WO2022138535A1 - Modified liquid diene-based polymer, and method for producing same - Google Patents
Modified liquid diene-based polymer, and method for producing same Download PDFInfo
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- WO2022138535A1 WO2022138535A1 PCT/JP2021/046940 JP2021046940W WO2022138535A1 WO 2022138535 A1 WO2022138535 A1 WO 2022138535A1 JP 2021046940 W JP2021046940 W JP 2021046940W WO 2022138535 A1 WO2022138535 A1 WO 2022138535A1
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- WO
- WIPO (PCT)
- Prior art keywords
- group
- terminal
- polymer
- modified liquid
- liquid diene
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 124
- 150000001993 dienes Chemical class 0.000 title claims abstract description 103
- 239000007788 liquid Substances 0.000 title claims abstract description 101
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 125000000524 functional group Chemical group 0.000 claims abstract description 120
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 36
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 25
- 125000003277 amino group Chemical group 0.000 claims abstract description 25
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 56
- 239000000377 silicon dioxide Substances 0.000 abstract description 28
- 230000000274 adsorptive effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 34
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 125000004122 cyclic group Chemical group 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000011191 terminal modification Methods 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 5
- 239000012039 electrophile Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 150000002900 organolithium compounds Chemical class 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000005103 alkyl silyl group Chemical group 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- -1 ethylene, propylene, butene Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IDVJQEHLTBUQAQ-UHFFFAOYSA-N (2,2-diethoxyazasilolidin-1-yl)-trimethylsilane Chemical compound CCO[Si]1(OCC)CCCN1[Si](C)(C)C IDVJQEHLTBUQAQ-UHFFFAOYSA-N 0.000 description 1
- TUHNTFBFUHRNMN-UHFFFAOYSA-N (2,2-dimethoxyazasilolidin-1-yl)-trimethylsilane Chemical compound CO[Si]1(OC)CCCN1[Si](C)(C)C TUHNTFBFUHRNMN-UHFFFAOYSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- RPFDGUHLVQGZLU-UHFFFAOYSA-N 2,2-dimethoxy-1-phenylazasilolidine Chemical compound CO[Si]1(OC)CCCN1C1=CC=CC=C1 RPFDGUHLVQGZLU-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- PYWOMDDOXZOOJZ-UHFFFAOYSA-N [Li]C1=CC=C([Li])C=C1 Chemical compound [Li]C1=CC=C([Li])C=C1 PYWOMDDOXZOOJZ-UHFFFAOYSA-N 0.000 description 1
- LXXUYORAHKLDLS-UHFFFAOYSA-N [Li]C1CCC([Li])C(CC)C1 Chemical compound [Li]C1CCC([Li])C(CC)C1 LXXUYORAHKLDLS-UHFFFAOYSA-N 0.000 description 1
- QWFRFVPEFDDMQD-UHFFFAOYSA-N [Li]CCCCCCCCCC[Li] Chemical compound [Li]CCCCCCCCCC[Li] QWFRFVPEFDDMQD-UHFFFAOYSA-N 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- ARCHVGRSBFXDTP-UHFFFAOYSA-N [Li]c1cc([Li])cc([Li])c1 Chemical compound [Li]c1cc([Li])cc([Li])c1 ARCHVGRSBFXDTP-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000006365 alkylene oxy carbonyl group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZEFNMRMJJKIGBT-UHFFFAOYSA-N dilithium;pentane Chemical compound [Li+].[Li+].[CH2-]CCC[CH2-] ZEFNMRMJJKIGBT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- WTTUTKBXMMXKBQ-UHFFFAOYSA-N lithium;stilbene Chemical compound C=1C=CC=CC=1C([Li])C([Li])C1=CC=CC=C1 WTTUTKBXMMXKBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 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
Definitions
- the present invention relates to a modified liquid diene polymer and a method for producing the same.
- Patent Document 1 a diene-based polymer having an adsorptivity to silica (silica adsorptivity) has been proposed (for example, Patent Document 1).
- the present inventors have found that the above-mentioned problems can be solved by a diene-based polymer having a specific functional group at both the terminal and the main chain, and have reached the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
- a modified liquid diene polymer which is a liquid diene polymer.
- the modified liquid diene-based polymer according to (1) or (2) above which has a weight average molecular weight of 1,000 to 100,000.
- the number of functional groups represents the total of the average number of the functional groups A at the terminal per molecule and the average number of the functional groups B at the main chain per molecule.
- a terminal-modified liquid diene-based polymer which is a liquid diene-based polymer having at least one functional group A and Radical initiator and By reacting with a compound represented by the formula (2) described later, the functional group B represented by the above formula (1) is introduced into the main chain of the terminal-modified liquid diene polymer, and the above (1)
- a method for producing a modified liquid diene polymer which comprises the modified liquid diene polymer according to any one of (4) to (4).
- the modified liquid diene polymer of the present invention and a method for producing the same will be described.
- the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- each component may be used alone or in combination of two or more.
- the amount of the component means the total amount unless otherwise specified.
- the hydrocarbon group alkyl group, alkylene group, alkyl group in alkoxy group, etc.
- the hydrocarbon group may have a hetero atom, and its shape (linear, branched, cyclic) may be. Not particularly limited.
- the modified liquid diene-based polymer of the present invention (hereinafter, also referred to as “polymer of the present invention”) is At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. It has one functional group A and The main chain has a functional group B represented by the formula (1) described later. It is a liquid diene polymer.
- the polymer of the present invention has a specific functional group at both the terminal and the main chain. From the studies of the present inventors, such a polymer of the present invention has extremely high silica adsorptivity as compared with a diene-based polymer having a specific functional group at either the terminal or the main chain. Has been found. That is, the polymer of the present invention is not a mere addition of a diene-based polymer having a specific functional group only at the terminal and a diene-based polymer having a specific functional group only at the main chain, but a terminal functional group.
- the skeleton (main chain structure) of the polymer of the present invention is not particularly limited as long as it is a diene-based polymer.
- the diene-based polymer is a polymer of a monomer containing a diene.
- the diene-based polymer may be a homopolymer or a copolymer, but is preferably a homopolymer for the reason that the effect of the present invention is more excellent.
- the diene examples include butadiene, isoprene, chloroprene and the like.
- the diene is preferably butadiene because the effect of the present invention is more excellent.
- the monomer other than the diene is not particularly limited, and examples thereof include aromatic vinyl (preferably styrene), acrylonitrile, ethylene, propylene, butene (preferably isobutylene) and the like.
- aromatic vinyl is preferable, and styrene is more preferable, because the effect of the present invention is more excellent.
- the content of diene in the above-mentioned monomer is not particularly limited, but for the reason that the effect of the present invention is more excellent, it is preferably 10% by mass or more, more preferably 50% by mass or more, and 90% by mass or more. It is more preferable to have.
- the content of diene in the monomer is not particularly limited and is 100% by mass.
- the diene polymer examples include a butadiene polymer (BR), an isoprene polymer (IR), a chloroprene polymer (CR), an isoprene butadiene copolymer (IBR), and a butadiene styrene copolymer (SBR).
- BR butadiene polymer
- IR isoprene polymer
- CR chloroprene polymer
- IBR isoprene butadiene copolymer
- SBR butadiene styrene copolymer
- NBR acrylonitrile-butadiene copolymer
- isoprene isoprene copolymer examples include acrylonitrile-butadiene copolymer (NBR) and isoprene isoprene copolymer.
- the diene-based polymer is preferably a polymer of a monomer containing at least one selected from the group consisting of butadiene and isoprene because the effect of the present invention is more excellent, and the weight of the monomer containing butadiene is preferable. It is more preferably a coalescence, and even more preferably a butadiene polymer.
- the polymer of the present invention represents an amino group (-NR 2 : R is a hydrogen atom or a substituent (particularly a hydrocarbon group having 1 to 10 carbon atoms) at the terminal, and the two Rs are different even if they are the same. (May be), hydroxyl group (-OH), carboxy group (-COOH), alkoxysilyl group (-Si (R 1 ) m (R 2 ) n : R 1 represents an alkoxy group (particularly 1 to 10 carbon atoms).
- R 2 represents a hydrogen atom or a substituent (particularly a hydrocarbon group having 1 to 10 carbon atoms), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n is 3.
- a plurality of R 1s when m is an integer of 2 or more may be the same or different, and two R 2s when n is 2 may be the same or different).
- the polymer of the present invention may have a functional group A at only one end or a functional group A at a plurality of ends, but for the reason that the effect of the present invention is more excellent, only one end is used. It is preferable to have a functional group A.
- the functional group A is preferably an amino group, an alkoxysilyl group, or an alkoxysilyl group having an amino group, and more preferably an alkoxysilyl group having an amino group, for the reason that the effect of the present invention is more excellent.
- the functional group A is preferably a group derived from cyclic silazane, and more preferably a group represented by the following formula (M), for the reason that the effect of the present invention is more excellent.
- R 1 and R 2 each independently represent a hydrogen atom or a substituent.
- L represents a divalent organic group.
- R 1 and R 2 each independently represent a hydrogen atom or a substituent.
- the above substituent is not particularly limited as long as it is a monovalent substituent, but for example, a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, an acyl group, an imide group, a phosphino group and a phosphinyl. Examples thereof include a group, a silyl group, a hydrocarbon group which may have a hetero atom, and the like.
- Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the heteroatom of the hydrocarbon group which may have the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.
- Examples of the hydrocarbon group which may have the heteroatom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined.
- the aliphatic hydrocarbon group may be linear, branched or cyclic.
- the aliphatic hydrocarbon group examples include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), and the like. Examples thereof include a linear or branched alkynyl group (particularly, 2 to 30 carbon atoms).
- the aromatic hydrocarbon group examples include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
- R 1 has a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), and an alkylsilyl group (preferably 1 to 10 carbon atoms) because the effect of the present invention is more excellent. , It is preferably an aromatic hydrocarbon group (preferably 6 to 18 carbon atoms), and more preferably a hydrogen atom.
- the plurality of R 1s may be the same or different.
- R 2 is preferably a hydrocarbyloxy group (-OR group: R is a hydrocarbon group) and an alkoxy group (preferably having 1 carbon atom) because the effect of the present invention is more excellent. ⁇ 10) is more preferable.
- L represents a single bond or a divalent organic group.
- the divalent organic group include an aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 10 carbon atoms), an aromatic hydrocarbon group (for example, an arylene group, preferably 6 to 18 carbon atoms), and the like.
- Alkyleneoxy group (-Cm H 2m O-: m is a positive integer), alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.) and the like.
- L is preferably an alkylene group (preferably 1 to 10 carbon atoms) because the effect of the present invention is more excellent.
- n represents an integer of 0 to 2. n is preferably 2 because the effect of the present invention is more excellent.
- m represents an integer of 1 to 3. m is preferably 1 for the reason that the effect of the present invention is more excellent.
- the number of terminal functional groups of the polymer of the present invention is preferably 0.1 to 2, more preferably 0.5 to 1, and further preferably 1 for the reason that the effect of the present invention is more excellent. preferable.
- the number of terminal functional groups represents the number of functional groups A having at the terminal (average number per molecule).
- the polymer of the present invention has a functional group B represented by the following formula (1) in the main chain.
- R 1 represents an alkylene group having 1 to 10 carbon atoms
- R 2 , R 3 and R 4 independently represent an alkoxy group having 1 to 10 carbon atoms
- * represents a bond. Represents a position.
- R 1 represents an alkylene group having 1 to 10 carbon atoms.
- the above R 1 is preferably an alkylene group having 2 to 5 carbon atoms because the effect of the present invention is more excellent.
- R 2 , R 3 and R 4 each independently represent an alkoxy group having 1 to 10 carbon atoms. It is preferable that R 2 , R 3 and R 4 are independently alkoxy groups having 1 to 5 carbon atoms, respectively, for the reason that the effect of the present invention is more excellent.
- the number of main chain functional groups of the polymer of the present invention is preferably 0.1 to 100, more preferably 1 to 20, and preferably 2 to 10 for the reason that the effect of the present invention is more excellent. More preferred.
- the number of functional groups in the main chain represents the number of functional groups B in the main chain (the average number per molecule).
- the number of functional groups of the polymer of the present invention is preferably 0.1 to 100, more preferably 1 to 20, and even more preferably 2 to 10 because the effect of the present invention is more excellent. ..
- the number of functional groups represents the total of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). ..
- the ratio of the above-mentioned number of main chain functional groups to the above-mentioned number of terminal functional groups may be 1 to 10 for the reason that the effect of the present invention is more excellent. It is preferably 2 to 5, and more preferably 2 to 5.
- the weight average molecular weight (Mw) of the polymer of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 80,000 because the effect of the present invention is more excellent. It is more preferably 20,000 to 50,000.
- the number average molecular weight of the polymer of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 80,000, and more preferably 20, It is more preferably 000 to 50,000.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are standard polystyrene-equivalent values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
- GPC gel permeation chromatography
- the polymer of the present invention is liquid at 20 ° C. and 1 atm.
- the method for producing the polymer of the present invention is not particularly limited, but the obtained polymer of the present invention has more excellent silica adsorptivity. At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal.
- a terminal-modified liquid diene polymer which is a liquid diene polymer having one kind of functional group A, and a terminal-modified liquid diene polymer.
- the functional group B represented by the formula (1) described above is introduced into the main chain of the terminal-modified liquid diene polymer, and the present invention
- a method for obtaining a polymer (hereinafter, also referred to as “production method 1”) is preferable.
- production method 1 a hydrogen atom is extracted from the ⁇ carbon atom of the double bond of the terminal-modified liquid diene polymer by a radical initiator, and the compound represented by the formula (2) reacts there with the terminal.
- the functional group B represented by the formula (1) is introduced into the main chain of the modified liquid diene polymer.
- the reaction of the above-mentioned production method 1 is preferably carried out in bulk or in an organic solvent because the obtained polymer of the present invention has more excellent silica adsorptivity.
- the obtained polymer of the present invention having better silica adsorptivity is also referred to as “the effect of the present invention is more excellent”.
- the terminal-modified liquid diene-based polymer has an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group at the terminal, an aldehyde group, an epoxy group, a nitro group, and an amino.
- the definition, specific examples and preferred embodiments of the skeleton and the functional group A are the same as those of the polymer of the present invention described above.
- radical initiator is not particularly limited, and specific examples thereof include benzoyl peroxide, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide, 2,5.
- the amount of the radical initiator added is not particularly limited, but is preferably 0.1 to 10% by mass with respect to the terminal-modified liquid diene polymer described above for the reason that the effect of the present invention is more excellent. More preferably, it is ⁇ 5% by mass.
- R 1 represents an alkylene group having 1 to 10 carbon atoms
- R 2 , R 3 and R 4 independently represent an alkoxy group having 1 to 10 carbon atoms.
- R 1 , R 2 , R 3 and R 4 in the formula (2) are the same as those in the above formula (1).
- Specific examples of the compound represented by the above formula (2) include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
- the amount of the compound represented by the above formula (2) to be added is not particularly limited, but is 1 to 50% by mass with respect to the above-mentioned terminal-modified liquid diene polymer for the reason that the effect of the present invention is more excellent. It is preferable, and it is more preferable that it is 1 to 10% by mass.
- the manufacturing method 1 is preferably a method including the following steps (1) to (3) (hereinafter, also referred to as “manufacturing method 2”) because the effect of the present invention is more excellent.
- a functional group A derived from the specific electrophoretic agent is introduced into the terminal of the liquid diene polymer, and the terminal-modified liquid which is a liquid diene polymer having the functional group A at the end is a terminal-modified liquid.
- Step for obtaining a diene polymer (3) Main chain modification step The terminal modification is carried out by reacting the terminal-modified liquid diene polymer with a radical initiator and the compound represented by the above formula (2).
- a liquid diene polymer having the functional group B represented by the above formula (1) introduced into the main chain of the liquid diene polymer, having the functional group A at the terminal and having the functional group B in the main chain.
- the monomer polymerization step is a step of polymerizing a monomer containing a diene using an organolithium compound to obtain a liquid diene-based polymer having an active terminal.
- the diene is preferably a conjugated diene because the effect of the present invention is more excellent, and specific examples and suitable embodiments thereof are the diene system of the skeleton of the polymer of the present invention described above. Same as polymer. Further, regarding the above-mentioned monomer containing diene, specific examples and suitable embodiments of the monomer other than diene are the same as those of the above-mentioned diene-based polymer having the skeleton of the polymer of the present invention.
- organolithium compound The above-mentioned organolithium compound is not particularly limited, and specific examples thereof include monoorganolithium compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, and benzyllithium; 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4-dilithio Benzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-trilithio-2,4,6- Examples thereof include poly
- monoorganolithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium are preferable, and n-butyllithium is more preferable, because the effect of the present invention is more excellent.
