JP5324426B2 - 高分子量結合ブロックコポリマー組成物 - Google Patents
高分子量結合ブロックコポリマー組成物 Download PDFInfo
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- JP5324426B2 JP5324426B2 JP2009505803A JP2009505803A JP5324426B2 JP 5324426 B2 JP5324426 B2 JP 5324426B2 JP 2009505803 A JP2009505803 A JP 2009505803A JP 2009505803 A JP2009505803 A JP 2009505803A JP 5324426 B2 JP5324426 B2 JP 5324426B2
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 16
- 150000001993 dienes Chemical class 0.000 claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000004606 Fillers/Extenders Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- -1 benzene Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000011925 1,2-addition Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004786 P-Li Inorganic materials 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004796 P—Li Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002900 organolithium compounds Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 125000005359 phenoxyalkyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- KBSUPJLTDMARAI-UHFFFAOYSA-N tribromo(methyl)silane Chemical compound C[Si](Br)(Br)Br KBSUPJLTDMARAI-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
(1) A−(B−A)n または
(2) (A−B)n
(式中、Aは、モノビニル芳香族炭化水素を含むポリマーブロックであり、Bは、共役ジエン単位を含むポリマーブロックであり、nは1から5の整数である。)で表され;(ii)は、ゴムに対する軟化剤であり、(iii)はオレフィン系ポリマーであり、(i)/(ii)の重量比は20/80から80/20であり、(iii)の量は、(i)および(ii)の100重量部の合計を基準にして、1から300重量部である。
(a)200,000から300,000のピーク見掛け分子量を有する、一般式(A−B)で表される線状ジブロックコポリマー(I)、
(b)一般式(A−B)2Xで表される、線状2腕ブロックコポリマー(II)、
(c)式(A−B)3Xで表される、3腕ブロックコポリマー(III)、
(d)式(A−B)n>3Xで表される、3腕を超えるブロックコポリマー(IV)、
(e)前記線状ジブロックコポリマー(I)未満のピーク見掛け分子量を有する側面ポリマー構造(SPS)、
を含み、Aは、主としてポリ(モノビニル芳香族炭化水素)のブロックを表し、前記ポリ(モノビニル芳香族炭化水素)含有量は20から35重量%の範囲にあり、Bは、主としてポリ(共役ジエン)のブロックを表し、Xは、3官能および/または4官能カップリング剤の残基であり、前記ブロックコポリマー組成物は、450,000から800,000の範囲の重量平均分子量Mwを有し、ブロックコポリマーの相対量は、前記全ブロックコポリマー組成物の重量に対して、それぞれ、Iは5から15重量%であり、IIおよびIIIは合わせて70から90重量%であり、IIIは10重量%超であり、IVは10重量%未満であり、SPSは10重量%未満であることに相当し、それぞれの成分の合計は100%になる、ブロックコポリマー組成物に関する。
Mn=Σ(wi)/Σ(wi/Mi)
Mw=Σ(wi *Mi)/Σ(wi)
Mz=Σ(wi *Mi *Mi)/Σ(wi *Mi)
RLi
(式中、Rは、1から20個の炭素原子を有する、脂肪族、環状脂肪族、アルキル置換環状脂肪族、芳香族またはアルキル置換芳香族炭化水素基であり、sec−ブチルが好ましい。)を有する有機リチウム化合物である。
HSBCポリマーの説明
「HSBC」という表現は、選択的に水素化されたブロックコポリマーの組成物に対して使用される。この項において説明される全てのHSBCは、ポリ(共役ジエン)の完全に水素化されたブロックを介して一緒に結合した外側の非水素化ポリスチレン(「PS」)ブロックで主に構成されるブロックコポリマーを含む組成物である。組成物は、若干の純粋なPSの形態の側面材料(以降においてSPSとして総称的に称されるその様な側面材料)を含んでもよい。
容易なHSBC製造:その他の高MwHSBCよりも低い溶液粘度
表6において示される通り、非常に驚くべきことに、400kg/mol超のMwを示す、高MwHSBC間で最も低い溶液粘度を示すのは最もMwが高いHSBC4である。これは、重合および水素化工程が共に溶媒において行われるので、その様なHSBCの製造中の著しい利点である。
油性ゲルとしての用途
