CN106189039B - block copolymer composition - Google Patents
block copolymer composition Download PDFInfo
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- CN106189039B CN106189039B CN201510318697.1A CN201510318697A CN106189039B CN 106189039 B CN106189039 B CN 106189039B CN 201510318697 A CN201510318697 A CN 201510318697A CN 106189039 B CN106189039 B CN 106189039B
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- Prior art keywords
- block copolymer
- weight
- carbon
- acid
- compound
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 150000001993 dienes Chemical class 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 13
- 229930195729 fatty acid Natural products 0.000 claims abstract description 13
- 239000000194 fatty acid Substances 0.000 claims abstract description 13
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000000470 constituent Substances 0.000 claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical group OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 6
- 239000010452 phosphate Substances 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract 1
- -1 dioctylphosphoric acid ester Chemical class 0.000 description 31
- 239000000178 monomer Substances 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 150000008301 phosphite esters Chemical class 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 206010023126 Jaundice Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class 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
- LKWAUAQGDRJTGQ-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C=C1.CC1=CC=C(C=C)C=C1 LKWAUAQGDRJTGQ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- IHWDIGHWDQPQMQ-UHFFFAOYSA-N 1-octadecylsulfanyloctadecane Chemical class CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCC IHWDIGHWDQPQMQ-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- QWQQRBYTGIOUFI-UHFFFAOYSA-N 3-[[3-(2,3-dihydroxypropylsulfanylmethyl)-4-hydroxy-2,5-dimethylphenyl]methylsulfanyl]propane-1,2-diol Chemical compound CC1=CC(CSCC(O)CO)=C(C)C(CSCC(O)CO)=C1O QWQQRBYTGIOUFI-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- VYRAOUAYUGPOCF-UHFFFAOYSA-N 4,4-dimethylpentanoic acid Chemical compound CC(CCC(=O)O)(C)C.CC(CCC(=O)O)(C)C VYRAOUAYUGPOCF-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- WUOLOTPSJRRXAC-UHFFFAOYSA-N C(C)(C)(C)C1=CC=C(C=C)C=C1.C(C)(C)(C)C1=CC=C(C=C)C=C1 Chemical compound C(C)(C)(C)C1=CC=C(C=C)C=C1.C(C)(C)(C)C1=CC=C(C=C)C=C1 WUOLOTPSJRRXAC-UHFFFAOYSA-N 0.000 description 1
- VLMKZCPQJZCMIJ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)C(C(=O)O)CSCCC(=O)O Chemical class C(CCCCCCCCCCCCCCC)C(C(=O)O)CSCCC(=O)O VLMKZCPQJZCMIJ-UHFFFAOYSA-N 0.000 description 1
- DGTRMXWLYKQLKX-UHFFFAOYSA-N CC(CC(=O)O)CC(C)(C)C.CC(CC(=O)O)CC(C)(C)C Chemical compound CC(CC(=O)O)CC(C)(C)C.CC(CC(=O)O)CC(C)(C)C DGTRMXWLYKQLKX-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- RQPCXPDUSNVHSU-UHFFFAOYSA-N [O].[K] Chemical compound [O].[K] RQPCXPDUSNVHSU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- VQKFNUFAXTZWDK-UHFFFAOYSA-N alpha-methylfuran Natural products CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- WLGSIWNFEGRXDF-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O WLGSIWNFEGRXDF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- USYGCQJTEZRGHF-UHFFFAOYSA-N n-diaminophosphoryl-n-methylhexan-1-amine Chemical compound CCCCCCN(C)P(N)(N)=O USYGCQJTEZRGHF-UHFFFAOYSA-N 0.000 description 1
- NWZZFAQUBMRYNU-UHFFFAOYSA-N n-octadecylnonadec-18-en-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC=C NWZZFAQUBMRYNU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical class CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
- CSWFWSPPZMEYAY-UHFFFAOYSA-N octadecyl dihydrogen phosphite Chemical class CCCCCCCCCCCCCCCCCCOP(O)O CSWFWSPPZMEYAY-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- YSWYYGKGAYSAOJ-UHFFFAOYSA-N phosphane Chemical compound P.P YSWYYGKGAYSAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- VMUGSFOXLAAGRW-UHFFFAOYSA-N propanoic acid;3-sulfanylpropanoic acid Chemical compound CCC(O)=O.OC(=O)CCS VMUGSFOXLAAGRW-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 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