- the amount of the organic lithium compound used is not particularly limited, but it is preferably 0.001 to 10 mol% with respect to the above-mentioned monomer for the reason that the effect of the present invention is more excellent.
- the polymerization of the above-mentioned monomer is stopped by using a specific electrophoretic agent, so that the end of the above-mentioned liquid diene-based polymer (liquid diene-based polymer having an active end) is formed.
- This is a step of introducing a functional group A derived from the specific electrophoretic agent to obtain a terminal-modified liquid diene polymer which is a liquid diene polymer having the functional group A at the terminal.
- the specific electrophile (hereinafter, also referred to as "specific electrophile”) is a compound that becomes a functional group A by reacting with the active terminal of a liquid diene polymer.
- the specific electropoxide is an amine
- the functional group A is an amino group
- the specific electropoxide is a ketone
- the functional group A is a hydroxyl group
- the specific electropoxide is an acetal.
- the functional group A becomes a carboxy group (however, hydrolysis is required after reacting with the active terminal of the liquid diene polymer)
- the specific electrophilic agent is an alkoxysilane
- the functional group A is an alkoxysilyl.
- the functional group A becomes an aldehyde group
- the specific electrophoretic agent is an epoxide
- the functional group A becomes an epoxy group and the specific electrophoretic agent is an amino.
- the functional group A becomes an alkoxysilyl group having an amino group.
- the specific electrophilic agent is cyclic silazane
- the functional group A becomes an amino group
- the cyclic silazane has an alkoxysilyl group
- the functional group A becomes an alkoxysilyl group having an amino group.
- the specific electrophile is preferably cyclic silazan for the reason that the effect of the present invention is more excellent.
- the cyclic silazane is preferably a compound represented by the following formula (S) because the effect of the present invention is more excellent.
- R 1 to R 3 independently represent a hydrogen atom or a substituent. Specific examples and preferred embodiments of the substituent are the same as those of R 1 and R 2 in the above-mentioned formula (M).
- L represents a divalent organic group. Specific examples and preferred embodiments of the divalent organic group are the same as L in the above-mentioned formula (M).
- R 1 has an alkyl group (preferably 1 to 10 carbon atoms), an alkylsilyl group (preferably 1 to 10 carbon atoms), and an aromatic group because the effect of the present invention is more excellent. It is preferably a hydrocarbon group (preferably 6 to 18 carbon atoms), and more preferably an alkylsilyl group.
- R 2 and R 3 are preferably hydrocarbyloxy groups (-OR group: R is a hydrocarbon group) independently of each other, and are preferably alkoxy groups, for the reason that the effect of the present invention is more excellent. (Preferably, the number of carbon atoms is 1 to 10).
- L is preferably an alkylene group (preferably 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 3 to 5 carbon atoms) because the effect of the present invention is more excellent. ..
- Examples of the compound represented by the above formula (S) include Nn-butyl-1,1-dimethoxy-2-azasilacyclopentane and N-phenyl-1,1-dimethoxy-2-azasilacyclopentane. , N-trimethylsilyl-1,1-dimethoxy-2-azasilacyclopentane, N-trimethylsilyl-1,1-diethoxy-2-azasilacyclopentane and the like.
- the silicon atom of cyclic silazane is considered to exhibit electrophilicity.
- the amount of the specific electrophile with respect to the organolithium compound is not particularly limited, but for the reason that the effect of the present invention is more excellent, the molar ratio is preferably 0.1 to 10 and more preferably 1 to 5. preferable.
- the main chain of the terminal-modified liquid diene polymer is formed by reacting the terminal-modified liquid diene polymer with the radical initiator and the compound represented by the above formula (2).
- a modified liquid diene polymer which is a liquid diene polymer having the functional group A at the terminal and the functional group B in the backbone is introduced into the above-mentioned functional group B represented by the formula (1). This is the process of obtaining.
- the main chain modification step is the same as the above-mentioned production method 1.
- the polymer of the present invention is useful for rubber compositions, tires and the like.
- a modified liquid diene polymer was produced as follows. Since Examples 1 and 2 are liquid diene-based polymers having a functional group A at the terminal and a functional group B in the main chain, they fall under the polymer of the present invention. On the other hand, Comparative Example 1 does not have a functional group A at the terminal, and therefore does not correspond to the polymer of the present invention. Further, Comparative Examples 2 to 5 do not correspond to the polymer of the present invention because they do not have a functional group B in the main chain.
- Example 1 As described below, the modified liquid diene polymer of Example 1 was produced.
- An average of two functional groups B represented by the above formula (1) per molecule (however, in formula (1), R 1 is a propylene group and R 2 , R 3 and R 4 are ethoxy groups. ) was obtained as a modified liquid butadiene polymer (Mw: 40,000). In the obtained modified liquid butadiene polymer, the sum of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). was 3.
- Example 2 A modified liquid butadiene polymer was produced according to the same procedure as in Example 1 except that the amount of 3-mercaptopropyltriethoxysilane added was changed to 7.4 g in the backbone modification step.
- the obtained modified liquid butadiene polymer has a functional group (functional group A) represented by the above formula (m1) at one end, and has an average of 4 above-mentioned formulas (1) per molecule in the main chain.
- Modified liquid butadiene weight which is a liquid butadiene polymer having a functional group B represented by (where R 1 is a propylene group and R 2 , R 3 and R 4 are ethoxy groups in the formula (1)). It was a coalescence (Mw: 40,000).
- the sum of the number of functional groups A at the terminal average number per molecule
- the number of functional groups B in the main chain average number per molecule.
- modified liquid butadiene polymer was produced according to the same procedure as in Example 2 except that methanol was used instead of cyclic silazane in the terminal modification step.
- the obtained modified liquid butadiene copolymer has no functional group at the terminal and has an average of 4 functional groups B per molecule per molecule in the main chain represented by the above-mentioned formula (1) (however, the formula (1)).
- R 1 is a propylene group
- R 2 , R 3 and R 4 are ethoxy groups
- Mw main chain modified liquid butadiene polymer
- modified liquid butadiene copolymer was produced according to the same procedure as in Example 1 except that the main chain modification step was not performed.
- the obtained modified liquid butadiene polymer is a liquid butadiene polymer having a functional group (functional group A) represented by the above formula (m1) at one end and no functional group B in the main chain. It was a modified liquid butadiene polymer (terminal modified liquid butadiene polymer) (Mw: 40,000).
- the obtained modified liquid isoprene butadiene copolymer has a functional group (functional group A) represented by the above formula (m1) at one end thereof and does not have a functional group B in the main chain. It was a modified liquid isoprene butadiene copolymer (terminal-modified liquid isoprene butadiene copolymer) (Mw: 40,000) which is a polymer (random copolymer).
- ⁇ Comparative Example 4> Add 560 mL of 1,3-butadiene, 30 mL of n-butyllithium, and 0.1 mL of 2,2-di (2-tetrahydrofuryl) propane to 4.2 kg of cyclohexane, heat and stir (60 ° C., 12 hours), and then isoprene.
- a liquid isoprene butadiene copolymer (block copolymer) having an active terminal was obtained by adding 650 ml and heating and stirring (60 ° C., 12 hours). Then, a terminal modification step was carried out according to the same procedure of Example 1 to obtain a modified liquid isoprene butadiene copolymer.
- the obtained modified liquid isoprene butadiene copolymer has a functional group (functional group A) represented by the above formula (m1) at one end thereof and does not have a functional group B in the main chain. It was a modified liquid isoprene butadiene copolymer (terminal-modified liquid isoprene butadiene copolymer) (Mw: 40,000) which is a polymer (block copolymer).
- the number of main chain functional groups represents the number of functional groups B in the main chain (average number per molecule) for each modified liquid diene polymer.
- Examples 1 and 2 having a functional group A at the terminal and a functional group B in the main chain showed excellent silica adsorptivity.
- Examples in which the total of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule) is 4 or more. 2 showed better silica adsorptivity.
Abstract
The present invention addresses the problem of providing: a diene-based polymer having excellent adsorptive properties onto silica; and a method for producing the diene-based polymer. A modified liquid diene-based polymer according to the present invention has at least one functional group A selected from the group consisting of an amino group, a hydroxyl group, a carboxyl group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group and an alkoxysilyl group having an amino group at a terminal thereof and also has a functional group B represented by formula (1) in the main chain thereof. In formula (1), R1 represents an alkylene group having 1 to 10 carbon atoms; R2, R3 and R4 independently represent an alkoxy group having 1 to 10 carbon atoms; and * represents a binding position.
Description
本発明は、変性液状ジエン系重合体及びその製造方法に関する。
The present invention relates to a modified liquid diene polymer and a method for producing the same.
従来、シリカへの吸着性（シリカ吸着性）を有するジエン系重合体が提案されている（例えば、特許文献１）。
Conventionally, a diene-based polymer having an adsorptivity to silica (silica adsorptivity) has been proposed (for example, Patent Document 1).
このようななか、本発明者らが特許文献１に記載のジエン系重合体について検討したところ、様々な用途への応用を考えると、シリカ吸着性のさらなる向上が望ましいことが明らかになった。
Under these circumstances, when the present inventors examined the diene-based polymer described in Patent Document 1, it became clear that further improvement in silica adsorptivity is desirable in consideration of application to various uses.
そこで、本発明は、上記実情を鑑みて、シリカ吸着性に優れるジエン系重合体、及び、その製造方法を提供することを目的とする。
Therefore, in view of the above circumstances, it is an object of the present invention to provide a diene-based polymer having excellent silica adsorptivity and a method for producing the same.
本発明者らは、上記課題について鋭意検討した結果、末端と主鎖の両方に特定の官能基を有するジエン系重合体によって上記課題が解決できることを見出し、本発明に至った。
すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of diligent studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a diene-based polymer having a specific functional group at both the terminal and the main chain, and have reached the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.
すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of diligent studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a diene-based polymer having a specific functional group at both the terminal and the main chain, and have reached the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.
（１） 末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有し、
主鎖に、後述する式（１）で表される官能基Ｂを有する、
液状ジエン系重合体である、変性液状ジエン系重合体。
（２） 上記液状ジエン系重合体が、ブタジエン及びイソプレンからなる群より選択される少なくとも１種を含有するモノマーの重合体である、上記（１）に記載の変性液状ジエン系重合体。
（３） 重量平均分子量が、１，０００～１００，０００である、上記（１）又は（２）に記載の変性液状ジエン系重合体。
（４） 官能基数が、２～１０である、上記（１）～（３）のいずれかに記載の変性液状ジエン系重合体。ここで、上記官能基数は、末端に有する上記官能基Ａの１分子あたりの平均の数と、主鎖に有する上記官能基Ｂの１分子あたりの平均の数との合計を表す。
（５） 末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体と、
ラジカル開始剤と、
後述する式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上記式（１）で表される官能基Ｂを導入し、上記（１）～（４）のいずれかに記載の変性液状ジエン系重合体を得る、変性液状ジエン系重合体の製造方法。 (1) Select from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. Has at least one functional group A to be
The main chain has a functional group B represented by the formula (1) described later.
A modified liquid diene polymer, which is a liquid diene polymer.
(2) The modified liquid diene polymer according to (1) above, wherein the liquid diene polymer is a polymer of a monomer containing at least one selected from the group consisting of butadiene and isoprene.
(3) The modified liquid diene-based polymer according to (1) or (2) above, which has a weight average molecular weight of 1,000 to 100,000.
(4) The modified liquid diene-based polymer according to any one of (1) to (3) above, wherein the number of functional groups is 2 to 10. Here, the number of functional groups represents the total of the average number of the functional groups A at the terminal per molecule and the average number of the functional groups B at the main chain per molecule.
(5) Select from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. A terminal-modified liquid diene-based polymer which is a liquid diene-based polymer having at least one functional group A and
Radical initiator and
By reacting with a compound represented by the formula (2) described later, the functional group B represented by the above formula (1) is introduced into the main chain of the terminal-modified liquid diene polymer, and the above (1) A method for producing a modified liquid diene polymer, which comprises the modified liquid diene polymer according to any one of (4) to (4).
主鎖に、後述する式（１）で表される官能基Ｂを有する、
液状ジエン系重合体である、変性液状ジエン系重合体。
（２） 上記液状ジエン系重合体が、ブタジエン及びイソプレンからなる群より選択される少なくとも１種を含有するモノマーの重合体である、上記（１）に記載の変性液状ジエン系重合体。
（３） 重量平均分子量が、１，０００～１００，０００である、上記（１）又は（２）に記載の変性液状ジエン系重合体。
（４） 官能基数が、２～１０である、上記（１）～（３）のいずれかに記載の変性液状ジエン系重合体。ここで、上記官能基数は、末端に有する上記官能基Ａの１分子あたりの平均の数と、主鎖に有する上記官能基Ｂの１分子あたりの平均の数との合計を表す。
（５） 末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体と、
ラジカル開始剤と、
後述する式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上記式（１）で表される官能基Ｂを導入し、上記（１）～（４）のいずれかに記載の変性液状ジエン系重合体を得る、変性液状ジエン系重合体の製造方法。 (1) Select from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. Has at least one functional group A to be
The main chain has a functional group B represented by the formula (1) described later.
A modified liquid diene polymer, which is a liquid diene polymer.
(2) The modified liquid diene polymer according to (1) above, wherein the liquid diene polymer is a polymer of a monomer containing at least one selected from the group consisting of butadiene and isoprene.
(3) The modified liquid diene-based polymer according to (1) or (2) above, which has a weight average molecular weight of 1,000 to 100,000.
(4) The modified liquid diene-based polymer according to any one of (1) to (3) above, wherein the number of functional groups is 2 to 10. Here, the number of functional groups represents the total of the average number of the functional groups A at the terminal per molecule and the average number of the functional groups B at the main chain per molecule.
(5) Select from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. A terminal-modified liquid diene-based polymer which is a liquid diene-based polymer having at least one functional group A and
Radical initiator and
By reacting with a compound represented by the formula (2) described later, the functional group B represented by the above formula (1) is introduced into the main chain of the terminal-modified liquid diene polymer, and the above (1) A method for producing a modified liquid diene polymer, which comprises the modified liquid diene polymer according to any one of (4) to (4).
以下に示すように、本発明によれば、シリカ吸着性に優れるジエン系重合体、及び、その製造方法を提供することができる。
As shown below, according to the present invention, it is possible to provide a diene-based polymer having excellent silica adsorptivity and a method for producing the same.
以下、本発明の変性液状ジエン系重合体、及び、その製造方法について説明する。
なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
また、本明細書において、各成分は、１種を単独で用いても、２種以上を併用してもよい。ここで、各成分について２種以上を併用する場合、その成分について量とは、特段の断りが無い限り、合計の量を指す。
また、本明細書において、炭化水素基（アルキル基、アルキレン基、アルコキシ基中のアルキル基等）は、ヘテロ原子を有していてもよく、その形状（直鎖状、分岐状、環状）は特に限定されない。 Hereinafter, the modified liquid diene polymer of the present invention and a method for producing the same will be described.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, each component may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the amount of the component means the total amount unless otherwise specified.
Further, in the present specification, the hydrocarbon group (alkyl group, alkylene group, alkyl group in alkoxy group, etc.) may have a hetero atom, and its shape (linear, branched, cyclic) may be. Not particularly limited.
なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
また、本明細書において、各成分は、１種を単独で用いても、２種以上を併用してもよい。ここで、各成分について２種以上を併用する場合、その成分について量とは、特段の断りが無い限り、合計の量を指す。
また、本明細書において、炭化水素基（アルキル基、アルキレン基、アルコキシ基中のアルキル基等）は、ヘテロ原子を有していてもよく、その形状（直鎖状、分岐状、環状）は特に限定されない。 Hereinafter, the modified liquid diene polymer of the present invention and a method for producing the same will be described.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, each component may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the amount of the component means the total amount unless otherwise specified.
Further, in the present specification, the hydrocarbon group (alkyl group, alkylene group, alkyl group in alkoxy group, etc.) may have a hetero atom, and its shape (linear, branched, cyclic) may be. Not particularly limited.
［変性液状ジエン系重合体］
本発明の変性液状ジエン系重合体（以下、「本発明の重合体」とも言う）は、
末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有し、
主鎖に、後述する式（１）で表される官能基Ｂを有する、
液状ジエン系重合体である。 [Modified liquid diene polymer]
The modified liquid diene-based polymer of the present invention (hereinafter, also referred to as “polymer of the present invention”) is
At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. It has one functional group A and
The main chain has a functional group B represented by the formula (1) described later.
It is a liquid diene polymer.