高MwHSBCを、例えば、パラフィン系油等の液体炭化水素の種々のタイプでゲルを調製するために使用する。これらの「HSBCゲル」は、200℃での高流動性、室温ならびに高温でのゲルの外観(滴点は、ゲルが液体になり始める温度を測定する。)のバランスを示さねばならない。市販品として有効な溶液であるためには、これらのゲルは混合することが容易でなければならず、HSBCの最少量を含まねばならない。また、ゲルは、できる限り、著しい油滲出なしで油を保持しなければならない。
化合物における用途
以下および表9において示される通り、本発明によるHSBCは、また、液体炭化水素およびその他のポリマー材料と組合せた場合に、著しく改善された機械的性能、特に、高温での機械的性能を与えた。
動的加硫を伴う、および伴わない化合物における用途
この実施例においては、本発明によるHSBCが、また、動的加硫を伴い、および伴わずに、液体炭化水素およびその他のポリマーのポリオレフィン系材料と組合された場合に、著しく改善された機械的性能、特により高温での機械的性能を与えることを示す。
化合物における用途
以降の表11において示される通り、本発明によるHSBCは、液体炭化水素、その他のポリマー材料と一緒にプロピレンを基にしたポリマーと組合された場合に、特に高温でのなお更に著しく改善された機械的性能および油抵抗性を与えた。
加工性能の評価
この実施例においては、そして表12において示される通り、幾つかの化合物の加工性能を、メルトフローレートの基準;低圧下、一般的な加工温度で化合物が流動する容易さに基づいて評価した。
Claims (4)
- (a)230,000から275,000のピーク見掛け分子量を有し、一般式(A−B)で表される線状ジブロックコポリマー(I)、
(b)一般式(A−B)2Xで表される、線状2腕ブロックコポリマー(II)、
(c)式(A−B)3Xで表される、3腕ブロックコポリマー(III)、
(d)式(A−B)n>3Xで表される、3腕を超えるブロックコポリマー(IV)、
(e)前記線状ジブロックコポリマー(I)未満のピーク見掛け分子量を有する副ポリマー構造物(SPS)、ここで、該副ポリマー構造物は、線状ジブロックコポリマー(I)の調製の経過の間に生じた停止機構により同様に形成されたポリマーであり、式A’、A及びAB’で表され、Aは上記の通りであり、A’はAと類似するがより小さい分子量を有するものであり、およびB’はBと類似するがより小さい分子量を有するものである
を含み、Aは、主としてポリ(モノビニル芳香族炭化水素)のブロックを表し、前記ポリ(モノビニル芳香族炭化水素)含有量は20から35重量%の範囲にあり、Bは、主としてポリ(共役ジエン)のブロックを表し、Xは、3官能および/または4官能カップリング剤の残基である高分子量結合ブロックコポリマー組成物であり、前記ブロックコポリマー組成物は、450,000から800,000の範囲の重量平均分子量Mwを有し、ブロックコポリマーの相対量は、前記全ブロックコポリマー組成物の重量に対して、それぞれ、Iは5から15重量%であり、IIおよびIIIは合わせて70から90重量%であり、IIIは10重量%超であり、IVは10重量%未満であり、SPSは10重量%未満であることに相当し、それぞれの成分の合計は100%になる、高分子量結合ブロックコポリマー組成物。 - 230,000から275,000のピーク見掛け分子量を有し、一般式RLi(式中Rはリビングジブロックコポリマーを表す)のリビングジブロックコポリマーの形態の線状ジブロックコポリマー(I)の調製、および該リビングジブロックコポリマーと、4官能および/または3官能シランカップリング剤とをカップリングすることを含み、前記カップリング剤は、2:1から1:1の範囲におけるSi:Li(結合される前記最初のリビングジブロックコポリマーの活性末端を表す。)の当量比で使用される、請求項1に記載の高分子量結合ブロックコポリマー組成物の製造方法。
- エキステンダー油、ポリ(オレフィン)、ポリ(モノビニル芳香族)樹脂、炭化水素溶媒、またはこれらの混合物と混合された、請求項1に記載の高分子量結合ブロックコポリマー組成物由来の成型品。
- エキステンダー油、ポリ(オレフィン)、ポリ(モノビニル芳香族)樹脂、炭化水素溶媒、またはこれらの混合物と混合された、請求項1に記載の高分子量結合ブロックコポリマー組成物由来のゲル。
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WO2012067609A1 (en) * | 2010-11-17 | 2012-05-24 | Kraton Polymers Us, Llc | Thermaoplastic elastomer composition with improved compression set values |
FR2980378B1 (fr) * | 2011-09-22 | 2016-02-26 | Rexam Healthcare La Verpillier | Dispositif de distribution de liquide sous forme de gouttes |
ES2816007T3 (es) * | 2017-01-25 | 2021-03-31 | Tsrc Corp | Composición termoplástica de elastómero para espuma entrecruzada y uso de la misma |
US20180334521A1 (en) | 2017-05-17 | 2018-11-22 | Kuraray Co., Ltd. | Vulcanizable composition and moldable thermoplastic elastomer product therefrom |
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