C)20~200質量部を含有する、ゴム組成物。
- 前記フィラー(C)が、カーボンブラック及びシリカから選ばれる少なくとも1種である、請求項7に記載のゴム組成物。
- 前記フィラー(C)が、平均粒径5~100nmのカーボンブラック及び平均粒径が0.5~200nmのシリカから選ばれる少なくとも1種である、請求項8に記載のゴム組成物。
- 前記フィラー(C)がシリカを含み、シリカ100質量部に対し、シランカップリング剤を0.1~30質量部含有する、請求項8又は9に記載のゴム組成物。
- 前記固形ゴム(A)が、天然ゴム、スチレンブタジエンゴム、ブタジエンゴム及びイソプレンゴムから選ばれる少なくとも1種である、請求項7~10のいずれか1項に記載のゴム組成物。
- 前記固形ゴム(A)が、重量平均分子量が100,000~2,500,000のスチレンブタジエンゴムである、請求項11に記載のゴム組成物。
- 前記固形ゴム(A)が、スチレン含量が0.1~70質量%であるスチレンブタジエンゴムである、請求項11又は12に記載のゴム組成物。
- 請求項7~13のいずれか1項に記載のゴム組成物を架橋させた架橋物。
- 請求項7~13のいずれか1項に記載のゴム組成物又は請求項14に記載の架橋物を少なくとも一部に用いたタイヤ。
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RU2020131780A RU2788390C2 (ru) | 2018-03-07 | 2019-03-04 | Модифицированный жидкий диеновый полимер и каучуковая композиция |
EP19764978.3A EP3763744A4 (en) | 2018-03-07 | 2019-03-04 | MODIFIED LIQUID SERVICE POLYMER AND RUBBER COMPOSITION |
US16/978,188 US11970561B2 (en) | 2018-03-07 | 2019-03-04 | Modified liquid diene polymer and rubber composition |
CN201980017374.5A CN111801356B (zh) | 2018-03-07 | 2019-03-04 | 改性液体二烯系聚合物和橡胶组合物 |
BR112020017663-0A BR112020017663A2 (pt) | 2018-03-07 | 2019-03-04 | Polímero de dieno líquido modificado e composição de borracha |
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