本発明の変性液状ジエン系重合体（以下、「本発明の重合体」とも言う）は、
末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有し、
主鎖に、後述する式（１）で表される官能基Ｂを有する、
液状ジエン系重合体である。 [Modified liquid diene polymer]
The modified liquid diene-based polymer of the present invention (hereinafter, also referred to as “polymer of the present invention”) is
At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. It has one functional group A and
The main chain has a functional group B represented by the formula (1) described later.
It is a liquid diene polymer.
本発明の重合体は、上述のとおり、末端及び主鎖の両方に特定の官能基を有する。本発明者らの検討から、このような本発明の重合体は、末端及び主鎖のどちらか一方のみに特定の官能基を有するジエン系重合体と比較して、シリカ吸着性が極めて高いことが知見されている。すなわち、本発明の重合体は、末端のみに特定の官能基を有するジエン系重合体と主鎖のみに特定の官能基を有するジエン系重合体との単なる足し合わせではなく、末端の官能基のシリカ吸着性と主鎖の官能基のシリカ吸着性との相乗的な効果により、極めて高いシリカ吸着性を示す。このことは、後述する表１にも具体的に示されている。すなわち、比較例１～２及び実施例１～２（いずれもＭｗが４０，０００）を対比すると、主鎖のみに官能基を有する比較例１はシリカ吸着性が８であり、末端のみに官能基を有する比較例２はシリカ吸着性が１５であるのに対して、末端及び主鎖の両方に官能基を有する実施例１～２のシリカ吸着性は５０を超え、単なる足し合わせを超える極めて高いシリカ吸着性を示す。その理由は明らかではないが、末端及び主鎖の両方に特定の官能基を有する場合、末端及び主鎖の両方がシリカと相互作用するため、ジエン系重合体の運動性が大幅に抑制され、ジエン系重合体とシリカとの結合がより強固になるためと考えられる。
As described above, the polymer of the present invention has a specific functional group at both the terminal and the main chain. From the studies of the present inventors, such a polymer of the present invention has extremely high silica adsorptivity as compared with a diene-based polymer having a specific functional group at either the terminal or the main chain. Has been found. That is, the polymer of the present invention is not a mere addition of a diene-based polymer having a specific functional group only at the terminal and a diene-based polymer having a specific functional group only at the main chain, but a terminal functional group. Due to the synergistic effect of the silica adsorptivity and the silica adsorptivity of the functional group of the main chain, it exhibits extremely high silica adsorptivity. This is specifically shown in Table 1 described later. That is, when Comparative Examples 1 and 2 and Examples 1 and 2 (both having a Mw of 40,000) are compared, Comparative Example 1 having a functional group only in the main chain has a silica adsorptivity of 8 and is functional only at the terminal. Comparative Example 2 having a group has a silica adsorptivity of 15, whereas the silica adsorptivity of Examples 1 and 2 having a functional group at both the terminal and the main chain exceeds 50, which is much more than mere addition. Shows high silica adsorption. The reason is not clear, but when both the terminal and the main chain have specific functional groups, both the terminal and the main chain interact with silica, so that the motility of the diene polymer is greatly suppressed. It is considered that the bond between the diene polymer and silica becomes stronger.
以下、本発明の重合体について詳述する。
Hereinafter, the polymer of the present invention will be described in detail.
〔骨格〕
本発明の重合体の骨格（主鎖構造）は、ジエン系重合体であれば特に制限されない。
ジエン系重合体とは、ジエンを含有するモノマーの重合体である。ジエン系重合体は、単独重合体（ホモポリマー）であっても、共重合体（コポリマー）であってもよいが、本発明の効果がより優れる理由から、単独重合体であることが好ましい。 [Skeleton]
The skeleton (main chain structure) of the polymer of the present invention is not particularly limited as long as it is a diene-based polymer.
The diene-based polymer is a polymer of a monomer containing a diene. The diene-based polymer may be a homopolymer or a copolymer, but is preferably a homopolymer for the reason that the effect of the present invention is more excellent.
本発明の重合体の骨格（主鎖構造）は、ジエン系重合体であれば特に制限されない。
ジエン系重合体とは、ジエンを含有するモノマーの重合体である。ジエン系重合体は、単独重合体（ホモポリマー）であっても、共重合体（コポリマー）であってもよいが、本発明の効果がより優れる理由から、単独重合体であることが好ましい。 [Skeleton]
The skeleton (main chain structure) of the polymer of the present invention is not particularly limited as long as it is a diene-based polymer.
The diene-based polymer is a polymer of a monomer containing a diene. The diene-based polymer may be a homopolymer or a copolymer, but is preferably a homopolymer for the reason that the effect of the present invention is more excellent.
上記ジエンの具体例としては、ブタジエン、イソプレン、クロロプレン等が挙げられる。上記ジエンは、本発明の効果がより優れる理由から、ブタジエンであることが好ましい。
上記ジエン以外のモノマーとしては特に制限されないが、芳香族ビニル（好ましくは、スチレン）、アクリロニトリル、エチレン、プロピレン、ブテン（好ましくは、イソブチレン）等が挙げられる。上記ジエン以外のモノマーは、本発明の効果がより優れる理由から、芳香族ビニルが好ましく、スチレンがより好ましい。
上記モノマー中のジエンの含有量は特に制限されないが、本発明の効果がより優れる理由から、１０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。モノマー中のジエンの含有量は特に制限されず、１００質量％である。 Specific examples of the diene include butadiene, isoprene, chloroprene and the like. The diene is preferably butadiene because the effect of the present invention is more excellent.
The monomer other than the diene is not particularly limited, and examples thereof include aromatic vinyl (preferably styrene), acrylonitrile, ethylene, propylene, butene (preferably isobutylene) and the like. As the monomer other than the diene, aromatic vinyl is preferable, and styrene is more preferable, because the effect of the present invention is more excellent.
The content of diene in the above-mentioned monomer is not particularly limited, but for the reason that the effect of the present invention is more excellent, it is preferably 10% by mass or more, more preferably 50% by mass or more, and 90% by mass or more. It is more preferable to have. The content of diene in the monomer is not particularly limited and is 100% by mass.
上記ジエン以外のモノマーとしては特に制限されないが、芳香族ビニル（好ましくは、スチレン）、アクリロニトリル、エチレン、プロピレン、ブテン（好ましくは、イソブチレン）等が挙げられる。上記ジエン以外のモノマーは、本発明の効果がより優れる理由から、芳香族ビニルが好ましく、スチレンがより好ましい。
上記モノマー中のジエンの含有量は特に制限されないが、本発明の効果がより優れる理由から、１０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。モノマー中のジエンの含有量は特に制限されず、１００質量％である。 Specific examples of the diene include butadiene, isoprene, chloroprene and the like. The diene is preferably butadiene because the effect of the present invention is more excellent.
The monomer other than the diene is not particularly limited, and examples thereof include aromatic vinyl (preferably styrene), acrylonitrile, ethylene, propylene, butene (preferably isobutylene) and the like. As the monomer other than the diene, aromatic vinyl is preferable, and styrene is more preferable, because the effect of the present invention is more excellent.
The content of diene in the above-mentioned monomer is not particularly limited, but for the reason that the effect of the present invention is more excellent, it is preferably 10% by mass or more, more preferably 50% by mass or more, and 90% by mass or more. It is more preferable to have. The content of diene in the monomer is not particularly limited and is 100% by mass.
上記ジエン系重合体の具体例としては、ブタジエン重合体（ＢＲ）、イソプレン重合体（ＩＲ）、クロロプレン重合体（ＣＲ）、イソプレンブタジエン共重合体（ＩＢＲ）、ブタジエンスチレン共重合体（ＳＢＲ）、アクリロニトリルブタジエン共重合体（ＮＢＲ）、イソブチレンイソプレン共重合体等が挙げられる。
Specific examples of the diene polymer include a butadiene polymer (BR), an isoprene polymer (IR), a chloroprene polymer (CR), an isoprene butadiene copolymer (IBR), and a butadiene styrene copolymer (SBR). Examples thereof include acrylonitrile-butadiene copolymer (NBR) and isoprene isoprene copolymer.
＜好適な態様＞
上記ジエン系重合体は、本発明の効果がより優れる理由から、ブタジエン及びイソプレンからなる群より選択される少なくとも１種を含有するモノマーの重合体であることが好ましく、ブタジエンを含有するモノマーの重合体であることがより好ましく、ブタジエン重合体であることがさらに好ましい。 <Preferable aspect>
The diene-based polymer is preferably a polymer of a monomer containing at least one selected from the group consisting of butadiene and isoprene because the effect of the present invention is more excellent, and the weight of the monomer containing butadiene is preferable. It is more preferably a coalescence, and even more preferably a butadiene polymer.
上記ジエン系重合体は、本発明の効果がより優れる理由から、ブタジエン及びイソプレンからなる群より選択される少なくとも１種を含有するモノマーの重合体であることが好ましく、ブタジエンを含有するモノマーの重合体であることがより好ましく、ブタジエン重合体であることがさらに好ましい。 <Preferable aspect>
The diene-based polymer is preferably a polymer of a monomer containing at least one selected from the group consisting of butadiene and isoprene because the effect of the present invention is more excellent, and the weight of the monomer containing butadiene is preferable. It is more preferably a coalescence, and even more preferably a butadiene polymer.
〔官能基Ａ〕
本発明の重合体は、末端に、アミノ基（－ＮＲ２：Ｒは水素原子又は置換基（特に炭素数１～１０の炭化水素基）を表し、２つのＲは同一であっても異なっていてもよい）、水酸基（－ＯＨ）、カルボキシ基（－ＣＯＯＨ）、アルコキシシリル基（－Ｓｉ（Ｒ１）ｍ（Ｒ２）ｎ：Ｒ１はアルコキシ基（特に炭素数１～１０）を表し、Ｒ２は水素原子又は置換基（特に炭素数１～１０の炭化水素基）を表し、ｍは１～３の整数を表し、ｎは０～２の整数を表し、ｍ＋ｎは３であり、ｍが２以上の整数である場合の複数のＲ１は同一であっても異なっていてもよく、ｎが２である場合の２つのＲ２は同一であっても異なっていてもよい）、カルボニル基（－ＣＯ－）を有する１価の基、アルデヒド基（－ＣＨＯ）、エポキシ基、ニトロ基（－ＮＯ２）、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する。 [Functional group A]
The polymer of the present invention represents an amino group (-NR 2 : R is a hydrogen atom or a substituent (particularly a hydrocarbon group having 1 to 10 carbon atoms) at the terminal, and the two Rs are different even if they are the same. (May be), hydroxyl group (-OH), carboxy group (-COOH), alkoxysilyl group (-Si (R 1 ) m (R 2 ) n : R 1 represents an alkoxy group (particularly 1 to 10 carbon atoms). , R 2 represents a hydrogen atom or a substituent (particularly a hydrocarbon group having 1 to 10 carbon atoms), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n is 3. A plurality of R 1s when m is an integer of 2 or more may be the same or different, and two R 2s when n is 2 may be the same or different). At least one selected from the group consisting of a monovalent group having a carbonyl group (-CO-), an aldehyde group (-CHO), an epoxy group, a nitro group (-NO 2 ), and an alkoxysilyl group having an amino group. It has a functional group A of the species.
本発明の重合体は、末端に、アミノ基（－ＮＲ２：Ｒは水素原子又は置換基（特に炭素数１～１０の炭化水素基）を表し、２つのＲは同一であっても異なっていてもよい）、水酸基（－ＯＨ）、カルボキシ基（－ＣＯＯＨ）、アルコキシシリル基（－Ｓｉ（Ｒ１）ｍ（Ｒ２）ｎ：Ｒ１はアルコキシ基（特に炭素数１～１０）を表し、Ｒ２は水素原子又は置換基（特に炭素数１～１０の炭化水素基）を表し、ｍは１～３の整数を表し、ｎは０～２の整数を表し、ｍ＋ｎは３であり、ｍが２以上の整数である場合の複数のＲ１は同一であっても異なっていてもよく、ｎが２である場合の２つのＲ２は同一であっても異なっていてもよい）、カルボニル基（－ＣＯ－）を有する１価の基、アルデヒド基（－ＣＨＯ）、エポキシ基、ニトロ基（－ＮＯ２）、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する。 [Functional group A]
The polymer of the present invention represents an amino group (-NR 2 : R is a hydrogen atom or a substituent (particularly a hydrocarbon group having 1 to 10 carbon atoms) at the terminal, and the two Rs are different even if they are the same. (May be), hydroxyl group (-OH), carboxy group (-COOH), alkoxysilyl group (-Si (R 1 ) m (R 2 ) n : R 1 represents an alkoxy group (particularly 1 to 10 carbon atoms). , R 2 represents a hydrogen atom or a substituent (particularly a hydrocarbon group having 1 to 10 carbon atoms), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n is 3. A plurality of R 1s when m is an integer of 2 or more may be the same or different, and two R 2s when n is 2 may be the same or different). At least one selected from the group consisting of a monovalent group having a carbonyl group (-CO-), an aldehyde group (-CHO), an epoxy group, a nitro group (-NO 2 ), and an alkoxysilyl group having an amino group. It has a functional group A of the species.
本発明の重合体は、１つの末端のみに官能基Ａを有しても、複数の末端に官能基Ａを有してもよいが、本発明の効果がより優れる理由から、１つの末端のみに官能基Ａを有するのが好ましい。
The polymer of the present invention may have a functional group A at only one end or a functional group A at a plurality of ends, but for the reason that the effect of the present invention is more excellent, only one end is used. It is preferable to have a functional group A.
＜好適な態様＞
上記官能基Ａは、本発明の効果がより優れる理由から、アミノ基、アルコキシシリル基、又は、アミノ基を有するアルコキシシリル基であることが好ましく、アミノ基を有するアルコキシシリル基であることがより好ましい。
上記官能基Ａは、本発明の効果がより優れる理由から、環状シラザンに由来する基であることが好ましく、下記式（Ｍ）で表される基であることがより好ましい。 <Preferable aspect>
The functional group A is preferably an amino group, an alkoxysilyl group, or an alkoxysilyl group having an amino group, and more preferably an alkoxysilyl group having an amino group, for the reason that the effect of the present invention is more excellent. preferable.
The functional group A is preferably a group derived from cyclic silazane, and more preferably a group represented by the following formula (M), for the reason that the effect of the present invention is more excellent.
上記官能基Ａは、本発明の効果がより優れる理由から、アミノ基、アルコキシシリル基、又は、アミノ基を有するアルコキシシリル基であることが好ましく、アミノ基を有するアルコキシシリル基であることがより好ましい。
上記官能基Ａは、本発明の効果がより優れる理由から、環状シラザンに由来する基であることが好ましく、下記式（Ｍ）で表される基であることがより好ましい。 <Preferable aspect>
The functional group A is preferably an amino group, an alkoxysilyl group, or an alkoxysilyl group having an amino group, and more preferably an alkoxysilyl group having an amino group, for the reason that the effect of the present invention is more excellent. preferable.
The functional group A is preferably a group derived from cyclic silazane, and more preferably a group represented by the following formula (M), for the reason that the effect of the present invention is more excellent.
上記式（Ｍ）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子または置換基を表す。
上記式（Ｍ）中、Ｌは、２価の有機基を表す。 In the above formula (M), R 1 and R 2 each independently represent a hydrogen atom or a substituent.
In the above formula (M), L represents a divalent organic group.
上記式（Ｍ）中、Ｌは、２価の有機基を表す。 In the above formula (M), R 1 and R 2 each independently represent a hydrogen atom or a substituent.
In the above formula (M), L represents a divalent organic group.
上述のとおり、式（Ｍ）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子または置換基を表す。
上記置換基は１価の置換基であれば特に制限されないが、例えば、ハロゲン原子、ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アミノ基、メルカプト基、アシル基、イミド基、ホスフィノ基、ホスフィニル基、シリル基、ヘテロ原子を有していてもよい炭化水素基などが挙げられる。
上記ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられる。
上記ヘテロ原子を有していてもよい炭化水素基のヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、リン原子などが挙げられる。
上記ヘテロ原子を有していてもよい炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、またはこれらを組み合わせた基などが挙げられる。
上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状または分岐状のアルキル基（特に、炭素数１～３０）、直鎖状または分岐状のアルケニル基（特に、炭素数２～３０）、直鎖状または分岐状のアルキニル基（特に、炭素数２～３０）などが挙げられる。
上記芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基などの炭素数６～１８の芳香族炭化水素基などが挙げられる。 As described above, in formula (M), R 1 and R 2 each independently represent a hydrogen atom or a substituent.
The above substituent is not particularly limited as long as it is a monovalent substituent, but for example, a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, an acyl group, an imide group, a phosphino group and a phosphinyl. Examples thereof include a group, a silyl group, a hydrocarbon group which may have a hetero atom, and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the heteroatom of the hydrocarbon group which may have the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.
