JP2010270211A - Isoprene-isobutene-styrylisoprene-phenylisoprene copolymers, methods for their production, and crosslinked rubber - Google Patents
Isoprene-isobutene-styrylisoprene-phenylisoprene copolymers, methods for their production, and crosslinked rubber Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 styryl isoprene Chemical compound 0.000 claims abstract description 18
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 14
- ACRSJMISSHCALU-UHFFFAOYSA-N 3-methylbuta-1,3-dienylbenzene Chemical compound CC(=C)C=CC1=CC=CC=C1 ACRSJMISSHCALU-UHFFFAOYSA-N 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 44
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 84
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- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 description 40
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 28
- 229910052794 bromium Inorganic materials 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 239000007795 chemical reaction product Substances 0.000 description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- 238000004132 cross linking Methods 0.000 description 12
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 11
- 229920005604 random copolymer Polymers 0.000 description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 125000005504 styryl group Chemical group 0.000 description 6
- 238000001542 size-exclusion chromatography Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000825 ultraviolet detection Methods 0.000 description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- QHFAXRHEKNHTDH-UHFFFAOYSA-N (2-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=C QHFAXRHEKNHTDH-UHFFFAOYSA-N 0.000 description 1
- DGUSBFIKLRIECS-UHFFFAOYSA-N (4-ethenylphenyl)boron Chemical compound [B]C1=CC=C(C=C)C=C1 DGUSBFIKLRIECS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical group Br1=CC=CC=C1 SODQFLRLAOALCF-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AGTIJKLADGVFEL-UHFFFAOYSA-N acetic acid;ditert-butyl-(2-phenylphenyl)phosphane;palladium Chemical compound [Pd].CC(O)=O.CC(C)(C)P(C(C)(C)C)C1=CC=CC=C1C1=CC=CC=[C-]1 AGTIJKLADGVFEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PENAXHPKEVTBLF-UHFFFAOYSA-L palladium(2+);prop-1-ene;dichloride Chemical compound [Pd+]Cl.[Pd+]Cl.[CH2-]C=C.[CH2-]C=C PENAXHPKEVTBLF-UHFFFAOYSA-L 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Abstract
Description
本発明は、新規なイソプレン−イソブテン−スチリルイソプレン−フェニルイソプレン共重合体、それらの製造方法、および架橋ゴムに関する。 The present invention relates to novel isoprene-isobutene-styrylisoprene-phenylisoprene copolymers, a process for producing them, and a crosslinked rubber.
一般に、電解コンデンサは、電極引き出し手段であるリード線を備えた電極箔を、セパレータを介して巻回してコンデンサ素子を形成し、駆動用電解液を含浸したコンデンサ素子を有底筒状の外装ケースに収納して、この外装ケースの開口部に封口体を装着し、その後、開口部を加締め加工によって封口して形成される。通常、この電解コンデンサ用封口体としては、イソプレン−イソブテン共重合体（式１）を樹脂架橋したゴム（特許文献１、２）やイソプレン−イソブテン−ジビニルベンゼン共重合体を過酸化物架橋したゴム（式２）（特許文献３、４、５）からなる封口ゴムが用いられる。 In general, an electrolytic capacitor has a bottomed cylindrical outer case in which a capacitor element is formed by winding an electrode foil provided with a lead wire as an electrode lead-out means through a separator, and impregnating a driving electrolyte solution. And a sealing body is attached to the opening of the outer case, and then the opening is sealed by caulking. Usually, as the sealing body for electrolytic capacitors, rubber obtained by resin-crosslinking isoprene-isobutene copolymer (formula 1) (Patent Documents 1 and 2) or rubber obtained by peroxide-crosslinking isoprene-isobutene-divinylbenzene copolymer. A sealing rubber made of (Formula 2) (Patent Documents 3, 4, and 5) is used.
このイソプレン−イソブテン共重合体を樹脂架橋したゴムは架橋に用いた残存樹脂の耐熱性が低いために、このゴムを用いた封口ゴムの耐熱性もまた低いという課題を有している。さらに、イソプレン−イソブテン−ジビニルベンゼン共重合体を過酸化物架橋したゴムはジビニルベンゼンの共重合時にジビニルベンゼンのビニル基による部分架橋が生じ、そのことによって混練時に分散性が低下するおそれがあるという課題もある。 The rubber obtained by resin crosslinking of this isoprene-isobutene copolymer has a problem that the heat resistance of the sealing rubber using this rubber is also low because the residual resin used for crosslinking has low heat resistance. Furthermore, rubber obtained by peroxide-crosslinking isoprene-isobutene-divinylbenzene copolymer is partially crosslinked by divinylbenzene vinyl groups during copolymerization of divinylbenzene, which may reduce dispersibility during kneading. There are also challenges.
そこで、出願人らは、国際特許出願ＰＣＴ／ＪＰ２００８／７１８３４において耐熱性が高く、分散性がよいゴムとして、「イソブテン、イソプレン、及びスチリルイソプレンよりなる三元共重合体」を提案している。 Therefore, the applicants have proposed “Ternary Copolymer Consisting of Isobutene, Isoprene, and Styrylisoprene” as rubber having high heat resistance and good dispersibility in International Patent Application PCT / JP2008 / 71834.