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
The invention provides a block copolymer composition, which comprises a block copolymer (A) and a compound (B). The block copolymer (A) comprises at least oneA vinyl aromatic polymer block and at least one conjugated diene polymer block. The compound (B) is at least one selected from the group consisting of a phosphate represented by formula (1) and a derivative thereof, a phosphite represented by formula (2) and a derivative thereof, a fatty acid having a C6-C9 alkyl group with a terminal C4, a derivative thereof, and a combination thereof,in the formulae (1) and (2), R1、R2、R3And R4Each independently is an alkyl group having 4 to 10 carbon atoms or a phenyl group. Thereby maintaining the transparency of the block copolymer composition and not generating fuming and odor during extrusion.
Description
Technical field
The present invention relates to a kind of block copolymer constituent more particularly to a kind of it can maintain transparency and will not when extrusion
Generate the block copolymer constituent of smoke phenomenon and stink.
Background technique
Conjugated diene/vinyl aromatic block copolymer resin is a kind of thermoplasticity polymer being widely used
Resin.Since conjugated diene/vinyl aromatic block copolymer resin transparency and impact resistant strength are good, so often quilt
It is formed for beverage container, clothes hanger, toy and other items.This kind of copolymer resin has many patents and refers to, such as TaiWan, China
574231 patent of patent announcement number or TaiWan, China patent announcement I300069 patent.
In the preparation process of above-mentioned block copolymer resin, usually by vinyl aromatic monomers, conjugated diene
The raw materials such as monomer, initiator and solvent, which are sequentially added in reactive tank, to react.Then, after polymerization reaction whole, then
The active terminator for terminating polymer chain is added.However, existing terminating agent for anionic polymerization (VAC) does not meet European Union EU NO
10/2011 (food contact container method), therefore need to seek other compounds, European Union EU NO 10/2011 can be met, needed simultaneously
Smoke phenomenon and stink will not be generated when extrusion.
Summary of the invention
The present invention provides a kind of block copolymer constituent, can maintain the transparency of block copolymer constituent, and in signature
Smoke phenomenon and stink will not be generated when out.
A kind of block copolymer constituent of the invention, including block copolymer (A) and compound (B).The block
Copolymer (A) include an at least vinyl aromatic polymers block and an at least conjugated diene polymer block, and on
State compound (B) be at least one selected from include phosphite ester shown in phosphate and its derivative, formula (2) shown in formula (1) and
Its derivative, with carbon number 6 to 9 and end is the fatty acid and its derivative of the alkyl of 4 grades of carbon, or combinations thereof,
In formula (1) and formula (2), R1、R2、R3With R4Respectively stand alone as the alkyl or phenyl of carbon number 4 to 10.
In one embodiment of this invention, in above-mentioned constituent with block copolymer constituent be 100 parts by weight, above-mentionedization
The content range of object (B) is closed between 10ppm~3000ppm.
In one embodiment of this invention, in above-mentioned constituent with block copolymer constituent be 100 parts by weight, above-mentionedization
The content range of object (B) is closed between 10ppm~2500ppm.
In one embodiment of this invention, above-mentioned R1With R2It is identical.
In one embodiment of this invention, above-mentioned R3With R4It is identical.
In one embodiment of this invention, phosphate shown in above-mentioned formula (1) is dioctylphosphoric acid ester.
In one embodiment of this invention, phosphite ester shown in above-mentioned formula (2) is diphenyl phosphite.