Examples of the hydrocarbon group which may have the heteroatom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), and the like. Examples thereof include a linear or branched alkynyl group (particularly, 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
上記置換基は１価の置換基であれば特に制限されないが、例えば、ハロゲン原子、ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アミノ基、メルカプト基、アシル基、イミド基、ホスフィノ基、ホスフィニル基、シリル基、ヘテロ原子を有していてもよい炭化水素基などが挙げられる。
上記ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられる。
上記ヘテロ原子を有していてもよい炭化水素基のヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、リン原子などが挙げられる。
上記ヘテロ原子を有していてもよい炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、またはこれらを組み合わせた基などが挙げられる。
上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状または分岐状のアルキル基（特に、炭素数１～３０）、直鎖状または分岐状のアルケニル基（特に、炭素数２～３０）、直鎖状または分岐状のアルキニル基（特に、炭素数２～３０）などが挙げられる。
上記芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基などの炭素数６～１８の芳香族炭化水素基などが挙げられる。 As described above, in formula (M), R 1 and R 2 each independently represent a hydrogen atom or a substituent.
The above substituent is not particularly limited as long as it is a monovalent substituent, but for example, a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, an acyl group, an imide group, a phosphino group and a phosphinyl. Examples thereof include a group, a silyl group, a hydrocarbon group which may have a hetero atom, and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the heteroatom of the hydrocarbon group which may have the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.
Examples of the hydrocarbon group which may have the heteroatom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), and the like. Examples thereof include a linear or branched alkynyl group (particularly, 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
上記式（Ｍ）中、Ｒ１は、本発明の効果がより優れる理由から、水素原子、アルキル基（好ましくは、炭素数１～１０）、アルキルシリル基（好ましくは、炭素数１～１０）、芳香族炭化水素基（好ましくは、炭素数６～１８）であることが好ましく、水素原子であることがより好ましい。
複数のＲ１は同一であっても異なっていてもよい。 In the above formula (M), R 1 has a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), and an alkylsilyl group (preferably 1 to 10 carbon atoms) because the effect of the present invention is more excellent. , It is preferably an aromatic hydrocarbon group (preferably 6 to 18 carbon atoms), and more preferably a hydrogen atom.
The plurality of R 1s may be the same or different.
複数のＲ１は同一であっても異なっていてもよい。 In the above formula (M), R 1 has a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), and an alkylsilyl group (preferably 1 to 10 carbon atoms) because the effect of the present invention is more excellent. , It is preferably an aromatic hydrocarbon group (preferably 6 to 18 carbon atoms), and more preferably a hydrogen atom.
The plurality of R 1s may be the same or different.
上記式（Ｍ）中、Ｒ２は、本発明の効果がより優れる理由から、ヒドロカルビルオキシ基（－ＯＲ基：Ｒは炭化水素基）であることが好ましく、アルコキシ基（好ましくは、炭素数１～１０）であることがより好ましい。
In the above formula (M), R 2 is preferably a hydrocarbyloxy group (-OR group: R is a hydrocarbon group) and an alkoxy group (preferably having 1 carbon atom) because the effect of the present invention is more excellent. ~ 10) is more preferable.
上述のとおり、上記式（Ｍ）中、Ｌは、単結合又は２価の有機基を表す。
２価の有機基としては、例えば、脂肪族炭化水素基（例えば、アルキレン基。好ましくは炭素数１～１０）、芳香族炭化水素基（例えば、アリーレン基。好ましくは炭素数６～１８）、－Ｏ－、－Ｓ－、－ＳＯ２－、－Ｎ（Ｒ）－（Ｒ：アルキル基）、－ＣＯ－、－ＮＨ－、－ＣＯＯ－、－ＣＯＮＨ－、またはこれらを組み合わせた基（例えば、アルキレンオキシ基（－ＣｍＨ２ｍＯ－：ｍは正の整数）、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など）などが挙げられる。
Ｌは、本発明の効果がより優れる理由から、アルキレン基（好ましくは、炭素数１～１０）であることが好ましい。 As described above, in the above formula (M), L represents a single bond or a divalent organic group.
Examples of the divalent organic group include an aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 10 carbon atoms), an aromatic hydrocarbon group (for example, an arylene group, preferably 6 to 18 carbon atoms), and the like. -O-, -S-, -SO 2- , -N (R)-(R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group combining these (for example). , Alkyleneoxy group (-Cm H 2m O-: m is a positive integer), alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.) and the like.
L is preferably an alkylene group (preferably 1 to 10 carbon atoms) because the effect of the present invention is more excellent.
２価の有機基としては、例えば、脂肪族炭化水素基（例えば、アルキレン基。好ましくは炭素数１～１０）、芳香族炭化水素基（例えば、アリーレン基。好ましくは炭素数６～１８）、－Ｏ－、－Ｓ－、－ＳＯ２－、－Ｎ（Ｒ）－（Ｒ：アルキル基）、－ＣＯ－、－ＮＨ－、－ＣＯＯ－、－ＣＯＮＨ－、またはこれらを組み合わせた基（例えば、アルキレンオキシ基（－ＣｍＨ２ｍＯ－：ｍは正の整数）、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など）などが挙げられる。
Ｌは、本発明の効果がより優れる理由から、アルキレン基（好ましくは、炭素数１～１０）であることが好ましい。 As described above, in the above formula (M), L represents a single bond or a divalent organic group.
Examples of the divalent organic group include an aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 10 carbon atoms), an aromatic hydrocarbon group (for example, an arylene group, preferably 6 to 18 carbon atoms), and the like. -O-, -S-, -SO 2- , -N (R)-(R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group combining these (for example). , Alkyleneoxy group (-Cm H 2m O-: m is a positive integer), alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.) and the like.
L is preferably an alkylene group (preferably 1 to 10 carbon atoms) because the effect of the present invention is more excellent.
上記式（Ｍ）中、ｎは、０～２の整数を表す。
ｎは、本発明の効果がより優れる理由から、２であることが好ましい。 In the above equation (M), n represents an integer of 0 to 2.
n is preferably 2 because the effect of the present invention is more excellent.
ｎは、本発明の効果がより優れる理由から、２であることが好ましい。 In the above equation (M), n represents an integer of 0 to 2.
n is preferably 2 because the effect of the present invention is more excellent.
上記式（Ｍ）中、ｍは、１～３の整数を表す。
ｍは、本発明の効果がより優れる理由から、１であることが好ましい。 In the above equation (M), m represents an integer of 1 to 3.
m is preferably 1 for the reason that the effect of the present invention is more excellent.
ｍは、本発明の効果がより優れる理由から、１であることが好ましい。 In the above equation (M), m represents an integer of 1 to 3.
m is preferably 1 for the reason that the effect of the present invention is more excellent.
上記式（Ｍ）中、ｎ及びｍは、ｎ＋ｍ＝３の関係式を満たす。
In the above equation (M), n and m satisfy the relational expression of n + m = 3.
上記式（Ｍ）中、＊は、結合位置を表す。
In the above formula (M), * represents the bonding position.
＜末端官能基数＞
本発明の重合体の末端官能基数は、本発明の効果がより優れる理由から、０．１～２であることが好ましく、０．５～１であることがより好ましく、１であることがさらに好ましい。
ここで、末端官能基数とは、末端に有する官能基Ａの数（１分子あたりの平均の数）を表す。 <Number of terminal functional groups>
The number of terminal functional groups of the polymer of the present invention is preferably 0.1 to 2, more preferably 0.5 to 1, and further preferably 1 for the reason that the effect of the present invention is more excellent. preferable.
Here, the number of terminal functional groups represents the number of functional groups A having at the terminal (average number per molecule).
本発明の重合体の末端官能基数は、本発明の効果がより優れる理由から、０．１～２であることが好ましく、０．５～１であることがより好ましく、１であることがさらに好ましい。
ここで、末端官能基数とは、末端に有する官能基Ａの数（１分子あたりの平均の数）を表す。 <Number of terminal functional groups>
The number of terminal functional groups of the polymer of the present invention is preferably 0.1 to 2, more preferably 0.5 to 1, and further preferably 1 for the reason that the effect of the present invention is more excellent. preferable.
Here, the number of terminal functional groups represents the number of functional groups A having at the terminal (average number per molecule).
〔官能基Ｂ〕
本発明の重合体は、主鎖に、下記式（１）で表される官能基Ｂを有する。 [Functional group B]
The polymer of the present invention has a functional group B represented by the following formula (1) in the main chain.
本発明の重合体は、主鎖に、下記式（１）で表される官能基Ｂを有する。 [Functional group B]
The polymer of the present invention has a functional group B represented by the following formula (1) in the main chain.
式（１）中、Ｒ１は、炭素数１～１０のアルキレン基を表し、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、炭素数１～１０のアルコキシ基を表し、＊は、結合位置を表す。
In the formula (1), R 1 represents an alkylene group having 1 to 10 carbon atoms, R 2 , R 3 and R 4 independently represent an alkoxy group having 1 to 10 carbon atoms, and * represents a bond. Represents a position.
上述のとおり、上記式（１）中、Ｒ１は、炭素数１～１０のアルキレン基を表す。
上記Ｒ１は、本発明の効果がより優れる理由から、炭素数２～５のアルキレン基であることが好ましい。 As described above, in the above formula (1), R 1 represents an alkylene group having 1 to 10 carbon atoms.
The above R 1 is preferably an alkylene group having 2 to 5 carbon atoms because the effect of the present invention is more excellent.
上記Ｒ１は、本発明の効果がより優れる理由から、炭素数２～５のアルキレン基であることが好ましい。 As described above, in the above formula (1), R 1 represents an alkylene group having 1 to 10 carbon atoms.
The above R 1 is preferably an alkylene group having 2 to 5 carbon atoms because the effect of the present invention is more excellent.
上述のとおり、上記式（１）中、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、炭素数１～１０のアルコキシ基を表す。Ｒ２、Ｒ３及びＲ４は、本発明の効果がより優れる理由から、それぞれ独立に、炭素数１～５のアルコキシ基であることが好ましい。
As described above, in the above formula (1), R 2 , R 3 and R 4 each independently represent an alkoxy group having 1 to 10 carbon atoms. It is preferable that R 2 , R 3 and R 4 are independently alkoxy groups having 1 to 5 carbon atoms, respectively, for the reason that the effect of the present invention is more excellent.
＜主鎖官能基数＞
本発明の重合体の主鎖官能基数は、本発明の効果がより優れる理由から、０．１～１００であることが好ましく、１～２０であることがより好ましく、２～１０であることがさらに好ましい。
ここで、主鎖官能基数とは、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）を表す。 <Number of backbone functional groups>
The number of main chain functional groups of the polymer of the present invention is preferably 0.1 to 100, more preferably 1 to 20, and preferably 2 to 10 for the reason that the effect of the present invention is more excellent. More preferred.
Here, the number of functional groups in the main chain represents the number of functional groups B in the main chain (the average number per molecule).
本発明の重合体の主鎖官能基数は、本発明の効果がより優れる理由から、０．１～１００であることが好ましく、１～２０であることがより好ましく、２～１０であることがさらに好ましい。
ここで、主鎖官能基数とは、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）を表す。 <Number of backbone functional groups>
The number of main chain functional groups of the polymer of the present invention is preferably 0.1 to 100, more preferably 1 to 20, and preferably 2 to 10 for the reason that the effect of the present invention is more excellent. More preferred.
Here, the number of functional groups in the main chain represents the number of functional groups B in the main chain (the average number per molecule).
〔官能基数〕
本発明の重合体の官能基数は、本発明の効果がより優れる理由から、０．１～１００であることが好ましく、１～２０であることがより好ましく、２～１０であることがさらに好ましい。
ここで、官能基数とは、末端に有する官能基Ａの数（１分子あたりの平均の数）と、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）との合計を表す。 [Number of functional groups]
The number of functional groups of the polymer of the present invention is preferably 0.1 to 100, more preferably 1 to 20, and even more preferably 2 to 10 because the effect of the present invention is more excellent. ..
Here, the number of functional groups represents the total of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). ..
本発明の重合体の官能基数は、本発明の効果がより優れる理由から、０．１～１００であることが好ましく、１～２０であることがより好ましく、２～１０であることがさらに好ましい。
ここで、官能基数とは、末端に有する官能基Ａの数（１分子あたりの平均の数）と、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）との合計を表す。 [Number of functional groups]
The number of functional groups of the polymer of the present invention is preferably 0.1 to 100, more preferably 1 to 20, and even more preferably 2 to 10 because the effect of the present invention is more excellent. ..
Here, the number of functional groups represents the total of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). ..
〔主鎖官能基数／末端官能基数〕
本発明の重合体において、上述した末端官能基数に対する上述した主鎖官能基数の割合（主鎖官能基数／末端官能基数）は、本発明の効果がより優れる理由から、１～１０であることが好ましく、２～５であることがより好ましい。 [Number of main chain functional groups / number of terminal functional groups]
In the polymer of the present invention, the ratio of the above-mentioned number of main chain functional groups to the above-mentioned number of terminal functional groups (number of main chain functional groups / number of terminal functional groups) may be 1 to 10 for the reason that the effect of the present invention is more excellent. It is preferably 2 to 5, and more preferably 2 to 5.
本発明の重合体において、上述した末端官能基数に対する上述した主鎖官能基数の割合（主鎖官能基数／末端官能基数）は、本発明の効果がより優れる理由から、１～１０であることが好ましく、２～５であることがより好ましい。 [Number of main chain functional groups / number of terminal functional groups]
In the polymer of the present invention, the ratio of the above-mentioned number of main chain functional groups to the above-mentioned number of terminal functional groups (number of main chain functional groups / number of terminal functional groups) may be 1 to 10 for the reason that the effect of the present invention is more excellent. It is preferably 2 to 5, and more preferably 2 to 5.
〔分子量〕
本発明の重合体の重量平均分子量（Ｍｗ）は、本発明の効果がより優れる理由から、１，０００～１００，０００であることが好ましく、１０，０００～８０，０００であることがより好ましく、２０，０００～５０，０００であることがさらに好ましい。
本発明の重合体の数平均分子量は、本発明の効果がより優れる理由から、１，０００～１００，０００であることが好ましく、１０，０００～８０，０００であることがより好ましく、２０，０００～５０，０００であることがさらに好ましい。
なお、本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、以下の条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により得られる標準ポリスチレン換算値とする。
・溶媒：テトラヒドロフラン
・検出器：ＲＩ検出器 [Molecular weight]
The weight average molecular weight (Mw) of the polymer of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 80,000 because the effect of the present invention is more excellent. It is more preferably 20,000 to 50,000.
The number average molecular weight of the polymer of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 80,000, and more preferably 20, It is more preferably 000 to 50,000.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are standard polystyrene-equivalent values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
・ Solvent: Tetrahydrofuran ・ Detector: RI detector
本発明の重合体の重量平均分子量（Ｍｗ）は、本発明の効果がより優れる理由から、１，０００～１００，０００であることが好ましく、１０，０００～８０，０００であることがより好ましく、２０，０００～５０，０００であることがさらに好ましい。
本発明の重合体の数平均分子量は、本発明の効果がより優れる理由から、１，０００～１００，０００であることが好ましく、１０，０００～８０，０００であることがより好ましく、２０，０００～５０，０００であることがさらに好ましい。
なお、本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、以下の条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により得られる標準ポリスチレン換算値とする。
・溶媒：テトラヒドロフラン
・検出器：ＲＩ検出器 [Molecular weight]
The weight average molecular weight (Mw) of the polymer of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 80,000 because the effect of the present invention is more excellent. It is more preferably 20,000 to 50,000.
The number average molecular weight of the polymer of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 80,000, and more preferably 20, It is more preferably 000 to 50,000.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are standard polystyrene-equivalent values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
・ Solvent: Tetrahydrofuran ・ Detector: RI detector
〔液状〕
本発明の重合体は、２０℃、１気圧において、液状である。 [Liquid]
The polymer of the present invention is liquid at 20 ° C. and 1 atm.
本発明の重合体は、２０℃、１気圧において、液状である。 [Liquid]
The polymer of the present invention is liquid at 20 ° C. and 1 atm.