しかしながら、この種のゴムは架橋密度と引張強度に相関関係があり、引張強度を最適化するために、架橋密度を調製したいという要求がある。 However, this type of rubber has a correlation between the crosslinking density and the tensile strength, and there is a demand to adjust the crosslinking density in order to optimize the tensile strength.
そこで、本発明は、イソブテン、イソプレン、及びスチリルイソプレンよりなる三元共重合体の架橋密度を調製することができる共重合体、及びそれらの製造方法を提供することを目的とする。 Then, an object of this invention is to provide the copolymer which can adjust the crosslinking density of the terpolymer which consists of isobutene, isoprene, and styryl isoprene, and those manufacturing methods.
前記の課題を解決する第１の発明のイソプレン−イソブテン−スチリルイソプレン−フェニルイソプレン共重合体は、イソプレン−イソブテン共重合体の塩素化物または臭化物と、４−ビニルフェニルボロン酸とフェニルボロン酸の混合物とのスズキカップリング反応によって生成するスチリル化フェニル化四元ランダム共重合体（Ｓｔ，Ｐｈ−ＱＣ：Ｓｔｙｒｅｎａｔｅｄ Ｐｈｅｎｙｌ Ｑｕａｒｔｅｒｎａｒｙ Ｃｏｐｏｌｙｍｅｒ）であり、また、四元ランダム共重合体が架橋されていてもよい。 The isoprene-isobutene-styrylisoprene-phenylisoprene copolymer of the first invention for solving the above-mentioned problems is a chlorinated product or bromide of isoprene-isobutene copolymer, and a mixture of 4-vinylphenylboronic acid and phenylboronic acid. A styrylated phenyl quaternary random copolymer (St, Ph-QC) produced by a Suzuki coupling reaction with quaternary random copolymer may be crosslinked.
また、前記の課題を解決すべく、第２の発明であるイソプレン−イソブテン−スチリルイソプレン−フェニルイソプレン共重合体の製造方法は、Ｐｄ（ＰＰｈ３）４：テトラキストリフェニルホスフィンパラジウム、またはビス［ミュー−クロロ［５−ヒドロキシ−２−［１−（ヒドロキシイミノ）エチル］フェニル］パラジウム］のいずれか少なくとも一つを含む触媒を用いて請求項１に記載のイソプレン−イソブテン−スチリルイソプレン−フェニルイソプレン共重合体を製造する方法である。さらに、本発明のスチリル化フェニル化四元ランダム共重合体は、四元ランダム共重合体が架橋することで製造される。 In order to solve the above-mentioned problem, the method for producing the isoprene-isobutene-styrylisoprene-phenylisoprene copolymer according to the second invention is made of Pd (PPh 3 ) 4 : tetrakistriphenylphosphine palladium or bis [mu] The isoprene-isobutene-styrylisoprene-phenylisoprene copolymer according to claim 1 using a catalyst containing at least one of -chloro [5-hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium]. It is a method for producing a polymer. Furthermore, the styrylated phenylated quaternary random copolymer of the present invention is produced by crosslinking the quaternary random copolymer.
さらに、前記の課題を解決すべく、第３の発明である架橋ゴムは、これらのイソプレン−イソブテン−スチリルイソプレン−フェニルイソプレン共重合体を含有する。 Furthermore, in order to solve the above-described problems, the crosslinked rubber according to the third invention contains these isoprene-isobutene-styrylisoprene-phenylisoprene copolymers.
本発明に示されるように、本発明の素材により耐熱性が高く、分散性がよいゴムを得ることができる。 As shown in the present invention, a rubber having high heat resistance and good dispersibility can be obtained by the material of the present invention.
イソプレン−イソブテン共重合体のハロゲン化物（Ｘ−ＩＩＲ、Ｘ＝Ｂｒ，Ｃｌ）に対して、パラジウム触媒ビス［ミュー−クロロ［５−ヒドロキシ−２−［１−（ヒドロキシイミノ）エチル］フェニル］パラジウム］とテトラヒドロフラン（ＴＨＦ）を加えて攪拌し、４−ビニルフェニルボロン酸とフェニルボロン酸とボロン酸との混合物を調製してスチリル化フェニル化四元ランダム共重合体が得られる。この際の反応式を式（３）に示す。 Palladium-catalyzed bis [mu-chloro [5-hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium against isoprene-isobutene copolymer halide (X-IIR, X = Br, Cl) ] And tetrahydrofuran (THF) are added and stirred to prepare a mixture of 4-vinylphenylboronic acid, phenylboronic acid and boronic acid to obtain a styrylated phenylated quaternary random copolymer. The reaction formula at this time is shown in Formula (3).