In one embodiment of this invention, above-mentioned with carbon number 6 to 9 and end be the fatty acid of the alkyl of 4 grades of carbon is tool
There is carbon number 6 to 9 and end is the fatty acid of the alkyl of 4 grades of carbon, main chain with 3 grades of carbon structures.
In one embodiment of this invention, above-mentioned with carbon number 6 to 9 and end is that 4 grades of carbon, main chain have 3 grades of carbon structures
Alkyl fatty acid be 3,5,5 Trimethylhexanoic acid.
In one embodiment of this invention, above-mentioned block copolymer (A) contains 25 weight of vinyl aromatic monomers unit
Measure % to 80 weight % and 20 weight % of conjugated diene monomeric unit to 75 weight %.
In one embodiment of this invention, the weight average molecular weight of above-mentioned block copolymer (A) is 110,000 to 170,000.
Include the compound (B) of specific structure based on above-mentioned, in block copolymer constituent provided by the invention, uses this
Kind compound (B) can maintain the transparency of block copolymer constituent in the molding of production block copolymer constituent, and
And smoke phenomenon and stink will not be generated in extrusion.
To make the foregoing features and advantages of the present invention clearer and more comprehensible, special embodiment below is described in detail below.
Specific embodiment
Hereinafter, will be described in the embodiment of the present invention.However, these embodiments are illustrative, and the present invention discloses not
It is limited to this.
In one embodiment of this invention, block copolymer constituent includes block copolymer (A) and compound (B).
The block copolymer (A) and the compound (B) will be described below.
Block copolymer (A)
Block copolymer (A) of the invention includes an at least vinyl aromatic polymers block and at least one conjugation two
Alkene based polymer block.The block copolymer (A) preferably contains vinyl aromatic monomers unit 25 weight % to 80 weights
% and 20 weight % of conjugated diene monomeric unit to 75 weight % is measured, vinyl aromatic monomers unit 27 is more preferably contained
Weight % to 78 weight % and 22 weight % of conjugated diene monomeric unit most preferably contain vinyl aromatic to 73 weight %
30 weight % of race's monomeric unit to 75 weight % and 25 weight % of conjugated diene monomeric unit to 70 weight %.Above-mentioned ethylene
Base aromatic monomer unit and conjugated diene monomeric unit refer to the vinyl aromatic list having polymerize in block copolymer (A)
The structural unit of body and conjugation diene monomer.When vinyl aromatic monomers unit content 25 weight % to 80 weight % with
And conjugated diene monomer unit content within the scope of 20 weight % to 75 weight % when, the resistance to punching of low temperature of block copolymer (A)
The physical property such as hit intensity, transparency and folding resistance balance is good.
The molecular structure of block copolymer (A) of the invention is preferably linear molecular structure, this is to block copolymer (A)
Mobility and the physical property balance such as folding resistance on have good effect.
The molecular structure of block copolymer (A) of the invention for example contains the molecular structure of (branch) of disagreeing, will be advantageous
In the melt strength and extrusion appearance of block copolymer (A).In addition, block copolymer (A) of the invention, is preferably free of ethylene
Alternation block (Tapered block) person of base aromatic monomer and conjugation diene monomer, so that softening point and low temperature are resistance to
The physical property such as impact strength balance.
Above-mentioned vinyl aromatic monomers it is specific for example: styrene (styrene, abbreviation SM), ortho-methyl styrene
(o-methyl styrene), p-methylstyrene (p-methyl styrene), p- t-butyl styrene (p-tert-
Butyl styrene), 1,3- dibutyl styrene (1,3-di-butyl styrene), α-methylstyrene (α-methyl
Styrene), ethyl styrene, 2,4-DMS, Alpha-Methyl-p-methylstyrene, bromo- styrene, wherein and with
Styrene is preferable.Above-mentioned vinyl aromatic monomers can be used alone a kind of or several uses of mixing.