［本発明の重合体の製造方法］
本発明の重合体を製造する方法は特に制限されないが、得られる本発明の重合体のシリカ吸着性がより優れる理由から、
末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体と、
ラジカル開始剤と、
後述する式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上述した式（１）で表される官能基Ｂを導入し、本発明の重合体を得る方法（以下、「製造方法１」とも言う）が好ましい。
上記製造方法１においては、ラジカル開始剤によって末端変性液状ジエン系重合体の二重結合のα炭素原子から水素原子が引き抜かれ、そこに式（２）で表される化合物が反応して、末端変性液状ジエン系重合体の主鎖に式（１）で表される官能基Ｂが導入される。
上記製造方法１の反応は、得られる本発明の重合体のシリカ吸着性がより優れる理由から、バルク又は有機溶媒中で行うのが好ましい。
以下、「得られる本発明の重合体のシリカ吸着性がより優れる」ことを「本発明の効果がより優れる」とも言う。 [Method for Producing Polymer of the Present Invention]
The method for producing the polymer of the present invention is not particularly limited, but the obtained polymer of the present invention has more excellent silica adsorptivity.
At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. A terminal-modified liquid diene polymer which is a liquid diene polymer having one kind of functional group A, and a terminal-modified liquid diene polymer.
Radical initiator and
By reacting with a compound represented by the formula (2) described later, the functional group B represented by the formula (1) described above is introduced into the main chain of the terminal-modified liquid diene polymer, and the present invention A method for obtaining a polymer (hereinafter, also referred to as “production method 1”) is preferable.
In the above production method 1, a hydrogen atom is extracted from the α carbon atom of the double bond of the terminal-modified liquid diene polymer by a radical initiator, and the compound represented by the formula (2) reacts there with the terminal. The functional group B represented by the formula (1) is introduced into the main chain of the modified liquid diene polymer.
The reaction of the above-mentioned production method 1 is preferably carried out in bulk or in an organic solvent because the obtained polymer of the present invention has more excellent silica adsorptivity.
Hereinafter, "the obtained polymer of the present invention having better silica adsorptivity" is also referred to as "the effect of the present invention is more excellent".
本発明の重合体を製造する方法は特に制限されないが、得られる本発明の重合体のシリカ吸着性がより優れる理由から、
末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体と、
ラジカル開始剤と、
後述する式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上述した式（１）で表される官能基Ｂを導入し、本発明の重合体を得る方法（以下、「製造方法１」とも言う）が好ましい。
上記製造方法１においては、ラジカル開始剤によって末端変性液状ジエン系重合体の二重結合のα炭素原子から水素原子が引き抜かれ、そこに式（２）で表される化合物が反応して、末端変性液状ジエン系重合体の主鎖に式（１）で表される官能基Ｂが導入される。
上記製造方法１の反応は、得られる本発明の重合体のシリカ吸着性がより優れる理由から、バルク又は有機溶媒中で行うのが好ましい。
以下、「得られる本発明の重合体のシリカ吸着性がより優れる」ことを「本発明の効果がより優れる」とも言う。 [Method for Producing Polymer of the Present Invention]
The method for producing the polymer of the present invention is not particularly limited, but the obtained polymer of the present invention has more excellent silica adsorptivity.
At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. A terminal-modified liquid diene polymer which is a liquid diene polymer having one kind of functional group A, and a terminal-modified liquid diene polymer.
Radical initiator and
By reacting with a compound represented by the formula (2) described later, the functional group B represented by the formula (1) described above is introduced into the main chain of the terminal-modified liquid diene polymer, and the present invention A method for obtaining a polymer (hereinafter, also referred to as “production method 1”) is preferable.
In the above production method 1, a hydrogen atom is extracted from the α carbon atom of the double bond of the terminal-modified liquid diene polymer by a radical initiator, and the compound represented by the formula (2) reacts there with the terminal. The functional group B represented by the formula (1) is introduced into the main chain of the modified liquid diene polymer.
The reaction of the above-mentioned production method 1 is preferably carried out in bulk or in an organic solvent because the obtained polymer of the present invention has more excellent silica adsorptivity.
Hereinafter, "the obtained polymer of the present invention having better silica adsorptivity" is also referred to as "the effect of the present invention is more excellent".
以下、製造方法１で使用される各成分について説明する。
Hereinafter, each component used in the manufacturing method 1 will be described.
〔末端変性液状ジエン系重合体〕
上述のとおり、上記末端変性液状ジエン系重合体は、末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する液状ジエン系重合体である。
上記末端変性液状ジエン系重合体において、骨格及び官能基Ａの定義、具体例及び好適な態様は、上述した本発明の重合体と同じである。 [Terminal-modified liquid diene polymer]
As described above, the terminal-modified liquid diene-based polymer has an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group at the terminal, an aldehyde group, an epoxy group, a nitro group, and an amino. A liquid diene-based polymer having at least one functional group A selected from the group consisting of an alkoxysilyl group having a group.
In the terminal-modified liquid diene polymer, the definition, specific examples and preferred embodiments of the skeleton and the functional group A are the same as those of the polymer of the present invention described above.
上述のとおり、上記末端変性液状ジエン系重合体は、末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する液状ジエン系重合体である。
上記末端変性液状ジエン系重合体において、骨格及び官能基Ａの定義、具体例及び好適な態様は、上述した本発明の重合体と同じである。 [Terminal-modified liquid diene polymer]
As described above, the terminal-modified liquid diene-based polymer has an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group at the terminal, an aldehyde group, an epoxy group, a nitro group, and an amino. A liquid diene-based polymer having at least one functional group A selected from the group consisting of an alkoxysilyl group having a group.
In the terminal-modified liquid diene polymer, the definition, specific examples and preferred embodiments of the skeleton and the functional group A are the same as those of the polymer of the present invention described above.
〔ラジカル開始剤〕
上記ラジカル開始剤は特に限定されず、その具体例としては、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ジクミルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、２，５－ジメチル－２，５－ジ－ｔ－ブチルパーオキシヘキサン、２，５－ジメチル－２，５－ジ－ｔ－ブチルパーオキシ－３－ヘキシン、２，４－ジクロロ－ベンゾイルパーオキサイド、ジ－ｔ－ブチルパーオキシ－ジ－イソプロピルベンゼン、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチル－シクロヘキサン、ｎ－ブチル－４，４－ビス（ｔ－ブチルパーオキシ）バレレート、２，２－ビス（ｔ－ブチルパーオキシ）ブタンなどの有機過酸化物、アゾジカーボンアミド、アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２’－アゾビス－（２－アミジノプロパン）ジハイドロクロライド、ジメチル２，２’－アゾビス（イソブチレート）、アゾビス－シアン吉草酸、１，１’－アゾビス－（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス－（２，４－ジメチルバレロニトリル）、アゾビスメチルブチロニトリル、２，２’－アゾビス－（４－メトキシ－２，４－ジメチルバレロニトリル）などのラジカル発生剤、等が挙げられる。
上記ラジカル開始剤は、本発明の効果がより優れる理由から、アゾビスイソブチロニトリル（ＡＩＢＮ）であることが好ましい。 [Radical initiator]
The radical initiator is not particularly limited, and specific examples thereof include benzoyl peroxide, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide, 2,5. -Dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxy-3-hexine, 2,4-dichloro-benzoyl peroxide, di- t-Butylperoxy-di-isopropylbenzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl-cyclohexane, n-butyl-4,4-bis (t-butylperoxy) Valerate, organic peroxides such as 2,2-bis (t-butylperoxy) butane, azodicarbonamide, azobisisobutyronitrile (AIBN), 2,2'-azobis- (2-amidinopropane) Dihydrochloride, dimethyl 2,2'-azobis (isobutylate), azobis-cyan valerate, 1,1'-azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis- (2,4-dimethyl) Valeronitrile), azobismethylbutyronitrile, radical generators such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), and the like.
The radical initiator is preferably azobisisobutyronitrile (AIBN) because the effect of the present invention is more excellent.
上記ラジカル開始剤は特に限定されず、その具体例としては、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ジクミルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、２，５－ジメチル－２，５－ジ－ｔ－ブチルパーオキシヘキサン、２，５－ジメチル－２，５－ジ－ｔ－ブチルパーオキシ－３－ヘキシン、２，４－ジクロロ－ベンゾイルパーオキサイド、ジ－ｔ－ブチルパーオキシ－ジ－イソプロピルベンゼン、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチル－シクロヘキサン、ｎ－ブチル－４，４－ビス（ｔ－ブチルパーオキシ）バレレート、２，２－ビス（ｔ－ブチルパーオキシ）ブタンなどの有機過酸化物、アゾジカーボンアミド、アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２’－アゾビス－（２－アミジノプロパン）ジハイドロクロライド、ジメチル２，２’－アゾビス（イソブチレート）、アゾビス－シアン吉草酸、１，１’－アゾビス－（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス－（２，４－ジメチルバレロニトリル）、アゾビスメチルブチロニトリル、２，２’－アゾビス－（４－メトキシ－２，４－ジメチルバレロニトリル）などのラジカル発生剤、等が挙げられる。
上記ラジカル開始剤は、本発明の効果がより優れる理由から、アゾビスイソブチロニトリル（ＡＩＢＮ）であることが好ましい。 [Radical initiator]
The radical initiator is not particularly limited, and specific examples thereof include benzoyl peroxide, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide, 2,5. -Dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxy-3-hexine, 2,4-dichloro-benzoyl peroxide, di- t-Butylperoxy-di-isopropylbenzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl-cyclohexane, n-butyl-4,4-bis (t-butylperoxy) Valerate, organic peroxides such as 2,2-bis (t-butylperoxy) butane, azodicarbonamide, azobisisobutyronitrile (AIBN), 2,2'-azobis- (2-amidinopropane) Dihydrochloride, dimethyl 2,2'-azobis (isobutylate), azobis-cyan valerate, 1,1'-azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis- (2,4-dimethyl) Valeronitrile), azobismethylbutyronitrile, radical generators such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), and the like.
The radical initiator is preferably azobisisobutyronitrile (AIBN) because the effect of the present invention is more excellent.
＜添加量＞
上記ラジカル開始剤の添加量は特に制限されないが、本発明の効果がより優れる理由から、上述した末端変性液状ジエン系重合体に対して、０．１～１０質量％であることが好ましく、１～５質量％であることがより好ましい。 <Addition amount>
The amount of the radical initiator added is not particularly limited, but is preferably 0.1 to 10% by mass with respect to the terminal-modified liquid diene polymer described above for the reason that the effect of the present invention is more excellent. More preferably, it is ~ 5% by mass.
上記ラジカル開始剤の添加量は特に制限されないが、本発明の効果がより優れる理由から、上述した末端変性液状ジエン系重合体に対して、０．１～１０質量％であることが好ましく、１～５質量％であることがより好ましい。 <Addition amount>
The amount of the radical initiator added is not particularly limited, but is preferably 0.1 to 10% by mass with respect to the terminal-modified liquid diene polymer described above for the reason that the effect of the present invention is more excellent. More preferably, it is ~ 5% by mass.
〔式（２）で表される化合物〕
上述のとおり、製造方法１では、式（２）で表される化合物が使用される。 [Compound represented by formula (2)]
As described above, in the production method 1, the compound represented by the formula (2) is used.
上述のとおり、製造方法１では、式（２）で表される化合物が使用される。 [Compound represented by formula (2)]
As described above, in the production method 1, the compound represented by the formula (2) is used.
式（２）中、Ｒ１は、炭素数１～１０のアルキレン基を表し、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、炭素数１～１０のアルコキシ基を表す。
In the formula (2), R 1 represents an alkylene group having 1 to 10 carbon atoms, and R 2 , R 3 and R 4 independently represent an alkoxy group having 1 to 10 carbon atoms.
式（２）中のＲ１、Ｒ２、Ｒ３及びＲ４の定義、具体例及び好適な態様は、上述した式（１）と同じである。
The definitions, specific examples and suitable embodiments of R 1 , R 2 , R 3 and R 4 in the formula (2) are the same as those in the above formula (1).
＜具体例＞
上記式（２）で表される化合物の具体例としては、メルカプトプロピルトリメトキシシラン、メルカプトプロピルトリエトキシシラン等が挙げられる。 <Specific example>
Specific examples of the compound represented by the above formula (2) include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
上記式（２）で表される化合物の具体例としては、メルカプトプロピルトリメトキシシラン、メルカプトプロピルトリエトキシシラン等が挙げられる。 <Specific example>
Specific examples of the compound represented by the above formula (2) include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
＜添加量＞
上記式（２）で表される化合物の添加量は特に制限されないが、本発明の効果がより優れる理由から、上述した末端変性液状ジエン系重合体に対して、１～５０質量％であることが好ましく、１～１０質量％であることがより好ましい。 <Addition amount>
The amount of the compound represented by the above formula (2) to be added is not particularly limited, but is 1 to 50% by mass with respect to the above-mentioned terminal-modified liquid diene polymer for the reason that the effect of the present invention is more excellent. It is preferable, and it is more preferable that it is 1 to 10% by mass.
上記式（２）で表される化合物の添加量は特に制限されないが、本発明の効果がより優れる理由から、上述した末端変性液状ジエン系重合体に対して、１～５０質量％であることが好ましく、１～１０質量％であることがより好ましい。 <Addition amount>
The amount of the compound represented by the above formula (2) to be added is not particularly limited, but is 1 to 50% by mass with respect to the above-mentioned terminal-modified liquid diene polymer for the reason that the effect of the present invention is more excellent. It is preferable, and it is more preferable that it is 1 to 10% by mass.
〔好適な態様〕
上記製造方法１は、本発明の効果がより優れる理由から、下記（１）～（３）の工程を備える方法（以下、「製造方法２」とも言う）であることが好ましい。 [Preferable aspect]
The manufacturing method 1 is preferably a method including the following steps (1) to (3) (hereinafter, also referred to as “manufacturing method 2”) because the effect of the present invention is more excellent.
上記製造方法１は、本発明の効果がより優れる理由から、下記（１）～（３）の工程を備える方法（以下、「製造方法２」とも言う）であることが好ましい。 [Preferable aspect]
The manufacturing method 1 is preferably a method including the following steps (1) to (3) (hereinafter, also referred to as “manufacturing method 2”) because the effect of the present invention is more excellent.
（１）モノマー重合工程
有機リチウム化合物を用いてジエンを含有するモノマーを重合し、活性末端を有する液状ジエン系重合体を得る工程
（２）末端変性工程
特定の求電子剤を用いて上記モノマーの重合を停止することで、上記液状ジエン系重合体の末端に上記特定の求電子剤に由来する官能基Ａを導入し、末端に上記官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体を得る工程
（３）主鎖変性工程
上記末端変性液状ジエン系重合体と、ラジカル開始剤と、上述した式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上述した式（１）で表される官能基Ｂを導入し、末端に上記官能基Ａを有し主鎖に上記官能基Ｂを有する液状ジエン系重合体である変性液状ジエン系重合体を得る工程 (1) Monomer polymerization step A step of polymerizing a diene-containing monomer using an organic lithium compound to obtain a liquid diene-based polymer having an active terminal (2) a terminal modification step of the above monomer using a specific electrogenerator. By terminating the polymerization, a functional group A derived from the specific electrophoretic agent is introduced into the terminal of the liquid diene polymer, and the terminal-modified liquid which is a liquid diene polymer having the functional group A at the end is a terminal-modified liquid. Step for obtaining a diene polymer (3) Main chain modification step The terminal modification is carried out by reacting the terminal-modified liquid diene polymer with a radical initiator and the compound represented by the above formula (2). A liquid diene polymer having the functional group B represented by the above formula (1) introduced into the main chain of the liquid diene polymer, having the functional group A at the terminal and having the functional group B in the main chain. Step to obtain a modified liquid diene polymer
有機リチウム化合物を用いてジエンを含有するモノマーを重合し、活性末端を有する液状ジエン系重合体を得る工程
（２）末端変性工程
特定の求電子剤を用いて上記モノマーの重合を停止することで、上記液状ジエン系重合体の末端に上記特定の求電子剤に由来する官能基Ａを導入し、末端に上記官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体を得る工程
（３）主鎖変性工程
上記末端変性液状ジエン系重合体と、ラジカル開始剤と、上述した式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上述した式（１）で表される官能基Ｂを導入し、末端に上記官能基Ａを有し主鎖に上記官能基Ｂを有する液状ジエン系重合体である変性液状ジエン系重合体を得る工程 (1) Monomer polymerization step A step of polymerizing a diene-containing monomer using an organic lithium compound to obtain a liquid diene-based polymer having an active terminal (2) a terminal modification step of the above monomer using a specific electrogenerator. By terminating the polymerization, a functional group A derived from the specific electrophoretic agent is introduced into the terminal of the liquid diene polymer, and the terminal-modified liquid which is a liquid diene polymer having the functional group A at the end is a terminal-modified liquid. Step for obtaining a diene polymer (3) Main chain modification step The terminal modification is carried out by reacting the terminal-modified liquid diene polymer with a radical initiator and the compound represented by the above formula (2). A liquid diene polymer having the functional group B represented by the above formula (1) introduced into the main chain of the liquid diene polymer, having the functional group A at the terminal and having the functional group B in the main chain. Step to obtain a modified liquid diene polymer
以下、製造方法２の各工程について説明する。
Hereinafter, each process of manufacturing method 2 will be described.