次に、同様に、式（４）（５）、図１に示すように、イソプレン−イソブテン共重合体のハロゲン化物（Ｘ−ＩＩＲ，Ｘ＝Ｂｒ、Ｃｌ）として、ＪＳＲ（株）社のＪＳＲＢＲＯＭＯＢＵＴＹＬ２２４４臭素含量２％のイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）を４．５グラム用い、パラジウム触媒であるビス［ミュー−クロロ［５−ヒドロキシ−２−［１−（ヒドロキシイミノ）エチル］フェニル］パラジウム］を０．００４９グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して０．０１当量）とテトラヒドロフラン（ＴＨＦ）を３５０ｍｌ加えて攪拌し、ついでボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の総量はイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．５当量として、４−ビニルフェニルボロン酸を７５％とフェニルボロン酸を２５％の混合物を調製した。４−ビニルフェニルボロン酸を０．２８グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．１２５当量（１．５当量の７５％））、フェニルボロン酸を０．０７７グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して０．３７５当量（１．５当量の２５％）） とテトラブチルアンモニウムブロミド（ＴＢＡＢ）を０．２７グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して０．５当量）、水酸化カリウム水溶液（ＫＯＨ／Ｈ２Ｏ）をＫＯＨ０．１９グラム／Ｈ２Ｏ２．０ｍｌ（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対してＫＯＨ２当量）加えて、反応溶媒ＴＨＦ還流下（８０℃）で１５時間攪拌した。 Next, similarly, as shown in the formulas (4), (5) and FIG. 1, as isoprene-isobutene copolymer halides (X-IIR, X = Br, Cl), JSR BROMOBUTYL2244 of JSR Corporation. Using 4.5 grams of bromide (Br-IIR) of isoprene-isobutene copolymer having a bromine content of 2%, the palladium catalyst bis [mu-chloro [5-hydroxy-2- [1- (hydroxyimino) ethyl] Phenyl] palladium] in an amount of 0.0049 grams (0.01 equivalent to 1 equivalent of bromide of isoprene-isobutene copolymer (Br-IIR)) and 350 ml of tetrahydrofuran (THF) were added and stirred, and then boronic acid The total amount of the mixture of 4-vinylphenylboronic acid and phenylboronic acid as an ingredient is an isoprene-isobutene copolymer. 1.5 as an equivalent amount with respect to the bromine 1 equivalent of the bromide (Br-IIR), a 4-vinylphenyl boronic acid 75% and phenylboronic acid was prepared a mixture of 25%. 0.28 grams of 4-vinylphenylboronic acid (1.125 equivalents per 75 equivalents of bromide of isoprene-isobutene copolymer (Br-IIR) (75 equivalents of 1.5 equivalents)), phenylboronic acid 0.077 g (0.375 equivalents (1.5 equivalents of 25%) with respect to 1 equivalent of bromine of bromide (Br-IIR) of isoprene-isobutene copolymer) and 0 of tetrabutylammonium bromide (TBAB) .27 g (0.5 equivalent to 1 equivalent of bromine of isoprene-isobutene copolymer bromide (Br-IIR)), potassium hydroxide aqueous solution (KOH / H 2 O) was added to KOH 0.19 g / H 2 O 2 0.0 ml (2 equivalents of KOH to 1 equivalent of bromine of isoprene-isobutene copolymer bromide (Br-IIR)) was added, and the reaction solvent was refluxed with THF (80 ° C. In the mixture was stirred for 15 hours.
この際の反応式を式（５）に示す。但し、式（５）に示す共重合体の構造は主な構造であり、これに限定されるものではなく、異性体構造を有している。 The reaction formula at this time is shown in Formula (5). However, the structure of the copolymer shown in Formula (5) is a main structure, and is not limited to this, and has an isomer structure.