Above-mentioned conjugated diene monomer it is specific for example: 1,3-butadiene (1,3-butadiene, abbreviation BD), 2- methyl-
1,3-butadiene, 2,3- be bis--methyl-1,3- butadiene, 1,3-pentadiene, 1,3- hexadiene etc., wherein again with 1,3-butadiene
Or 2- methyl-1,3- butadiene are preferable.Above-mentioned conjugated diene monomer can be used alone a kind of or several uses of mixing.
The weight average molecular weight of block copolymer (A) of the present invention be preferably 110,000 to 170,000, more preferably 11.5 ten thousand to
16.5 ten thousand, most preferably 120,000 to 16.1 ten thousand.
Compound (B)
The compound of the present invention (B) is at least one selected from including phosphate and its derivative, following formula shown in following formula (1)
(2) phosphite ester and its derivative shown in, with carbon number 6 to 9 and end is the fatty acid and its derivative of the alkyl of 4 grades of carbon
Object, or combinations thereof.
Formula (1) is as follows:
In formula (1), R1With R2Respectively stand alone as the alkyl or phenyl of carbon number 4 to 10.
Above-mentioned R1With R2It is independent it is specific for example: butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl or phenyl；
Preferably octyl.
R in formula (1)1And R2It can be identical or different；Preferably R1And R2It is identical.
The concrete example of formula (1) for example dioctylphosphoric acid ester (Dioctyl phosphate) represented by following structural formula
Formula (2) is as follows:
In formula (2), R3With R4Respectively stand alone as the alkyl or phenyl of carbon number 4 to 10.
Above-mentioned R3With R4It is independent it is specific for example: butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl or phenyl.
Preferably phenyl.
R in formula (2)3With R4It can be identical or different；Preferably R3With R4It is identical.
The concrete example of formula (2) for example diphenyl phosphite (Diphenyl phosphonate) represented by following structural formula
It is above-mentioned with carbon number 6 to 9 and end be the concrete example of the fatty acid of the alkyl of 4 grades of carbon for example: 2,3,3- trimethyl
Butyric acid (2,3,3-trimethylbutanoic acid), 3,4,4- trimethyl valeric acid (3,4,4-trimethylpentanoic
Acid), 2,4,4- trimethyl valeric acid (2,4,4-trimethylpentanoic acid), 2- ethyl -2,3,3- trimethyl butyric acid
(2-ethyl-2,3,3-trimethylbutanoic acid), 3,5,5 Trimethylhexanoic acid (3,5,5-
Trimethylhexanoic acid), 2,2,4,4- tetramethyl valeric acid (2,2,4,4-tetramethylpentanoic
Acid), 4,4- dimethyl valeric acid (4,4-dimethylpentanoic acid), 5,5- dimethylhexanoic acid (5,5-
Dimethylhexanoic acid), 6,6- dimethyl enanthic acid (6,6-dimethylheptanoic acid) etc..Wherein again with
With carbon number 6 to 9 and end is that have the fatty acid of alkyl of 3 grades of carbon structures be preferable for 4 grades of carbon, main chain.
In one embodiment, above-mentioned with carbon number 6 to 9 and end is that 4 grades of carbon, main chain have the alkyl of 3 grades of carbon structures
Fatty acid, for example 3,5,5- tri-methyl hexanoic acids (3,5,5-trimethylhexanoic acid) represented by following structural formula
Derivative in above compound (B) refers to phosphite ester or tool shown in phosphate shown in formula (1), formula (2)
After thering is carbon number 6 to 9 and end to be replaced for the hydrogen ion in the fatty acid of the alkyl of 4 grades of carbon by alkali metal ion, it is formed by salt
Class.The concrete example of derivative for example, above-mentioned 3, after the hydrogen ion in 5,5- tri-methyl hexanoic acids is replaced by lithium ion, be formed by 3,
5,5- tri-methyl hexanoic acid lithium.