＜モノマー重合工程＞
モノマー重合工程は、有機リチウム化合物を用いてジエンを含有するモノマーを重合し、活性末端を有する液状ジエン系重合体を得る工程である。 <Monomer polymerization process>
The monomer polymerization step is a step of polymerizing a monomer containing a diene using an organolithium compound to obtain a liquid diene-based polymer having an active terminal.
モノマー重合工程は、有機リチウム化合物を用いてジエンを含有するモノマーを重合し、活性末端を有する液状ジエン系重合体を得る工程である。 <Monomer polymerization process>
The monomer polymerization step is a step of polymerizing a monomer containing a diene using an organolithium compound to obtain a liquid diene-based polymer having an active terminal.
（ジエンを含有するモノマー）
上記ジエンを含有するモノマーについて、ジエンは、本発明の効果がより優れる理由から、共役ジエンであることが好ましく、その具体例及び好適な態様は、上述した本発明の重合体の骨格のジエン系重合体と同じである。
また、上記ジエンを含有するモノマーについて、ジエン以外のモノマーの具体例及び好適な態様は、上述した本発明の重合体の骨格のジエン系重合体と同じである。 (Monomer containing diene)
Regarding the above-mentioned monomer containing a diene, the diene is preferably a conjugated diene because the effect of the present invention is more excellent, and specific examples and suitable embodiments thereof are the diene system of the skeleton of the polymer of the present invention described above. Same as polymer.
Further, regarding the above-mentioned monomer containing diene, specific examples and suitable embodiments of the monomer other than diene are the same as those of the above-mentioned diene-based polymer having the skeleton of the polymer of the present invention.
上記ジエンを含有するモノマーについて、ジエンは、本発明の効果がより優れる理由から、共役ジエンであることが好ましく、その具体例及び好適な態様は、上述した本発明の重合体の骨格のジエン系重合体と同じである。
また、上記ジエンを含有するモノマーについて、ジエン以外のモノマーの具体例及び好適な態様は、上述した本発明の重合体の骨格のジエン系重合体と同じである。 (Monomer containing diene)
Regarding the above-mentioned monomer containing a diene, the diene is preferably a conjugated diene because the effect of the present invention is more excellent, and specific examples and suitable embodiments thereof are the diene system of the skeleton of the polymer of the present invention described above. Same as polymer.
Further, regarding the above-mentioned monomer containing diene, specific examples and suitable embodiments of the monomer other than diene are the same as those of the above-mentioned diene-based polymer having the skeleton of the polymer of the present invention.
（有機リチウム化合物）
上記有機リチウム化合物は特に制限されないが、その具体例としては、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔｅｒｔ－ブチルリチウム、ｎ－プロピルリチウム、ｉｓｏ－プロピルリチウム、ベンジルリチウム等のモノ有機リチウム化合物；１，４－ジリチオブタン、１，５－ジリチオペンタン、１，６－ジリチオヘキサン、１，１０－ジリチオデカン、１，１－ジリチオジフェニレン、ジリチオポリブタジエン、ジリチオポリイソプレン、１，４－ジリチオベンゼン、１，２－ジリチオ－１，２－ジフェニルエタン、１，４－ジリチオ－２－エチルシクロヘキサン、１，３，５－トリリチオベンゼン、１，３，５－トリリチオ－２，４，６－トリエチルベンゼン等の多官能性有機リチウム化合物が挙げられる。なかでも、本発明の効果がより優れる理由から、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔｅｒｔ－ブチルリチウムのモノ有機リチウム化合物が好ましく、ｎ－ブチルリチウムがより好ましい。 (Organolithium compound)
The above-mentioned organolithium compound is not particularly limited, and specific examples thereof include monoorganolithium compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, and benzyllithium; 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4-dilithio Benzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-trilithio-2,4,6- Examples thereof include polyfunctional organolithium compounds such as triethylbenzene. Of these, monoorganolithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium are preferable, and n-butyllithium is more preferable, because the effect of the present invention is more excellent.
上記有機リチウム化合物は特に制限されないが、その具体例としては、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔｅｒｔ－ブチルリチウム、ｎ－プロピルリチウム、ｉｓｏ－プロピルリチウム、ベンジルリチウム等のモノ有機リチウム化合物；１，４－ジリチオブタン、１，５－ジリチオペンタン、１，６－ジリチオヘキサン、１，１０－ジリチオデカン、１，１－ジリチオジフェニレン、ジリチオポリブタジエン、ジリチオポリイソプレン、１，４－ジリチオベンゼン、１，２－ジリチオ－１，２－ジフェニルエタン、１，４－ジリチオ－２－エチルシクロヘキサン、１，３，５－トリリチオベンゼン、１，３，５－トリリチオ－２，４，６－トリエチルベンゼン等の多官能性有機リチウム化合物が挙げられる。なかでも、本発明の効果がより優れる理由から、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔｅｒｔ－ブチルリチウムのモノ有機リチウム化合物が好ましく、ｎ－ブチルリチウムがより好ましい。 (Organolithium compound)
The above-mentioned organolithium compound is not particularly limited, and specific examples thereof include monoorganolithium compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, and benzyllithium; 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4-dilithio Benzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-trilithio-2,4,6- Examples thereof include polyfunctional organolithium compounds such as triethylbenzene. Of these, monoorganolithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium are preferable, and n-butyllithium is more preferable, because the effect of the present invention is more excellent.
有機リチウム化合物の使用量は特に制限されないが、本発明の効果がより優れる理由から、上記モノマーに対して、０．００１～１０モル％であることが好ましい。
The amount of the organic lithium compound used is not particularly limited, but it is preferably 0.001 to 10 mol% with respect to the above-mentioned monomer for the reason that the effect of the present invention is more excellent.
＜末端変性工程＞
末端変性工程は、特定の求電子剤を用いて上記モノマー（ジエンを含有するモノマー）の重合を停止することで、上記液状ジエン系重合体（活性末端を有する液状ジエン系重合体）の末端に上記特定の求電子剤に由来する官能基Ａを導入し、末端に上記官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体を得る工程である。 <Terminal denaturation process>
In the terminal modification step, the polymerization of the above-mentioned monomer (monomer containing a diene) is stopped by using a specific electrophoretic agent, so that the end of the above-mentioned liquid diene-based polymer (liquid diene-based polymer having an active end) is formed. This is a step of introducing a functional group A derived from the specific electrophoretic agent to obtain a terminal-modified liquid diene polymer which is a liquid diene polymer having the functional group A at the terminal.
末端変性工程は、特定の求電子剤を用いて上記モノマー（ジエンを含有するモノマー）の重合を停止することで、上記液状ジエン系重合体（活性末端を有する液状ジエン系重合体）の末端に上記特定の求電子剤に由来する官能基Ａを導入し、末端に上記官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体を得る工程である。 <Terminal denaturation process>
In the terminal modification step, the polymerization of the above-mentioned monomer (monomer containing a diene) is stopped by using a specific electrophoretic agent, so that the end of the above-mentioned liquid diene-based polymer (liquid diene-based polymer having an active end) is formed. This is a step of introducing a functional group A derived from the specific electrophoretic agent to obtain a terminal-modified liquid diene polymer which is a liquid diene polymer having the functional group A at the terminal.
（特定求電子剤）
上記特定の求電子剤（以下、「特定求電子剤」とも言う）は、液状ジエン系重合体の活性末端と反応することで官能基Ａとなる化合物である。
例えば、上記特定求電子剤がアミンである場合、上記官能基Ａはアミノ基となり、上記特定求電子剤がケトンである場合、上記官能基Ａは水酸基となり、上記特定求電子剤がアセタールである場合、上記官能基Ａはカルボキシ基となり（ただし、液状ジエン系重合体の活性末端と反応した後に加水分解が必要）、上記特定求電子剤がアルコキシシランである場合、上記官能基Ａはアルコキシシリル基となり、上記特定求電子剤がアルデヒドである場合、上記官能基Ａはアルデヒド基となり、上記特定求電子剤がエポキシドである場合、上記官能基Ａはエポキシ基となり、上記特定求電子剤がアミノ基を有するアルコキシシランである場合、上記官能基Ａはアミノ基を有するアルコキシシリル基となる。
また、上記特定求電子剤が環状シラザンである場合、上記官能基Ａはアミノ基となり、上記環状シラザンがアルコキシシリル基を有する場合、上記官能基Ａはアミノ基を有するアルコキシシリル基となる。 (Specific electrophile)
The specific electrophile (hereinafter, also referred to as "specific electrophile") is a compound that becomes a functional group A by reacting with the active terminal of a liquid diene polymer.
For example, when the specific electropoxide is an amine, the functional group A is an amino group, and when the specific electropoxide is a ketone, the functional group A is a hydroxyl group and the specific electropoxide is an acetal. In this case, the functional group A becomes a carboxy group (however, hydrolysis is required after reacting with the active terminal of the liquid diene polymer), and when the specific electrophilic agent is an alkoxysilane, the functional group A is an alkoxysilyl. When the specific electrophilic agent is an aldehyde, the functional group A becomes an aldehyde group, and when the specific electrophoretic agent is an epoxide, the functional group A becomes an epoxy group and the specific electrophoretic agent is an amino. In the case of an alkoxysilane having a group, the functional group A becomes an alkoxysilyl group having an amino group.
When the specific electrophilic agent is cyclic silazane, the functional group A becomes an amino group, and when the cyclic silazane has an alkoxysilyl group, the functional group A becomes an alkoxysilyl group having an amino group.
上記特定の求電子剤（以下、「特定求電子剤」とも言う）は、液状ジエン系重合体の活性末端と反応することで官能基Ａとなる化合物である。
例えば、上記特定求電子剤がアミンである場合、上記官能基Ａはアミノ基となり、上記特定求電子剤がケトンである場合、上記官能基Ａは水酸基となり、上記特定求電子剤がアセタールである場合、上記官能基Ａはカルボキシ基となり（ただし、液状ジエン系重合体の活性末端と反応した後に加水分解が必要）、上記特定求電子剤がアルコキシシランである場合、上記官能基Ａはアルコキシシリル基となり、上記特定求電子剤がアルデヒドである場合、上記官能基Ａはアルデヒド基となり、上記特定求電子剤がエポキシドである場合、上記官能基Ａはエポキシ基となり、上記特定求電子剤がアミノ基を有するアルコキシシランである場合、上記官能基Ａはアミノ基を有するアルコキシシリル基となる。
また、上記特定求電子剤が環状シラザンである場合、上記官能基Ａはアミノ基となり、上記環状シラザンがアルコキシシリル基を有する場合、上記官能基Ａはアミノ基を有するアルコキシシリル基となる。 (Specific electrophile)
The specific electrophile (hereinafter, also referred to as "specific electrophile") is a compound that becomes a functional group A by reacting with the active terminal of a liquid diene polymer.
For example, when the specific electropoxide is an amine, the functional group A is an amino group, and when the specific electropoxide is a ketone, the functional group A is a hydroxyl group and the specific electropoxide is an acetal. In this case, the functional group A becomes a carboxy group (however, hydrolysis is required after reacting with the active terminal of the liquid diene polymer), and when the specific electrophilic agent is an alkoxysilane, the functional group A is an alkoxysilyl. When the specific electrophilic agent is an aldehyde, the functional group A becomes an aldehyde group, and when the specific electrophoretic agent is an epoxide, the functional group A becomes an epoxy group and the specific electrophoretic agent is an amino. In the case of an alkoxysilane having a group, the functional group A becomes an alkoxysilyl group having an amino group.
When the specific electrophilic agent is cyclic silazane, the functional group A becomes an amino group, and when the cyclic silazane has an alkoxysilyl group, the functional group A becomes an alkoxysilyl group having an amino group.
上記特定求電子剤は、本発明の効果がより優れる理由から、環状シラザンであることが好ましい。
The specific electrophile is preferably cyclic silazan for the reason that the effect of the present invention is more excellent.
上記環状シラザンは、本発明の効果がより優れる理由から、下記式（Ｓ）で表される化合物であることが好ましい。
The cyclic silazane is preferably a compound represented by the following formula (S) because the effect of the present invention is more excellent.
上記式（Ｓ）中、Ｒ１～Ｒ３は、それぞれ独立に、水素原子または置換基を表す。置換基の具体例及び好適な態様は上述した式（Ｍ）中のＲ１及びＲ２と同じである。
上記式（Ｓ）中、Ｌは、２価の有機基を表す。２価の有機基の具体例及び好適な態様は、上述した式（Ｍ）中のＬと同じである。 In the above formula (S), R 1 to R 3 independently represent a hydrogen atom or a substituent. Specific examples and preferred embodiments of the substituent are the same as those of R 1 and R 2 in the above-mentioned formula (M).
In the above formula (S), L represents a divalent organic group. Specific examples and preferred embodiments of the divalent organic group are the same as L in the above-mentioned formula (M).
上記式（Ｓ）中、Ｌは、２価の有機基を表す。２価の有機基の具体例及び好適な態様は、上述した式（Ｍ）中のＬと同じである。 In the above formula (S), R 1 to R 3 independently represent a hydrogen atom or a substituent. Specific examples and preferred embodiments of the substituent are the same as those of R 1 and R 2 in the above-mentioned formula (M).
In the above formula (S), L represents a divalent organic group. Specific examples and preferred embodiments of the divalent organic group are the same as L in the above-mentioned formula (M).
上記式（Ｓ）中、Ｒ１は、本発明の効果がより優れる理由から、アルキル基（好ましくは、炭素数１～１０）、アルキルシリル基（好ましくは、炭素数１～１０）、芳香族炭化水素基（好ましくは、炭素数６～１８）であることが好ましく、アルキルシリル基であることがより好ましい。
In the above formula (S), R 1 has an alkyl group (preferably 1 to 10 carbon atoms), an alkylsilyl group (preferably 1 to 10 carbon atoms), and an aromatic group because the effect of the present invention is more excellent. It is preferably a hydrocarbon group (preferably 6 to 18 carbon atoms), and more preferably an alkylsilyl group.
上記式（Ｓ）中、Ｒ２及びＲ３は、本発明の効果がより優れる理由から、それぞれ独立に、ヒドロカルビルオキシ基（－ＯＲ基：Ｒは炭化水素基）であることが好ましく、アルコキシ基（好ましくは、炭素数１～１０）であることがより好ましい。
In the above formula (S), R 2 and R 3 are preferably hydrocarbyloxy groups (-OR group: R is a hydrocarbon group) independently of each other, and are preferably alkoxy groups, for the reason that the effect of the present invention is more excellent. (Preferably, the number of carbon atoms is 1 to 10).
上記式（Ｓ）中、Ｌは、本発明の効果がより優れる理由から、アルキレン基（好ましくは炭素数１～１０、より好ましくは２～８、さらに好ましくは３～５）であることが好ましい。
In the above formula (S), L is preferably an alkylene group (preferably 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 3 to 5 carbon atoms) because the effect of the present invention is more excellent. ..
上記式（Ｓ）で表される化合物としては、例えば、Ｎ－ｎ－ブチル－１，１－ジメトキシ－２－アザシラシクロペンタン、Ｎ－フェニル－１，１－ジメトキシ－２－アザシラシクロペンタン、Ｎ－トリメチルシリル－１，１－ジメトキシ－２－アザシラシクロペンタン、Ｎ－トリメチルシリル－１，１－ジエトキシ－２－アザシラシクロペンタンなどが挙げられる。
なお、環状シラザンのケイ素原子は求電子性を示すと考えられる。 Examples of the compound represented by the above formula (S) include Nn-butyl-1,1-dimethoxy-2-azasilacyclopentane and N-phenyl-1,1-dimethoxy-2-azasilacyclopentane. , N-trimethylsilyl-1,1-dimethoxy-2-azasilacyclopentane, N-trimethylsilyl-1,1-diethoxy-2-azasilacyclopentane and the like.
The silicon atom of cyclic silazane is considered to exhibit electrophilicity.
なお、環状シラザンのケイ素原子は求電子性を示すと考えられる。 Examples of the compound represented by the above formula (S) include Nn-butyl-1,1-dimethoxy-2-azasilacyclopentane and N-phenyl-1,1-dimethoxy-2-azasilacyclopentane. , N-trimethylsilyl-1,1-dimethoxy-2-azasilacyclopentane, N-trimethylsilyl-1,1-diethoxy-2-azasilacyclopentane and the like.
The silicon atom of cyclic silazane is considered to exhibit electrophilicity.