次に、同様に、イソプレン−イソブテン共重合体のハロゲン化物（Ｘ−ＩＩＲ，Ｘ＝Ｂｒ、Ｃｌ）として、ＪＳＲ（株）社のＪＳＲＢＲＯＭＯＢＵＴＹＬ２２４４臭素含量２％のイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）を４．５グラム用い、パラジウム触媒であるビス［ミュー−クロロ［５−ヒドロキシ−２−［１−（ヒドロキシイミノ）エチル］フェニル］パラジウム］を０．００４９グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して０．０１当量）とテトラヒドロフラン（ＴＨＦ）を３５０ｍｌ加えて攪拌し、ついでボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の総量はイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．５当量として、４−ビニルフェニルボロン酸を５０％とフェニルボロン酸を５０％の混合物を調製した。４−ビニルフェニルボロン酸を０．１８６グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して０．７５当量（１．５当量の５０％））、フェニルボロン酸を０．１５４グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して０．７５当量（１．５当量の５０％））とテトラブチルアンモニウムブロミド（ＴＢＡＢ）を０．２７グラム（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して０．５当量）、水酸化カリウム水溶液（ＫＯＨ／Ｈ２Ｏ）をＫＯＨ０．１９グラム／Ｈ２Ｏ２．０ｍｌ（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対してＫＯＨ２当量）加えて反応溶媒ＴＨＦ還流下（８０℃）で１５時間攪拌した。
Next, in the same manner, as the isoprene-isobutene copolymer halide (X-IIR, X = Br, Cl), the bromide of the isoprene-isobutene copolymer (Br) having a bromine content of 2%, JSRBROBOBTYL2244, manufactured by JSR Corporation. -IIR) is used in an amount of 4.5 grams, and the palladium catalyst bis [mu-chloro [5-hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium] is 0.0049 grams (isoprene-isobutene copolymer). 350 ml of tetrahydrofuran (THF) and 350 ml of combined bromide (Br-IIR) with 0.01 equivalent of bromine were added and stirred, and then a mixture of 4-vinylphenylboronic acid and phenylboronic acid as a boronic acid component was added. The total amount is 1 bromine of bromide (Br-IIR) of isoprene-isobutene copolymer. 1.5 as an equivalent amount, 4-vinylphenyl boronic acid was prepared a mixture of 50% with a phenyl
また、ボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の総量はイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．５当量として、４−ビニルフェニルボロン酸を２５％とフェニルボロン酸を７５％、および４−ビニルフェニルボロン酸を０％とフェニルボロン酸を１００％の混合物を調製し、同様に反応を行った。また４−ビニルフェニルボロン酸を１００％とフェニルボロン酸を０％の混合物を調製し、同様に反応を行った。 The total amount of the mixture of 4-vinylphenylboronic acid and phenylboronic acid as the boronic acid component is 1.5 equivalents relative to 1 equivalent of bromine of the isoprene-isobutene copolymer bromide (Br-IIR). A mixture of 25% phenylboronic acid and 75% phenylboronic acid and 0% 4-vinylphenylboronic acid and 100% phenylboronic acid was prepared and reacted in the same manner. A mixture of 100% 4-vinylphenylboronic acid and 0% phenylboronic acid was prepared and reacted in the same manner.
パラジウム触媒の使用量は、イソプレン−イソブテン共重合体のハロゲン化物（Ｘ−ＩＩＲ，Ｘ＝Ｂｒ，Ｃｌ）のハロゲン濃度に対して、０．０００１倍〜５倍、好ましくは、０．００１倍〜１倍である。パラジウム触媒は、Ｐｄ（ＰＰｈ３）４：テトラキストリフェニルホスフィンパラジウム、ビス［ミュー−クロロ［５−ヒドロキシ−２−［１−（ヒドロキシイミノ）エチル］フェニル］パラジウム］、２−［ビス（２，４−ジ−ｔｅｒｔ−ブチル−フェノキシ）ホスフィノオキシ］−３，５−ジ（ｔｅｒｔ−ブチル）フェニル−パラジウム（ＩＩ）クロリド、クロロ（η２−Ｐ，Ｃ−トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト）（トリシクロヘキシルホスヒィン）パラジウム（ＩＩ）、２−（２’−ジ−ｔｅｒｔ−ブチルホスヒィン）ビフェニルパラジウム（ＩＩ）アセテート、ジ−η−クロロビス［５−クロロ−２−［（４−クロロフェニル）（ヒドロキシイミノ−ｋＮ）メチル］フェニル−ｋＣ］パラジウム、［１，１’−ビス（ジ−ｔｅｒｔ−ブチルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリド、［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリドジクロロメタン錯体（１：１）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリド、ビス（ベンゾニトリル）パラジウム（ＩＩ）ジクロリド、アリルパラジウム（ＩＩ）クロリド、酢酸パラジウム（ＩＩ）、トリス（ジベンジリデンアセトン）ジパラジウム（０）、テトラキス（トリフェニルホスフィン）パラジウム（０）、ビス（ジベンジリデンアセトン）パラジウム（０）などであり、好ましくはＰｄ（ＰＰｈ３）４：テトラキストリフェニルホスフィンパラジウム、ビス［ミュー−クロロ［５−ヒドロキシ−２−［１−（ヒドロキシイミノ）エチル］フェニル］パラジウム］、更に好ましくはビス［ミュー−クロロ［５−ヒドロキシ−２−［１−（ヒドロキシイミノ）エチル］フェニル］パラジウム］である。 The amount of the palladium catalyst used is 0.0001 times to 5 times, preferably 0.001 times to the halogen concentration of the isoprene-isobutene copolymer halide (X-IIR, X = Br, Cl). 1x. The palladium catalyst is Pd (PPh 3 ) 4 : tetrakistriphenylphosphine palladium, bis [mu-chloro [5-hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium], 2- [bis (2, 4-di-tert-butyl-phenoxy) phosphinooxy] -3,5-di (tert-butyl) phenyl-palladium (II) chloride, chloro (η2-P, C-tris (2,4-di-tert) -Butylphenyl) phosphite) (tricyclohexylphosphine) palladium (II), 2- (2'-di-tert-butylphosphine) biphenylpalladium (II) acetate, di-η-chlorobis [5-chloro-2- [(4-chlorophenyl) (hydroxyimino-kN) methyl] phenyl-kC] palladium, [ , 1′-bis (di-tert-butylphosphino) ferrocene] palladium (II) dichloride, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane complex (1: 1), bis (Triphenylphosphine) palladium (II) dichloride, bis (benzonitrile) palladium (II) dichloride, allyl palladium (II) chloride, palladium (II) acetate, tris (dibenzylideneacetone) dipalladium (0), tetrakis (tri Phenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), etc., preferably Pd (PPh 3 ) 4 : tetrakistriphenylphosphine palladium, bis [mu-chloro [5-hydroxy-2- [ 1- (Hydroxy Imino) ethyl] phenyl] palladium, more preferably bis [mu - chloro [5-hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium.