Above compound (B) can be used alone a kind of or several uses of mixing.
In block copolymer constituent of the invention, with above-mentioned block copolymer constituent for 100 parts by weight, compound
(B) content range is preferably between 10ppm~3000ppm；Between more preferably 10ppm~2500ppm；Most preferably 15ppm~
Between 2200ppm.When the content of above compound (B) is within the scope of 10ppm~3000ppm, there is preferable polymerization
Effect, the excellent transparency of obtained block copolymer constituent, and smoke phenomenon and stink will not be generated in extrusion.
The preparation of block copolymer constituent
The preparation method of block copolymer constituent of the invention includes first carrying out the polymerization reaction of block copolymer (A),
Then it adds the compound of the present invention (B), after removing solvent seasoning, can be prepared by block copolymer composition of the invention
Object.More specifically, the polymerization reaction of block copolymer (A) is dissolved in solvent by monomer in block copolymer constituent of the invention
Middle carry out polymerization reaction, then adds the compound of the present invention (B), forms polymer cement, above-mentioned glue in solvent later
The modes such as slurry usually contains the solid content of 10 weight of weight %~35 %, and aforementioned rubber cement can be depressurized or be heated are further concentrated in advance
The solid content of 50 weight of weight %~99 %, then with vacuum drying oven, remove volatilization extruder, or import remaining molten to remove in hot water
Agent can be prepared by block copolymer constituent of the invention.
It is by vinyl aromatic monomers, conjugated diene monomer, initiator and solvent etc. when carrying out polymerization reaction
Raw material is sequentially added in reactive tank and reacts.In each stage monomer fully reacting and then the reaction monomers of progress next stage
Pan feeding.It whether fully reacting, can judge according to reaction temperature, represent fully reacting when reaction temperature stops and rising.Poly-
The polymerization temperature in reaction is closed for example between -40 DEG C~150 DEG C, preferably 40~120 DEG C；Polymerization time and polymerization pressure are then
It is different and different with polymerizing condition, wherein polymerization time is usually preferably 0.1~10 hour in 20 hours, more preferably
0.5~5 hour.In addition, being mixed into for impurity need to be prevented in polymerization, and such as: water, acids, carbon dioxide etc..
After polymerization reaction whole, the compound (B) in block copolymer constituent of the present invention is added.
Initiator (C)
In block copolymer constituent of the invention, block copolymer (A) is when carrying out polymerization reaction, used initiation
Agent (C) can for example enumerate organic alkali metal compound, and general formula can be indicated with RM, wherein R represent carbon number 1 to 20 alkyl,
Naphthenic base, aryl, preferably alkyl；And M represents alkali metal, such as lithium, sodium, preferably lithium.The dosage of above-mentioned initiator (C) according to
The molecular weight of required each block or block copolymer (A) determines, typically with respect to the 0.01~1.0 of 100 weight parts monomers
Parts by weight.
In aforementioned organic alkali metal compound, organo-lithium compound it is specific for example: n-propyl lithium, n-BuLi are (referred to as
N-BuLi), s-butyl lithium, tert-butyl lithium, n-pentyl lithium, hexyllithium, benzyl lithium (benzyl lithium), phenyl lithium,
The double lithiums of tolyl lithium (tolyl lithium), two lithium of trimethylene, two lithium of tetramethylene, butadiene and the double lithiums of isoprene etc.,
It is wherein preferable with n-BuLi.A kind of or several uses of mixing in addition, above-mentioned initiator (C) can be used alone.
Solvent (D)
In block copolymer constituent of the invention, block copolymer (A) is when carrying out polymerization reaction, used solvent
(D) such as can enumerate: pentane, hexane, octane, hexamethylene, wherein being preferable with hexamethylene.Above-mentioned solvent (D) can individually make
With a kind of or several uses of mixing.