上記有機リチウム化合物に対する特定求電子剤の量は特に制限されないが、本発明の効果がより優れる理由から、モル比で、０．１～１０であることが好ましく、１～５であることがより好ましい。
The amount of the specific electrophile with respect to the organolithium compound is not particularly limited, but for the reason that the effect of the present invention is more excellent, the molar ratio is preferably 0.1 to 10 and more preferably 1 to 5. preferable.
＜主鎖変性工程＞
主鎖変性工程は、上記末端変性液状ジエン系重合体と、ラジカル開始剤と、上述した式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上述した式（１）で表される官能基Ｂを導入し、末端に上記官能基Ａを有し主鎖に上記官能基Ｂを有する液状ジエン系重合体である変性液状ジエン系重合体を得る工程である。
上記主鎖変性工程は、上述した製造方法１と同じである。 <Main chain modification process>
In the backbone modification step, the main chain of the terminal-modified liquid diene polymer is formed by reacting the terminal-modified liquid diene polymer with the radical initiator and the compound represented by the above formula (2). A modified liquid diene polymer which is a liquid diene polymer having the functional group A at the terminal and the functional group B in the backbone is introduced into the above-mentioned functional group B represented by the formula (1). This is the process of obtaining.
The main chain modification step is the same as the above-mentioned production method 1.
主鎖変性工程は、上記末端変性液状ジエン系重合体と、ラジカル開始剤と、上述した式（２）で表される化合物とを反応させることで、上記末端変性液状ジエン系重合体の主鎖に上述した式（１）で表される官能基Ｂを導入し、末端に上記官能基Ａを有し主鎖に上記官能基Ｂを有する液状ジエン系重合体である変性液状ジエン系重合体を得る工程である。
上記主鎖変性工程は、上述した製造方法１と同じである。 <Main chain modification process>
In the backbone modification step, the main chain of the terminal-modified liquid diene polymer is formed by reacting the terminal-modified liquid diene polymer with the radical initiator and the compound represented by the above formula (2). A modified liquid diene polymer which is a liquid diene polymer having the functional group A at the terminal and the functional group B in the backbone is introduced into the above-mentioned functional group B represented by the formula (1). This is the process of obtaining.
The main chain modification step is the same as the above-mentioned production method 1.
［用途］
本発明の重合体は、ゴム組成物、タイヤ等に有用である。 [Use]
The polymer of the present invention is useful for rubber compositions, tires and the like.
本発明の重合体は、ゴム組成物、タイヤ等に有用である。 [Use]
The polymer of the present invention is useful for rubber compositions, tires and the like.
以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
〔変性液状ジエン系重合体の製造〕
以下のとおり、変性液状ジエン系重合体を製造した。
なお、実施例１～２は、末端に官能基Ａを有し、主鎖に官能基Ｂを有する、液状ジエン系重合体であるため、本発明の重合体に該当する。一方、比較例１は、末端に官能基Ａを有さないため、本発明の重合体に該当しない。また、比較例２～５は、主鎖に官能基Ｂを有さないため、本発明の重合体に該当しない。 [Manufacturing of modified liquid diene polymer]
A modified liquid diene polymer was produced as follows.
Since Examples 1 and 2 are liquid diene-based polymers having a functional group A at the terminal and a functional group B in the main chain, they fall under the polymer of the present invention. On the other hand, Comparative Example 1 does not have a functional group A at the terminal, and therefore does not correspond to the polymer of the present invention. Further, Comparative Examples 2 to 5 do not correspond to the polymer of the present invention because they do not have a functional group B in the main chain.
以下のとおり、変性液状ジエン系重合体を製造した。
なお、実施例１～２は、末端に官能基Ａを有し、主鎖に官能基Ｂを有する、液状ジエン系重合体であるため、本発明の重合体に該当する。一方、比較例１は、末端に官能基Ａを有さないため、本発明の重合体に該当しない。また、比較例２～５は、主鎖に官能基Ｂを有さないため、本発明の重合体に該当しない。 [Manufacturing of modified liquid diene polymer]
A modified liquid diene polymer was produced as follows.
Since Examples 1 and 2 are liquid diene-based polymers having a functional group A at the terminal and a functional group B in the main chain, they fall under the polymer of the present invention. On the other hand, Comparative Example 1 does not have a functional group A at the terminal, and therefore does not correspond to the polymer of the present invention. Further, Comparative Examples 2 to 5 do not correspond to the polymer of the present invention because they do not have a functional group B in the main chain.
＜実施例１＞
下記のとおり、実施例１の変性液状ジエン系重合体を製造した。 <Example 1>
As described below, the modified liquid diene polymer of Example 1 was produced.
下記のとおり、実施例１の変性液状ジエン系重合体を製造した。 <Example 1>
As described below, the modified liquid diene polymer of Example 1 was produced.
（モノマー重合工程）
シクロヘキサン４．２ｋｇに１，３－ブタジエン１２００ｍＬ、ｎ－ブチルリチウム３０ｍＬ、２，２－ジ（２－テトラヒドロフリル）プロパン０．１ｍＬを添加し加熱攪拌（６０℃、２４時間）して、活性末端を有する液状ブタジエン重合体を得た。 (Monomer polymerization process)
To 4.2 kg of cyclohexane, 1200 mL of 1,3-butadiene, 30 mL of n-butyllithium, and 0.1 mL of 2,2-di (2-tetrahydrofuryl) propane were added and heated and stirred (60 ° C., 24 hours) to activate the terminal. A liquid butadiene polymer having the above was obtained.
シクロヘキサン４．２ｋｇに１，３－ブタジエン１２００ｍＬ、ｎ－ブチルリチウム３０ｍＬ、２，２－ジ（２－テトラヒドロフリル）プロパン０．１ｍＬを添加し加熱攪拌（６０℃、２４時間）して、活性末端を有する液状ブタジエン重合体を得た。 (Monomer polymerization process)
To 4.2 kg of cyclohexane, 1200 mL of 1,3-butadiene, 30 mL of n-butyllithium, and 0.1 mL of 2,2-di (2-tetrahydrofuryl) propane were added and heated and stirred (60 ° C., 24 hours) to activate the terminal. A liquid butadiene polymer having the above was obtained.
（末端変性工程）
次いで、環状シラザン（下記構造式、ここでＭｅはメチル基を表す）（上述した式（Ｓ）で表される化合物に該当）４０ｍＬを添加してブタジエンの重合を停止した。
重合溶液を多量のＭｅＯＨ（メタノール）に添加し精製を行い、５０℃で２４時間真空乾燥を行うことで、一方の末端に下記式（ｍ１）（ここで、＊は結合位置を表す）で表される官能基（上述した式（Ｍ）で表される基に該当）（官能基Ａ）を有する液状ブタジエン重合体である末端変性液状ブタジエン重合体（Ｍｗ：４０，０００）を得た。 (Terminal denaturation process)
Then, 40 mL of cyclic silazane (the following structural formula, where Me represents a methyl group) (corresponding to the compound represented by the above formula (S)) was added to terminate the polymerization of butadiene.
By adding the polymerization solution to a large amount of MeOH (methanol) for purification and vacuum drying at 50 ° C. for 24 hours, the following formula (m1) (where * represents the bond position) is expressed at one end. A terminal-modified liquid butadiene polymer (Mw: 40,000), which is a liquid butadiene polymer having a functional group (corresponding to the group represented by the above formula (M)) (functional group A), was obtained.
次いで、環状シラザン（下記構造式、ここでＭｅはメチル基を表す）（上述した式（Ｓ）で表される化合物に該当）４０ｍＬを添加してブタジエンの重合を停止した。
重合溶液を多量のＭｅＯＨ（メタノール）に添加し精製を行い、５０℃で２４時間真空乾燥を行うことで、一方の末端に下記式（ｍ１）（ここで、＊は結合位置を表す）で表される官能基（上述した式（Ｍ）で表される基に該当）（官能基Ａ）を有する液状ブタジエン重合体である末端変性液状ブタジエン重合体（Ｍｗ：４０，０００）を得た。 (Terminal denaturation process)
Then, 40 mL of cyclic silazane (the following structural formula, where Me represents a methyl group) (corresponding to the compound represented by the above formula (S)) was added to terminate the polymerization of butadiene.
By adding the polymerization solution to a large amount of MeOH (methanol) for purification and vacuum drying at 50 ° C. for 24 hours, the following formula (m1) (where * represents the bond position) is expressed at one end. A terminal-modified liquid butadiene polymer (Mw: 40,000), which is a liquid butadiene polymer having a functional group (corresponding to the group represented by the above formula (M)) (functional group A), was obtained.
（主鎖変性工程）
その後、ジクロロメタン５０ｍＬに、上記末端変性液状ブタジエン重合体５０ｇ、３－メルカプトプロピルトリエトキシシラン（上述した式（２）で表される化合物に該当）３．７ｇ、ＡＩＢＮ（アゾビスイソブチロニトリル）０．７ｇを添加し、加熱攪拌（８０℃、２４時間）した。
反応溶液を多量のＭｅＯＨ（メタノール）に添加し精製を行い、５０℃で２４時間真空乾燥を行うことで、一方の末端に上記式（ｍ１）で表される官能基を有し、主鎖に１分子あたり平均２個の上述した式（１）で表される官能基Ｂ（ただし、式（１）中、Ｒ１はプロピレン基であり、Ｒ２、Ｒ３及びＲ４はエトキシ基である）を有する液状ブタジエン重合体である変性液状ブタジエン重合体（Ｍｗ：４０，０００）を得た。得られた変性液状ブタジエン重合体において、末端に有する官能基Ａの数（１分子あたりの平均の数）と、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）との合計は３であった。 (Main chain modification step)
Then, in 50 mL of dichloromethane, 50 g of the terminal-modified liquid butadiene polymer, 3.7 g of 3-mercaptopropyltriethoxysilane (corresponding to the compound represented by the above formula (2)), AIBN (azobisisobutyronitrile). 0.7 g was added, and the mixture was heated and stirred (80 ° C., 24 hours).
By adding the reaction solution to a large amount of MeOH (methanol) for purification and vacuum drying at 50 ° C. for 24 hours, one end has a functional group represented by the above formula (m1), and the main chain has a functional group represented by the above formula (m1). An average of two functional groups B represented by the above formula (1) per molecule (however, in formula (1), R 1 is a propylene group and R 2 , R 3 and R 4 are ethoxy groups. ) Was obtained as a modified liquid butadiene polymer (Mw: 40,000). In the obtained modified liquid butadiene polymer, the sum of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). Was 3.
その後、ジクロロメタン５０ｍＬに、上記末端変性液状ブタジエン重合体５０ｇ、３－メルカプトプロピルトリエトキシシラン（上述した式（２）で表される化合物に該当）３．７ｇ、ＡＩＢＮ（アゾビスイソブチロニトリル）０．７ｇを添加し、加熱攪拌（８０℃、２４時間）した。
反応溶液を多量のＭｅＯＨ（メタノール）に添加し精製を行い、５０℃で２４時間真空乾燥を行うことで、一方の末端に上記式（ｍ１）で表される官能基を有し、主鎖に１分子あたり平均２個の上述した式（１）で表される官能基Ｂ（ただし、式（１）中、Ｒ１はプロピレン基であり、Ｒ２、Ｒ３及びＲ４はエトキシ基である）を有する液状ブタジエン重合体である変性液状ブタジエン重合体（Ｍｗ：４０，０００）を得た。得られた変性液状ブタジエン重合体において、末端に有する官能基Ａの数（１分子あたりの平均の数）と、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）との合計は３であった。 (Main chain modification step)
Then, in 50 mL of dichloromethane, 50 g of the terminal-modified liquid butadiene polymer, 3.7 g of 3-mercaptopropyltriethoxysilane (corresponding to the compound represented by the above formula (2)), AIBN (azobisisobutyronitrile). 0.7 g was added, and the mixture was heated and stirred (80 ° C., 24 hours).
By adding the reaction solution to a large amount of MeOH (methanol) for purification and vacuum drying at 50 ° C. for 24 hours, one end has a functional group represented by the above formula (m1), and the main chain has a functional group represented by the above formula (m1). An average of two functional groups B represented by the above formula (1) per molecule (however, in formula (1), R 1 is a propylene group and R 2 , R 3 and R 4 are ethoxy groups. ) Was obtained as a modified liquid butadiene polymer (Mw: 40,000). In the obtained modified liquid butadiene polymer, the sum of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). Was 3.
＜実施例２＞
主鎖変性工程において、３－メルカプトプロピルトリエトキシシランの添加量を７．４ｇに変更した点以外は、実施例１と同様の手順に従って、変性液状ブタジエン重合体を製造した。得られた変性液状ブタジエン重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に１分子あたり平均４個の上述した式（１）で表される官能基Ｂ（ただし、式（１）中、Ｒ１はプロピレン基であり、Ｒ２、Ｒ３及びＲ４はエトキシ基である）を有する液状ブタジエン重合体である変性液状ブタジエン重合体（Ｍｗ：４０，０００）であった。得られた変性液状ブタジエン重合体において、末端に有する官能基Ａの数（１分子あたりの平均の数）と、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）との合計は５であった。 <Example 2>
A modified liquid butadiene polymer was produced according to the same procedure as in Example 1 except that the amount of 3-mercaptopropyltriethoxysilane added was changed to 7.4 g in the backbone modification step. The obtained modified liquid butadiene polymer has a functional group (functional group A) represented by the above formula (m1) at one end, and has an average of 4 above-mentioned formulas (1) per molecule in the main chain. Modified liquid butadiene weight which is a liquid butadiene polymer having a functional group B represented by (where R 1 is a propylene group and R 2 , R 3 and R 4 are ethoxy groups in the formula (1)). It was a coalescence (Mw: 40,000). In the obtained modified liquid butadiene polymer, the sum of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). Was 5.
主鎖変性工程において、３－メルカプトプロピルトリエトキシシランの添加量を７．４ｇに変更した点以外は、実施例１と同様の手順に従って、変性液状ブタジエン重合体を製造した。得られた変性液状ブタジエン重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に１分子あたり平均４個の上述した式（１）で表される官能基Ｂ（ただし、式（１）中、Ｒ１はプロピレン基であり、Ｒ２、Ｒ３及びＲ４はエトキシ基である）を有する液状ブタジエン重合体である変性液状ブタジエン重合体（Ｍｗ：４０，０００）であった。得られた変性液状ブタジエン重合体において、末端に有する官能基Ａの数（１分子あたりの平均の数）と、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）との合計は５であった。 <Example 2>
A modified liquid butadiene polymer was produced according to the same procedure as in Example 1 except that the amount of 3-mercaptopropyltriethoxysilane added was changed to 7.4 g in the backbone modification step. The obtained modified liquid butadiene polymer has a functional group (functional group A) represented by the above formula (m1) at one end, and has an average of 4 above-mentioned formulas (1) per molecule in the main chain. Modified liquid butadiene weight which is a liquid butadiene polymer having a functional group B represented by (where R 1 is a propylene group and R 2 , R 3 and R 4 are ethoxy groups in the formula (1)). It was a coalescence (Mw: 40,000). In the obtained modified liquid butadiene polymer, the sum of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule). Was 5.
＜比較例１＞
末端変性工程において、環状シラザンの代わりにメタノールを用いた点以外は実施例２と同様の手順に従って、変性液状ブタジエン重合体を製造した。得られた変性液状ブタジエン共重合体は、末端に官能基を有さず、主鎖に１分子あたり平均４個の上述した式（１）で表される官能基Ｂ（ただし、式（１）中、Ｒ１はプロピレン基であり、Ｒ２、Ｒ３及びＲ４はエトキシ基である）を有する液状ブタジエン重合体である変性液状ブタジエン重合体（主鎖変性液状ブタジエン重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 1>
A modified liquid butadiene polymer was produced according to the same procedure as in Example 2 except that methanol was used instead of cyclic silazane in the terminal modification step. The obtained modified liquid butadiene copolymer has no functional group at the terminal and has an average of 4 functional groups B per molecule per molecule in the main chain represented by the above-mentioned formula (1) (however, the formula (1)). Among them, R 1 is a propylene group, and R 2 , R 3 and R 4 are ethoxy groups), which is a modified liquid butadiene polymer (main chain modified liquid butadiene polymer) (Mw: 40). It was 000).