さらに添加剤としてリチウム塩である塩化リチウム（ＬｉＣｌ）または臭化リチウム（ＬｉＢｒ）を添加するとパラジウム触媒の使用量を少なくしてもスズキカップリング反応が進行する。このリチウム塩の使用量は、イソプレン−イソブテン共重合体のハロゲン化物（Ｘ−ＩＩＲ，Ｘ＝Ｂｒ，Ｃｌ）のハロゲン濃度に対して、０．０００１倍〜１０倍、好ましくは０．００１倍〜１倍である。 Furthermore, when a lithium salt such as lithium chloride (LiCl) or lithium bromide (LiBr) is added as an additive, the Suzuki coupling reaction proceeds even if the amount of palladium catalyst used is reduced. The amount of lithium salt used is 0.0001 to 10 times, preferably 0.001 to 10 times the halogen concentration of the isoprene-isobutene copolymer halide (X-IIR, X = Br, Cl). 1x.
また、ボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の総量は、イソプレン−イソブテン共重合体のハロゲン化物（Ｘ−ＩＩＲ，Ｘ＝Ｂｒ，Ｃｌ）のハロゲン濃度に対して、１倍〜１０倍、好ましくは１倍〜５倍である。 The total amount of the mixture of 4-vinylphenylboronic acid and phenylboronic acid as the boronic acid component is 1 with respect to the halogen concentration of the isoprene-isobutene copolymer halide (X-IIR, X = Br, Cl). Double to 10 times, preferably 1 to 5 times.
さらに、塩基は、アルカリ金属やアルカリ土類金属などの水酸化物や炭酸塩、リン酸塩あるいはアンモニア、アミン類など塩基性を示す物質を示し、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、トリエチルアミン、ジイソプロピルアミンなどがあり、好ましくは水酸化カリウム、ジイソプロピルアミンである。この塩基の使用量は、イソプレン−イソブテン共重合体のハロゲン化物（Ｘ−ＩＩＲ，Ｘ＝Ｂｒ，Ｃｌ）のハロゲン濃度に対して、１倍〜５０倍、好ましくは、１倍〜１０倍である。本発明の反応で使用される溶媒は、反応を阻害しない溶媒であれば特に限定されないが、例えば、エーテル系溶媒（ＴＨＦ，１，２−ジメトキシエタン（ＤＭＥ）、ジエチルエーテル、ジオキサンなど）、含酸素系溶媒、含窒素系溶媒（Ｎ，Ｎ−ジメチルホルムアミト（ＤＭＦ）、アセトニトリルなど）、芳香族炭化水素系溶媒（トルエン、アセトンなど）、脂肪族炭化水素系溶媒等が挙げられる。通常、これらの溶媒を単独或いは混合して使用することができる。また、共溶媒として、水等の溶媒も使用することができる。 Furthermore, the base indicates a basic substance such as hydroxide, carbonate, phosphate, ammonia, amines such as alkali metal and alkaline earth metal, potassium hydroxide, sodium hydroxide, potassium carbonate, triethylamine. , Diisopropylamine and the like, preferably potassium hydroxide and diisopropylamine. The amount of the base used is 1 to 50 times, preferably 1 to 10 times the halogen concentration of the isoprene-isobutene copolymer halide (X-IIR, X = Br, Cl). . The solvent used in the reaction of the present invention is not particularly limited as long as it does not inhibit the reaction. For example, ether solvents (THF, 1,2-dimethoxyethane (DME), diethyl ether, dioxane, etc.), Examples thereof include oxygen-based solvents, nitrogen-containing solvents (N, N-dimethylformamito (DMF), acetonitrile, etc.), aromatic hydrocarbon solvents (toluene, acetone, etc.), aliphatic hydrocarbon solvents, and the like. Usually, these solvents can be used alone or in combination. A solvent such as water can also be used as a co-solvent.