Polar compound (E)
Rate of polymerization in polymerization of block copolymer (A) in block copolymer constituent of the invention, 1,2- ethylene
Base content can be adjusted by polar compound (E).The polar compound (E) can for example enumerate: ethers, amine (amine),
The potassium or sodium salt of thioether class, phosphine (phosphine) or phosphono amine, trialkylphosphine oxide.Be suitable for it is of the invention it is specific for example:
(a) ethers: dimethyl ether, Anaesthetie Ether, dibutyl ethers, diphenyl ether, tetrahydrofuran (tetrahydrofuran,
Abbreviation THF), oxinane, diethylene glycol dimethyl ether (diethylglycol dimethyl ester), ethylene glycol dibutyl
Ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, diphenyl ether etc..
(b) amine: tertiary amine, Trimethylamine, triethylamine, tripropylamine, tri-butylamine, four-methyl-ethylidine are double
Amine, diethylaniline, pyridine, ring tertiary amine etc..
(c) phosphine or phosphono amine: three-Phenylphosphines, hexylmethylphosphoramide etc..
(d) potassium or sodium salt of trialkylphosphine oxide: fourth oxygen potassium (potassium butoxide).
It is preferable with tetrahydrofuran in above several concrete examples.One kind or mixed in addition, polar compound (E) can be used alone
Close several uses.
Vinyl aromatic monomers and conjugated diene of the additive amount of above-mentioned polar compound (E) relative to 100 parts by weight
It is the total amount of monomer, preferably 0.005~10 parts by weight, more preferably 0.03~1 parts by weight, most preferably 0.06~0.6 parts by weight.
Additive (F)
Block copolymer constituent of the invention can be added additive appropriate (F), such as: antioxidant, chelating agent, cunning
Agent, antistatic agent, weather resisting agent etc..
Wherein, such as phenolic antioxidant, thioether antioxidant or phosphorous antioxidant can be used in antioxidant.
The additive amount of phenolic antioxidant with 0.005~2.0 parts by weight (relative to 100 parts by weight of block copolymer) be compared with
It is good, phenolic antioxidant it is specific for example: octadecyl (3,5- dual-tert-butyl -4- hydroxyphenyl)-propionic ester, triethylene glycol are double
[3- (3- tert-butyl -5- methyl -4- hydroxyphenyl) propionic ester], four [methylene base -3- (3,5- dual-tert-butyl -4- hydroxyphenyl) propionic acid
Ester] methane, 2- tert-butyl -6- (3- tert-butyl -2- hydroxyl -6- methylbenzyl) -4- aminomethyl phenyl acrylate, 2,2'- first
Support group-bis- (4- methyl-6-tert butyl phenol), 2,2'- sulphur bis- (4- methyl-6-tert butyl phenol), 2,6- di-t-butyl -4- methyl
Phenol, 2,2'- be thio-diethyl support group-bis- [3- (3,5- dual-tert-butyl -4- hydroxyphenyl) propionic esters], 2,2'- oxalamide-bis- [second
Base -3- (3,5- bis--tert-butyl -4- hydroxyphenyl) propionic ester] etc., wherein with octadecyl (3,5- dual-tert-butyl -4- hydroxyphenyl) -
Propionic ester is preferable.
The additive amount of thioether antioxidant is with 0.005~2.0 parts by weight (relative to 100 parts by weight of block copolymer)
It is good, thioether antioxidant it is specific for example: distearyl thiodipropionic acid ester, two palmityl thiodipropionic acid esters, five erythrites-
Four-(β-ten dimethyl-sulphur propionic ester), double octadecyl thioethers, bis- (n- the octyl group s-methyl) -6- sylvan [2,4- of 2,4-
Bis (n-octyl thio methyl) -6-methyl phenol], bis- (bis--hydroxypropyl of 2', 3'- sulfidomethyl) -3,6- of 2,4-
Dimethyl phenol (2,4-bis (2', 3'-di-hydroxy propylthio methyl) -3,6-di-methyl phenol), 2,
Bis- (2'- Acetoxvethyl sulfidomethyl) two-sylvan of -3,6- (2,4-bis (the 2'-acetyloxy ethyl thio of 4-
Methyl) -3,6-di-methyl phenol), bis- (the octyl group s-methyl)-o-cresols of 4,6- [4,6-bis (octyl thio
Methyl) -0-cresol] etc., wherein bis- (the octyl group s-methyl)-o-cresols of 6- are preferable with 4.