末端変性工程において、環状シラザンの代わりにメタノールを用いた点以外は実施例２と同様の手順に従って、変性液状ブタジエン重合体を製造した。得られた変性液状ブタジエン共重合体は、末端に官能基を有さず、主鎖に１分子あたり平均４個の上述した式（１）で表される官能基Ｂ（ただし、式（１）中、Ｒ１はプロピレン基であり、Ｒ２、Ｒ３及びＲ４はエトキシ基である）を有する液状ブタジエン重合体である変性液状ブタジエン重合体（主鎖変性液状ブタジエン重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 1>
A modified liquid butadiene polymer was produced according to the same procedure as in Example 2 except that methanol was used instead of cyclic silazane in the terminal modification step. The obtained modified liquid butadiene copolymer has no functional group at the terminal and has an average of 4 functional groups B per molecule per molecule in the main chain represented by the above-mentioned formula (1) (however, the formula (1)). Among them, R 1 is a propylene group, and R 2 , R 3 and R 4 are ethoxy groups), which is a modified liquid butadiene polymer (main chain modified liquid butadiene polymer) (Mw: 40). It was 000).
＜比較例２＞
主鎖変性工程を行わなかった点以外は実施例１と同様の手順に従って、変性液状ブタジエン共重合体を製造した。得られた変性液状ブタジエン重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に官能基Ｂを有さない液状ブタジエン重合体である変性液状ブタジエン重合体（末端変性液状ブタジエン重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 2>
A modified liquid butadiene copolymer was produced according to the same procedure as in Example 1 except that the main chain modification step was not performed. The obtained modified liquid butadiene polymer is a liquid butadiene polymer having a functional group (functional group A) represented by the above formula (m1) at one end and no functional group B in the main chain. It was a modified liquid butadiene polymer (terminal modified liquid butadiene polymer) (Mw: 40,000).
主鎖変性工程を行わなかった点以外は実施例１と同様の手順に従って、変性液状ブタジエン共重合体を製造した。得られた変性液状ブタジエン重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に官能基Ｂを有さない液状ブタジエン重合体である変性液状ブタジエン重合体（末端変性液状ブタジエン重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 2>
A modified liquid butadiene copolymer was produced according to the same procedure as in Example 1 except that the main chain modification step was not performed. The obtained modified liquid butadiene polymer is a liquid butadiene polymer having a functional group (functional group A) represented by the above formula (m1) at one end and no functional group B in the main chain. It was a modified liquid butadiene polymer (terminal modified liquid butadiene polymer) (Mw: 40,000).
＜比較例３＞
シクロヘキサン４．２ｋｇに１，３－ブタジエン５６０ｍｌ、イソプレン６５０ｍｌ、ｎ－ブチルリチウム３０ｍＬ、２，２－ジ（２－テトラヒドロフリル）プロパン０．１ｍＬを添加し加熱攪拌（６０℃、２４時間）して、活性末端を有する液状イソプレンブタジエン共重合体（ランダム共重合体）を得た。次いで、実施例１の同様の手順に従って、末端変性工程を行い、変性液状イソプレンブタジエン共重合体を得た。
得られた変性液状イソプレンブタジエン共重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に官能基Ｂを有さない液状イソプレンブタジエン共重合体（ランダム共重合体）である変性液状イソプレンブタジエン共重合体（末端変性液状イソプレンブタジエン共重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 3>
To 4.2 kg of cyclohexane, 560 ml of 1,3-butadiene, 650 ml of isoprene, 30 mL of n-butyllithium, and 0.1 mL of 2,2-di (2-tetrahydrofuryl) propane were added and heated and stirred (60 ° C., 24 hours). , A liquid isoprene butadiene copolymer having an active terminal (random copolymer) was obtained. Then, a terminal modification step was carried out according to the same procedure of Example 1 to obtain a modified liquid isoprene butadiene copolymer.
The obtained modified liquid isoprene butadiene copolymer has a functional group (functional group A) represented by the above formula (m1) at one end thereof and does not have a functional group B in the main chain. It was a modified liquid isoprene butadiene copolymer (terminal-modified liquid isoprene butadiene copolymer) (Mw: 40,000) which is a polymer (random copolymer).
シクロヘキサン４．２ｋｇに１，３－ブタジエン５６０ｍｌ、イソプレン６５０ｍｌ、ｎ－ブチルリチウム３０ｍＬ、２，２－ジ（２－テトラヒドロフリル）プロパン０．１ｍＬを添加し加熱攪拌（６０℃、２４時間）して、活性末端を有する液状イソプレンブタジエン共重合体（ランダム共重合体）を得た。次いで、実施例１の同様の手順に従って、末端変性工程を行い、変性液状イソプレンブタジエン共重合体を得た。
得られた変性液状イソプレンブタジエン共重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に官能基Ｂを有さない液状イソプレンブタジエン共重合体（ランダム共重合体）である変性液状イソプレンブタジエン共重合体（末端変性液状イソプレンブタジエン共重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 3>
To 4.2 kg of cyclohexane, 560 ml of 1,3-butadiene, 650 ml of isoprene, 30 mL of n-butyllithium, and 0.1 mL of 2,2-di (2-tetrahydrofuryl) propane were added and heated and stirred (60 ° C., 24 hours). , A liquid isoprene butadiene copolymer having an active terminal (random copolymer) was obtained. Then, a terminal modification step was carried out according to the same procedure of Example 1 to obtain a modified liquid isoprene butadiene copolymer.
The obtained modified liquid isoprene butadiene copolymer has a functional group (functional group A) represented by the above formula (m1) at one end thereof and does not have a functional group B in the main chain. It was a modified liquid isoprene butadiene copolymer (terminal-modified liquid isoprene butadiene copolymer) (Mw: 40,000) which is a polymer (random copolymer).
＜比較例４＞
シクロヘキサン４．２ｋｇに１，３－ブタジエン５６０ｍＬ、ｎ－ブチルリチウム３０ｍＬ、２，２－ジ（２－テトラヒドロフリル）プロパン０．１ｍＬを添加し加熱攪拌（６０℃、１２時間）して、その後イソプレン６５０ｍｌ添加し加熱攪拌（６０℃、１２時間）することで活性末端を有する液状イソプレンブタジエン共重合体（ブロック共重合体）を得た。次いで、実施例１の同様の手順に従って、末端変性工程を行い、変性液状イソプレンブタジエン共重合体を得た。
得られた変性液状イソプレンブタジエン共重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に官能基Ｂを有さない液状イソプレンブタジエン共重合体（ブロック共重合体）である変性液状イソプレンブタジエン共重合体（末端変性液状イソプレンブタジエン共重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 4>
Add 560 mL of 1,3-butadiene, 30 mL of n-butyllithium, and 0.1 mL of 2,2-di (2-tetrahydrofuryl) propane to 4.2 kg of cyclohexane, heat and stir (60 ° C., 12 hours), and then isoprene. A liquid isoprene butadiene copolymer (block copolymer) having an active terminal was obtained by adding 650 ml and heating and stirring (60 ° C., 12 hours). Then, a terminal modification step was carried out according to the same procedure of Example 1 to obtain a modified liquid isoprene butadiene copolymer.
The obtained modified liquid isoprene butadiene copolymer has a functional group (functional group A) represented by the above formula (m1) at one end thereof and does not have a functional group B in the main chain. It was a modified liquid isoprene butadiene copolymer (terminal-modified liquid isoprene butadiene copolymer) (Mw: 40,000) which is a polymer (block copolymer).
シクロヘキサン４．２ｋｇに１，３－ブタジエン５６０ｍＬ、ｎ－ブチルリチウム３０ｍＬ、２，２－ジ（２－テトラヒドロフリル）プロパン０．１ｍＬを添加し加熱攪拌（６０℃、１２時間）して、その後イソプレン６５０ｍｌ添加し加熱攪拌（６０℃、１２時間）することで活性末端を有する液状イソプレンブタジエン共重合体（ブロック共重合体）を得た。次いで、実施例１の同様の手順に従って、末端変性工程を行い、変性液状イソプレンブタジエン共重合体を得た。
得られた変性液状イソプレンブタジエン共重合体は、一方の末端に上記式（ｍ１）で表される官能基（官能基Ａ）を有し、主鎖に官能基Ｂを有さない液状イソプレンブタジエン共重合体（ブロック共重合体）である変性液状イソプレンブタジエン共重合体（末端変性液状イソプレンブタジエン共重合体）（Ｍｗ：４０，０００）であった。 <Comparative Example 4>
Add 560 mL of 1,3-butadiene, 30 mL of n-butyllithium, and 0.1 mL of 2,2-di (2-tetrahydrofuryl) propane to 4.2 kg of cyclohexane, heat and stir (60 ° C., 12 hours), and then isoprene. A liquid isoprene butadiene copolymer (block copolymer) having an active terminal was obtained by adding 650 ml and heating and stirring (60 ° C., 12 hours). Then, a terminal modification step was carried out according to the same procedure of Example 1 to obtain a modified liquid isoprene butadiene copolymer.
The obtained modified liquid isoprene butadiene copolymer has a functional group (functional group A) represented by the above formula (m1) at one end thereof and does not have a functional group B in the main chain. It was a modified liquid isoprene butadiene copolymer (terminal-modified liquid isoprene butadiene copolymer) (Mw: 40,000) which is a polymer (block copolymer).
〔シリカ吸着性〕
キシレン１５ｇ中に、得られた変性液状ジエン系重合体１．５ｇ、シリカ３．０ｇを溶解させ、１４０℃、２０分加熱攪拌した。その後濾過、回収し、８０℃、２４時間真空乾燥を行い、質量（最終質量）を測定した。そして、以下の計算式によってシリカ吸着性を求めた。
（シリカ吸着性）＝（最終質量－評価に用いたシリカの質量）／（評価に用いた変性液状ジエン系重合体の質量）×１００（単位は％）
結果を下記表１に示す。シリカ吸着性が大きい程、シリカ吸着性に優れることを表す。 [Silica adsorption]
1.5 g of the obtained modified liquid diene polymer and 3.0 g of silica were dissolved in 15 g of xylene, and the mixture was heated and stirred at 140 ° C. for 20 minutes. After that, it was filtered and collected, vacuum dried at 80 ° C. for 24 hours, and the mass (final mass) was measured. Then, the silica adsorptivity was determined by the following calculation formula.
(Silica adsorptivity) = (final mass-mass of silica used for evaluation) / (mass of modified liquid diene polymer used for evaluation) x 100 (unit:%)
The results are shown in Table 1 below. The larger the silica adsorptive property, the better the silica adsorptive property.
キシレン１５ｇ中に、得られた変性液状ジエン系重合体１．５ｇ、シリカ３．０ｇを溶解させ、１４０℃、２０分加熱攪拌した。その後濾過、回収し、８０℃、２４時間真空乾燥を行い、質量（最終質量）を測定した。そして、以下の計算式によってシリカ吸着性を求めた。
（シリカ吸着性）＝（最終質量－評価に用いたシリカの質量）／（評価に用いた変性液状ジエン系重合体の質量）×１００（単位は％）
結果を下記表１に示す。シリカ吸着性が大きい程、シリカ吸着性に優れることを表す。 [Silica adsorption]
1.5 g of the obtained modified liquid diene polymer and 3.0 g of silica were dissolved in 15 g of xylene, and the mixture was heated and stirred at 140 ° C. for 20 minutes. After that, it was filtered and collected, vacuum dried at 80 ° C. for 24 hours, and the mass (final mass) was measured. Then, the silica adsorptivity was determined by the following calculation formula.
(Silica adsorptivity) = (final mass-mass of silica used for evaluation) / (mass of modified liquid diene polymer used for evaluation) x 100 (unit:%)
The results are shown in Table 1 below. The larger the silica adsorptive property, the better the silica adsorptive property.
なお、表１中、主鎖官能基数は、各変性液状ジエン系重合体について、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）を表す。
In Table 1, the number of main chain functional groups represents the number of functional groups B in the main chain (average number per molecule) for each modified liquid diene polymer.
表１から分かるように、主鎖に官能基Ｂを有するが末端に官能基Ａを有さない比較例１、及び、末端に官能基Ａを有するが主鎖に官能基Ｂを有さない比較例２～４と比較して、末端に官能基Ａを有し主鎖に官能基Ｂを有する実施例１～２は、優れたシリカ吸着性を示した。なかでも、末端に有する官能基Ａの数（１分子あたりの平均の数）と、主鎖に有する官能基Ｂの数（１分子あたりの平均の数）との合計が４以上である実施例２は、より優れたシリカ吸着性を示した。
As can be seen from Table 1, Comparative Example 1 having a functional group B in the main chain but not having a functional group A at the terminal, and a comparison having a functional group A at the terminal but not having a functional group B in the main chain. Compared with Examples 2 to 4, Examples 1 and 2 having a functional group A at the terminal and a functional group B in the main chain showed excellent silica adsorptivity. Among them, Examples in which the total of the number of functional groups A at the terminal (average number per molecule) and the number of functional groups B in the main chain (average number per molecule) is 4 or more. 2 showed better silica adsorptivity.
Claims (5)
- 末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有し、
主鎖に、下記式（１）で表される官能基Ｂを有する、
液状ジエン系重合体である、変性液状ジエン系重合体。
式（１）中、Ｒ１は、炭素数１～１０のアルキレン基を表し、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、炭素数１～１０のアルコキシ基を表し、＊は、結合位置を表す。 At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. It has one functional group A and
The main chain has a functional group B represented by the following formula (1).
A modified liquid diene polymer, which is a liquid diene polymer.
In the formula (1), R 1 represents an alkylene group having 1 to 10 carbon atoms, R 2 , R 3 and R 4 independently represent an alkoxy group having 1 to 10 carbon atoms, and * represents a bond. Represents a position. - 前記液状ジエン系重合体が、ブタジエン及びイソプレンからなる群より選択される少なくとも１種を含有するモノマーの重合体である、請求項１に記載の変性液状ジエン系重合体。 The modified liquid diene polymer according to claim 1, wherein the liquid diene polymer is a polymer of a monomer containing at least one selected from the group consisting of butadiene and isoprene.
- 重量平均分子量が、１，０００～１００，０００である、請求項１又は２に記載の変性液状ジエン系重合体。 The modified liquid diene-based polymer according to claim 1 or 2, wherein the weight average molecular weight is 1,000 to 100,000.
- 官能基数が、２～１０である、請求項１～３のいずれか１項に記載の変性液状ジエン系重合体。ここで、前記官能基数は、末端に有する前記官能基Ａの１分子あたりの平均の数と、主鎖に有する前記官能基Ｂの１分子あたりの平均の数との合計を表す。 The modified liquid diene-based polymer according to any one of claims 1 to 3, wherein the number of functional groups is 2 to 10. Here, the number of functional groups represents the total of the average number of the functional groups A at the terminal per molecule and the average number of the functional groups B at the main chain per molecule.
- 末端に、アミノ基、水酸基、カルボキシ基、アルコキシシリル基、カルボニル基を有する１価の基、アルデヒド基、エポキシ基、ニトロ基、及び、アミノ基を有するアルコキシシリル基からなる群より選択される少なくとも１種の官能基Ａを有する液状ジエン系重合体である末端変性液状ジエン系重合体と、
ラジカル開始剤と、
下記式（２）で表される化合物とを反応させることで、前記末端変性液状ジエン系重合体の主鎖に前記式（１）で表される官能基Ｂを導入し、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を得る、変性液状ジエン系重合体の製造方法。
式（２）中、Ｒ１は、炭素数１～１０のアルキレン基を表し、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、炭素数１～１０のアルコキシ基を表す。 At least selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, an alkoxysilyl group, a monovalent group having a carbonyl group, an aldehyde group, an epoxy group, a nitro group, and an alkoxysilyl group having an amino group at the terminal. A terminal-modified liquid diene polymer which is a liquid diene polymer having one kind of functional group A, and a terminal-modified liquid diene polymer.
Radical initiator and
By reacting with the compound represented by the following formula (2), the functional group B represented by the formula (1) is introduced into the main chain of the terminal-modified liquid diene polymer, and claims 1 to 4 are introduced. A method for producing a modified liquid diene polymer, which comprises the method for obtaining the modified liquid diene polymer according to any one of the above items.
In the formula (2), R 1 represents an alkylene group having 1 to 10 carbon atoms, and R 2 , R 3 and R 4 independently represent an alkoxy group having 1 to 10 carbon atoms.
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| WO2019230700A1 (en) * | 2018-05-29 | 2019-12-05 | 株式会社クラレ | Reinforcing fibers and production method therefor, and molded article using same |
| WO2020040254A1 (en) * | 2018-08-24 | 2020-02-27 | 横浜ゴム株式会社 | Production method for aromatic vinyl-diene copolymer, and production method for rubber composition |
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| JP2018145233A (en) * | 2017-03-02 | 2018-09-20 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
| WO2019230700A1 (en) * | 2018-05-29 | 2019-12-05 | 株式会社クラレ | Reinforcing fibers and production method therefor, and molded article using same |
| WO2020040254A1 (en) * | 2018-08-24 | 2020-02-27 | 横浜ゴム株式会社 | Production method for aromatic vinyl-diene copolymer, and production method for rubber composition |
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