この反応生成物についてサイズ排除クロマトグラフィ（ＳＥＣ）のＲＩ（Ｒｅｆｒａｃｔｉｖｅ Ｉｎｄｅｘ示差屈折率）およびＵＶ（Ｕｌｔｒａ Ｖｉｏｌｅｔ：紫外光）検出器を用いて、２５４ｎｍでの測定を行った。ボロン酸成分として４−ビニルフェニルボロン酸を１００％（イソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．５当量）として反応を行った反応生成物（Ａｆｔｅｒ（Ｓｔ−ＩＩＲ））と出発材料としてイソプレン−イソブテン共重合体の臭化物（Ｂｅｆｏｒｅ（Ｂｒ−ＩＩＲ））との測定結果を図２に示す。図２に示すように、この反応生成物（Ｓｔ−ＩＩＲ）はイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）と比較して、ＲＩ検出ピーク強度がほとんど変化しないのに対し、ＵＶ検出ピーク強度には大きな変化が現れた。このことから、この反応生成物には紫外線に吸収を持つスチリル基が導入されたことがわかり、イソプレン−イソブテン共重合体の臭化物と４−ビニルフェニルボロン酸とのスズキカップリングによってスチリル化三元ランダム共重合体（式（６））（Ｓｔ−ＴＣ：Ｓｔｙｒｅｎａｔｅｄ Ｔｅｒｎａｒｙ Ｃｏｐｏｌｙｍｅｒ）が生成された。 The reaction product was measured at 254 nm using size exclusion chromatography (SEC) RI (Refractive Index differential refractive index) and UV (Ultra Violet) detectors. 4-vinylphenylboronic acid as the boronic acid component was reacted as 100% (1.5 equivalents relative to 1 equivalent of bromine of isoprene-isobutene copolymer (Br-IIR)) (After ( FIG. 2 shows the measurement results of St-IIR)) and isoprene-isobutene copolymer bromide (Before (Br-IIR)) as a starting material. As shown in FIG. 2, the reaction product (St-IIR) has almost no change in the RI detection peak intensity compared to the bromide of the isoprene-isobutene copolymer (Br-IIR), whereas the UV detection peak There was a big change in intensity. From this, it was found that a styryl group having absorption in ultraviolet rays was introduced into this reaction product, and styrylation ternary was obtained by Suzuki coupling of bromide of isoprene-isobutene copolymer and 4-vinylphenylboronic acid. A random copolymer (Formula (6)) (Stirted TC) was produced.
次にボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の総量はイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．５当量として、４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の比率を調製して反応を行った。４−ビニルフェニルボロン酸とフェニルボロン酸の混合比率の違いによるＳＥＣのＲＩ検出ピーク面積とＵＶ検出ピーク面積の比の比較を表１に示す。 Next, the total amount of the mixture of 4-vinylphenylboronic acid and phenylboronic acid as the boronic acid component is 1.5 equivalents relative to 1 equivalent of bromine of the isoprene-isobutene copolymer (Br-IIR). The reaction was carried out by adjusting the ratio of the mixture of phenylboronic acid and phenylboronic acid. Table 1 shows a comparison of the ratio of the SEC RI detection peak area and the UV detection peak area according to the difference in the mixing ratio of 4-vinylphenylboronic acid and phenylboronic acid.
表１より、４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の比率を調製してスズキカップリング反応を行うと、４−ビニルフェニルボロン酸の比率が多くなるにつれて、ＳＥＣのＲＩ検出ピーク面積とＵＶ検出ピーク面積の比（ＳＵＶ／ＳＲＩ）が大きくなり、反応生成物のスチリル基の量が異なることが確認できた。 From Table 1, when the ratio of the mixture of 4-vinylphenylboronic acid and phenylboronic acid was prepared and the Suzuki coupling reaction was performed, as the ratio of 4-vinylphenylboronic acid increased, the SEC RI detection peak area and It was confirmed that the ratio of UV detection peak area (SUV / SRI) was increased and the amount of styryl groups in the reaction product was different.
［反応式］
式（８）で得られた反応生成物について１Ｈ−ＮＭＲ分析結果を図３に示す。図３に示すように、ボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の総量はイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．５当量として、４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の比率を調製して反応を行った。４−ビニルフェニルボロン酸を７５％とフェニルボロン酸を２５％に調製して得られた反応生成物を実施例１、４−ビニルフェニルボロン酸を５０％とフェニルボロン酸を５０％に調製して得られた反応生成物を実施例２、４−ビニルフェニルボロン酸を２５％とフェニルボロン酸を７５％に調製して得られた反応生成物を実施例３、４−ビニルフェニルボロン酸を０％とフェニルボロン酸を１００％に調製して得られた反応生成物を比較例１、４−ビニルフェニルボロン酸を１００％とフェニルボロン酸を０％に調製して得られた反応生成物を比較例２とする。これらの反応生成物について１Ｈ−ＮＭＲのシグナルを比較すると、６．６５、５．６５、５．１５ｐｐｍ付近のスチリル基内のビニル基の水素に由来するシグナルが検出され、４−ビニルフェニルボロン酸の比率が多くなるにつれてピーク強度が大きくなっていくことが確認できた。また、スチリル基またはフェニル基が結合しているイソプレン基内のメチレンの水素に由来する３．４ｐｐｍ付近のシグナルは、スチリル基内のビニル基の水素に由来するシグナルが変化してもピーク強度がほとんど変化していないことからフェニル基が結合していることが確認できた。ただし、フェニルボロン酸を１００％に調製し反応させた比較例１では、イソプレン基内の臭素が結合していた炭素上のメチン水素に由来する４．３ｐｐｍ付近のシグナルが残存し、同一条件では反応が変化することが確認できた。この分析結果から、４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の比率を調製して得られた反応生成物（Ｓｔ，Ｐｈ−ＩＩＲ）にはスチリル基とフェニル基が導入されたことがわかり、イソプレン−イソブテン共重合体の臭化物と４−ビニルフェニルボロン酸とフェニルボロン酸とのスズキカップリング反応によってスチリル化フェニル化四元ランダム共重合体（式（７））（Ｓｔ，Ｐｈ−ＱＣ）が生成されることがわかった。またボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の比率を調製することでイソプレン−イソブテン共重合体のスチリル化率を変化させることができることがわかった。