Phosphorous antioxidant is phosphite ester system antioxidant or phosphate system antioxidant, additive amount with 0.015~
2.0 parts by weight (relative to 100 parts by weight of block copolymer) be it is preferable, phosphorous antioxidant it is specific for example: three (nonyl benzenes
Base) phosphite ester, dodecyl phosphite ester, cyclic annular neopentane tetralyl bis- (octadecyl phosphite esters), 4,4'- Aden
Base bis- (3- methyl-6-tert butyl phenyl-double tridecyl phosphite ester), three (2,4- tert-butyl-phenyl) phosphite esters, four (2,
4- tert-butyl-phenyl) -4,4'- stretches biphenyl phosphate, 9,10- dihydro-9-oxy -10- phosphoric acid phenanthrene -10- oxygen supports etc..
The additive amount of chelating agent take 0.001~2.0 parts by weight (relative to 100 parts by weight of block copolymer) as preferable, tool
Body is for example: dibenzoyl methane, sodium salt of ethylenediaminetetraacetic acid etc..
The additive amount of lubrication prescription is preferable, concrete example with 0.03~5.0 parts by weight (relative to 100 parts by weight of block copolymer)
Such as: calcium stearate, magnesium stearate, the metallic soaps of lithium stearate, ethylene distearyl amide, methylene distearyl amide, palm
The chemical combination of sour amide, butyl stearate, stearic acid palm ester, poly- propionic acid alcohol tristearate, behenic acid, stearic acid etc.
Object, polyethylene wax, octocosoic acid wax, Brazil wax (Carnauba wax), pertroleum wax etc..
All experiment is exemplified below to verify effect of the invention, but the scope of the invention is not limited to following realities
It tests.The present invention will be described in more detail for following instance.
Experimental example 1~11
The raw material used has:
1. vinyl aromatic monomers is styrene (abbreviation SM).
2. conjugated diene monomer is 1,3- butadiene (abbreviation BD).
3. initiator (C) is the n-BuLi (abbreviation n-BuLi) that concentration is 8 weight %.
4. polar compound (E) is tetrahydrofuran (abbreviation THF).
5. compound (B) has (1) dioctylphosphoric acid ester, (2) diphenyl phosphite, (3) 3,5,5 Trimethylhexanoic acid respectively.
6. solvent (D) uses thiacyclohexane.
Firstly, in the presence of nitrogen, polymerize in batch reactor, wherein reaction pressure about 1Kg/cm2~3Kg/cm2、
Reaction temperature is at 50 DEG C~120 DEG C, the reaction time about 60 minutes~150 minutes.Reactor volume is 160 liters, and solvent (D) uses
Thiacyclohexane, and charge order and raw material weight are according to shown in table 1.Above after the reaction was completed, 1 compound represented of table (B) is added.
After the reaction was completed, solid of the rubber cement obtained containing about 25 weight %, rubber cement is passed through in hot water later remove it is molten
Agent, recycling are obtained wet micelle again with extruder extrusion drying and dehydrating, are compared with the block copolymer constituent for being made of the invention
Compared with.
Test method
1. assay:
Take 1 gram of block copolymer constituent with acetone solution after, be subsequently added into methanol, make the polymer poly of high molecular weight
Collection sedimentation, takes upper liquid and with gas chromatograph (GC) (Hewlett Packard with flame ionization detector (FID)
Company's manufacture；Model 6890, tubing string HP-5) carry out quantitative analysis.