[Reaction formula]
FIG. 3 shows the 1 H-NMR analysis results of the reaction product obtained by the formula (8). As shown in FIG. 3, the total amount of the mixture of 4-vinylphenylboronic acid and phenylboronic acid as the boronic acid component is 1.5 equivalents relative to 1 equivalent of bromine of the isoprene-isobutene copolymer bromide (Br-IIR). The reaction was carried out by adjusting the ratio of a mixture of 4-vinylphenylboronic acid and phenylboronic acid. The reaction product obtained by preparing 75% 4-vinylphenylboronic acid and 25% phenylboronic acid was prepared in Example 1, 50% 4-vinylphenylboronic acid and 50% phenylboronic acid. The reaction product obtained in Example 2, 25% 4-vinylphenylboronic acid and 75% phenylboronic acid was prepared as Example 3, 4-vinylphenylboronic acid. The reaction product obtained by adjusting 0% and phenylboronic acid to 100% is Comparative Example 1, the reaction product obtained by adjusting 4-vinylphenylboronic acid to 100% and phenylboronic acid to 0%. Is referred to as Comparative Example 2. Comparing the signals of 1 H-NMR with respect to these reaction products, signals derived from hydrogen of the vinyl group in the styryl group around 6.65, 5.65, and 5.15 ppm were detected, and 4-vinylphenylboron was detected. It was confirmed that the peak intensity increased as the acid ratio increased. In addition, the signal around 3.4 ppm derived from the methylene hydrogen in the isoprene group to which the styryl group or phenyl group is bonded has a peak intensity even if the signal derived from the hydrogen of the vinyl group in the styryl group changes. The fact that there was almost no change confirmed that the phenyl group was bonded. However, in Comparative Example 1 in which phenylboronic acid was adjusted to 100% and reacted, a signal around 4.3 ppm derived from methine hydrogen on carbon to which bromine in the isoprene group was bonded remained, and under the same conditions, It was confirmed that the reaction changed. From this analysis result, it was found that a styryl group and a phenyl group were introduced into the reaction product (St, Ph-IIR) obtained by adjusting the ratio of the mixture of 4-vinylphenylboronic acid and phenylboronic acid. , A styrylated phenylated quaternary random copolymer (formula (7)) (St, Ph-QC) by Suzuki coupling reaction of bromide of isoprene-isobutene copolymer, 4-vinylphenylboronic acid and phenylboronic acid Was found to be generated. It was also found that the styrylation rate of the isoprene-isobutene copolymer can be changed by adjusting the ratio of a mixture of 4-vinylphenylboronic acid and phenylboronic acid as the boronic acid component.
次に、ボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の総量はイソプレン−イソブテン共重合体の臭化物（Ｂｒ−ＩＩＲ）の臭素１当量に対して１．５当量として、４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の比率を調製して反応を行った反応生成物についてジクルミルパーオキサイドを用いてレオメータでトルク特性を測定した結果を図４に示す。４−ビニルフェニルボロン酸を７５％とフェニルボロン酸を２５％に調製して得られた反応生成物を実施例１、４−ビニルフェニルボロン酸を５０％とフェニルボロン酸を５０％に調製して得られた反応生成物を実施例２、４−ビニルフェニルボロン酸を２５％とフェニルボロン酸を７５％に調製して得られた反応生成物を実施例３、４−ビニルフェニルボロン酸を０％とフェニルボロン酸を１００％に調製して得られた反応生成物を比較例１、４−ビニルフェニルボロン酸を１００％とフェニルボロン酸を０％に調製して得られた反応生成物を比較例２とする。最大トルクは実施例１が７．０９ｄＮｍ、実施例２が５．０３ｄＮｍ、実施例３が２．３０ｄＮｍ、比較例１はトルクの上昇が見られず、また試験後の試料が発泡しておりこの共重合体が過酸化物架橋しないことが確認された。比較例２は９．４３ｄＮｍであった。硬度は実施例１が３０度、実施例２が２６度、実施例３はトルクの上昇があり過酸化物架橋が確認されたが気泡を含んでいたので測定せず、比較例１は架橋していないため測定不可、比較例２は３５度であった。このことから、イソプレン−イソブテン共重合体の臭化物と４−ビニルフェニルボロン酸とフェニルボロン酸とのスズキカップリングによってスチリル化フェニル化四元ランダム共重合体（式（７））（Ｓｔ，Ｐｈ−ＱＣ）が生成し、この共重合体が過酸化物架橋してスチリル化フェニル化四元ランダム共重合体を架橋してなるゴムの生成が確認された。またボロン酸成分として４−ビニルフェニルボロン酸とフェニルボロン酸の混合物の比率を調製することでイソプレン−イソブテン共重合体のスチリル化率を変化させることができ、これにより過酸化物架橋の調製ができる。 Next, the total amount of the mixture of 4-vinylphenylboronic acid and phenylboronic acid as the boronic acid component is 1.5 equivalents relative to 1 equivalent of bromine of the isoprene-isobutene copolymer bromide (Br-IIR). FIG. 4 shows the results of measuring the torque characteristics with a rheometer using diclemyl peroxide for a reaction product obtained by reacting with a mixture of vinylphenylboronic acid and phenylboronic acid. The reaction product obtained by preparing 75% 4-vinylphenylboronic acid and 25% phenylboronic acid was prepared in Example 1, 50% 4-vinylphenylboronic acid and 50% phenylboronic acid. The reaction product obtained in Example 2, 25% 4-vinylphenylboronic acid and 75% phenylboronic acid was prepared as Example 3, 4-vinylphenylboronic acid. The reaction product obtained by adjusting 0% and phenylboronic acid to 100% is Comparative Example 1, the reaction product obtained by adjusting 4-vinylphenylboronic acid to 100% and phenylboronic acid to 0%. Is referred to as Comparative Example 2. The maximum torque is 7.09 dNm in Example 1, 5.03 dNm in Example 2, 2.30 dNm in Example 3, no torque increase is observed in Comparative Example 1, and the sample after the test is foamed. It was confirmed that the copolymer was not peroxide crosslinked. The comparative example 2 was 9.43 dNm. The hardness of Example 1 was 30 degrees, Example 2 was 26 degrees, and Example 3 had a torque increase and peroxide crosslinking was confirmed, but it was not measured because it contained bubbles, and Comparative Example 1 was crosslinked. Measurement was impossible, and Comparative Example 2 was 35 degrees. From this fact, a styrylated phenylated quaternary random copolymer (formula (7)) (St, Ph— by Suzuki coupling of bromide of isoprene-isobutene copolymer, 4-vinylphenylboronic acid and phenylboronic acid. QC) was formed, and it was confirmed that this copolymer was peroxide-crosslinked to form a rubber formed by crosslinking a styrylated phenylated quaternary random copolymer. Moreover, by adjusting the ratio of the mixture of 4-vinylphenylboronic acid and phenylboronic acid as the boronic acid component, the styrylation rate of the isoprene-isobutene copolymer can be changed. it can.
また、イソプレン−イソブテン共重合体の臭化物に変えて、イソプレン−イソブテン共重合体の塩化物と４−ビニルフェニルボロン酸とフェニルボロン酸とのスズキカップリング反応によって得られたスチリル化フェニル化四元ランダム共重合体でも、この共重合体が過酸化物架橋してスチリル化フェニル化四元ランダム共重合体を架橋してなるゴムの生成が確認された。 Further, in place of bromide of isoprene-isobutene copolymer, styrylated phenylated quaternary obtained by Suzuki coupling reaction of chloride of isoprene-isobutene copolymer, 4-vinylphenylboronic acid and phenylboronic acid. Even in the case of a random copolymer, it was confirmed that this copolymer was peroxide-crosslinked to form a rubber formed by crosslinking a styrylated phenylated quaternary random copolymer.
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| JPS4632408B1 (en) * | 1968-11-20 | 1971-09-21 | ||
| JP2000072883A (en) * | 1998-08-26 | 2000-03-07 | Masao Kizawa | Kneading of isoprene/isobutylene/divinylbenzene terpolymer rubber |
| JP2001502354A (en) * | 1996-10-25 | 2001-02-20 | スミスクライン・ビーチャム・コーポレイション | Compounds and methods |
| JP2003109879A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Sealing body for electrolytic capacitors |
| WO2009072476A1 (en) * | 2007-12-05 | 2009-06-11 | Nagaoka University Of Technology | Terpolymer composed of isobutene, isoprene and styrylisoprene, process for production thereof, and sealing member for electrolytic capacitor |
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| JPS4632408B1 (en) * | 1968-11-20 | 1971-09-21 | ||
| JP2001502354A (en) * | 1996-10-25 | 2001-02-20 | スミスクライン・ビーチャム・コーポレイション | Compounds and methods |
| JP2000072883A (en) * | 1998-08-26 | 2000-03-07 | Masao Kizawa | Kneading of isoprene/isobutylene/divinylbenzene terpolymer rubber |
| JP2003109879A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Sealing body for electrolytic capacitors |
| WO2009072476A1 (en) * | 2007-12-05 | 2009-06-11 | Nagaoka University Of Technology | Terpolymer composed of isobutene, isoprene and styrylisoprene, process for production thereof, and sealing member for electrolytic capacitor |
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