2. terminating measure of merit:
After block copolymer constituent is granulated with extruder extrusion, acquirement particle progress is hot-forming, terminates incomplete person
Test piece is easily turned to be yellow.As the result is shown in table 1.
Zero: test piece is without jaundice.
╳: test piece jaundice.
3. extrusion smokiness is tested:
Extrusion process observation its smokiness in aforementioned termination measure of merit.As the result is shown in table 1.
Zero: without smoke phenomenon.
╳: there is smoke phenomenon.
4. extrusion stink is tested:
Extrusion process observation its stink in aforementioned termination measure of merit.As the result is shown in table 1.
Zero: odorless.
╳: there is stink.
Comparative example 1~11
In addition to the compound being added after the reaction was completed is changed to (1) lauric acid (Lauric acid), (2) tributyl phosphate
(tributyl phosphate), (3) 3- mercaptan propionic acid (3-mercapto propionic acid), (4) trimethyl hexanol
(3,5,5-Trimethyl-1-hexanol), using raw material identical with experimental example 1~11, weight and charge order, see table
2。
Then termination effect, the extrusion hair of the block copolymer constituent of comparative example 1~11 are obtained with above-mentioned test method
The test result of cigarette and extrusion stink is shown in table 2.
Table 1
1 (Continued) of table
Table 2
2 (Continued) of table
From the result of Tables 1 and 2 it is found that the termination effect of block copolymer constituent of the invention is good, thus test piece without
Jaundice, can maintain the transparency of block copolymer constituent.Moreover, block copolymer constituent of the invention when extrusion not yet
Smoke phenomenon and stink can be generated.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (7)
1. a kind of block copolymer constituent characterized by comprising
Block copolymer (A), including at least a vinyl aromatic polymers block and at least a conjugated diene polymer
Block；And
Compound (B) is at least one selected from carbon number 6 to 9 and end is the fatty acid and its derivative of the alkyl of 4 grades of carbon.
2. block copolymer constituent according to claim 1, which is characterized in that be with the block copolymer constituent
100 parts by weight, the content range of the compound (B) is between 10ppm~3000ppm.
3. block copolymer constituent according to claim 1, which is characterized in that be with the block copolymer constituent
100 parts by weight, the content range of the compound (B) is between 10ppm~2500ppm.
4. block copolymer constituent according to claim 1, which is characterized in that described there is carbon number 6 to 9 and end to be
The fatty acid of the alkyl of 4 grades of carbon is with carbon number 6 to 9 and end is the fat of the alkyl of 4 grades of carbon, main chain with 3 grades of carbon structures
Acid.
5. block copolymer constituent according to claim 4, which is characterized in that described there is carbon number 6 to 9 and end to be
It is 3,5,5 Trimethylhexanoic acid that 4 grades of carbon, main chain, which have the fatty acid of the alkyl of 3 grades of carbon structures,.
6. block copolymer constituent according to claim 1, which is characterized in that the block copolymer (A) contains second
25 weight % of alkenyl aroma race monomeric unit to 80 weight % and conjugated diene monomeric unit 20 weight % to 75 weights
Measure %.
7. block copolymer constituent according to claim 1, which is characterized in that the weight of the block copolymer (A)
Average molecular weight is 110,000 to 170,000.
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| TW103146052A TWI518130B (en) | 2014-12-29 | 2014-12-29 | Block copolymer composition |
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| EP0387671A1 (en) * | 1989-03-13 | 1990-09-19 | The Dow Chemical Company | Process for preparing polymers by anionic polymerization |
| CN1242777A (en) * | 1996-12-31 | 2000-01-26 | 拜尔公司 | Process for making stabilized non-coloured rubber |
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|---|---|
| TW201623424A (en) | 2016-07-01 |
| CN106189039A (en) | 2016-12-07 |
| TWI518130B (en) | 2016-01-21 |
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