CN117069881A - Low cis-polybutadiene rubber and preparation method and application thereof - Google Patents
Low cis-polybutadiene rubber and preparation method and application thereof Download PDFInfo
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- CN117069881A CN117069881A CN202210507031.0A CN202210507031A CN117069881A CN 117069881 A CN117069881 A CN 117069881A CN 202210507031 A CN202210507031 A CN 202210507031A CN 117069881 A CN117069881 A CN 117069881A
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- Prior art keywords
- molecular weight
- polybutadiene rubber
- low cis
- low
- range
- Prior art date
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- Pending
Links
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 131
- 239000005064 Low cis polybutadiene Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920005669 high impact polystyrene Polymers 0.000 claims abstract description 65
- 239000004797 high-impact polystyrene Substances 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 238000009826 distribution Methods 0.000 claims abstract description 36
- 230000002902 bimodal effect Effects 0.000 claims abstract description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 50
- 239000003999 initiator Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 125000001979 organolithium group Chemical group 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 14
- 239000005062 Polybutadiene Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 10
- 241001550224 Apha Species 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims description 5
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YTUUEOBZXXUZJL-UHFFFAOYSA-N 2,3-diethylpentane-1,2,3-triol Chemical compound CCC(O)(CC)C(O)(CC)CO YTUUEOBZXXUZJL-UHFFFAOYSA-N 0.000 claims description 2
- GFTPTQVIOIDDRL-UHFFFAOYSA-N 2,3-dimethylbutane-1,2,3-triol Chemical compound CC(C)(O)C(C)(O)CO GFTPTQVIOIDDRL-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- 239000000243 solution Substances 0.000 description 42
- 229920001971 elastomer Polymers 0.000 description 35
- 239000005060 rubber Substances 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000012745 toughening agent Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- -1 variable metals Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 4
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000008177 pharmaceutical agent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical group CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101150095057 DPB2 gene Proteins 0.000 description 1
- 101150030825 DPB3 gene Proteins 0.000 description 1
- 101150115749 DPB4 gene Proteins 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of polymer preparation, and discloses a low cis-polybutadiene rubber, a preparation method and application thereof. The molecular weight of the low cis-polybutadiene rubber is in bimodal distribution and has the following characteristics: the ratio of the number average molecular weight of the bimodal high molecular weight component to the number average molecular weight of the low molecular weight component is from 5 to 6; the bimodal low molecular weight component has a number average molecular weight of 30000-50000 and a molecular weight distribution index of 1-1.1; the bimodal high molecular weight component has a number average molecular weight of 150000-300000 and a molecular weight distribution index of 1-1.1; low cis polybutadiene rubber at 100Mooney viscosity ML at C 1+4 45-65; the viscosity of the 5 wt% styrene solution at 25℃is 10-28 centipoise. The low cis-polybutadiene rubber has high branching degree, low 5% styrene solution viscosity and high Mooney viscosity, and can be suitable for high-gloss HIPS resin.
Description
Technical Field
The invention relates to the field of polymer preparation, in particular to low cis-polybutadiene rubber, and a preparation method and application thereof.
Background
Continuous bulk HIPS can be classified into high flow HIPS, high gloss HIPS, matte HIPS, high impact HIPS, and ultra high impact HIPS depending on the application. Polybutadiene rubber is the preferred toughening rubber for continuous bulk HIPS due to low glass transition temperature and good low-temperature impact resistance. According to the microstructure, the polybutadiene rubber for HIPS toughening is divided into high cis-polybutadiene rubber and low cis-polybutadiene rubber, wherein the low cis-polybutadiene rubber has low gel content, no transition metal, good color, random cis-trans distribution, no crystallization tendency, good low-temperature shock resistance, freely adjustable molecular weight, moderate 1, 2-structural unit content and high grafting and crosslinking reactivity, and is the preferred toughening rubber modified by the HIPS resin with a continuous body.
In a reasonable rubber particle size range, along with the increase of the rubber particle size, the rubber particles are easier to induce silver marks and shear bands, so that impact energy is better dissipated, and the impact resistance of HIPS resin is improved. The increase in the particle size of the rubber reduces the scattering effect on light, and the gloss of HIPS resin decreases. During HIPS production, the toughening rubber is dissolved in the styrene monomer and thermally initiated (or free radical initiated). In the initial stage of polymerization, the rubber phase is a continuous phase, and phase inversion starts to occur when the solution viscosity of the polystyrene phase is equal to that of the rubber phase as the grafting reaction proceeds, so that the greater the solution viscosity of the rubber, the later the time for phase inversion to occur, and more polystyrene is occluded in the rubber phase, thereby forming a larger rubber particle size. In general, the preparation of high gloss HIPS requires a toughening rubber having a 5% styrene solution viscosity of less than 50 centipoise to obtain rubber particles of less than 1 μm.
CN109503747A discloses a low cis-polybutadiene rubber with a Mooney viscosity of 40-65, a viscosity of 80-120 centipoise in a 5 wt% styrene solution at 25 ℃ and application thereof in HIPS/ABS resin. CN109251262a discloses a low cis polybutadiene rubber with a trimodal molecular weight distribution and its use in HIPS resins. CN109251263A discloses a low cis-polybutadiene rubber with weight average molecular weight of 17-38 ten thousand and molecular weight distribution of 2-3 and application thereof in HIPS/ABS resin. CN109503746A discloses a low cis-polybutadiene rubber with a Mooney viscosity of 40-65, a viscosity of 140-190 centipoise in a 5 wt.% styrene solution at 25 ℃ and its application in HIPS/ABS resin. CN106589247A discloses a low cis-polybutadiene rubber with a Mooney viscosity of 50-70, a viscosity of 40-60 centipoise in a 5 wt% styrene solution at 25 ℃ and application thereof in HIPS/ABS resin. In order to ensure that the Mooney viscosity of the product is in a proper range so as to obtain good processing performance, the 5% styrene solution viscosity of the product is high, and the application of the product in the field of high-gloss HIPS is limited.
The star products of the low cis-polybutadiene rubber formed in the market are almost all coupled by silicon tetrachloride to obtain the star low cis-polybutadiene rubber with four arms branched. For ultra-high gloss continuous bulk HIPS resins, it is desirable to reduce the 5% styrene solution viscosity of the toughening rubber as much as possible. The viscosity of the existing four-arm coupled star-shaped low cis-polybutadiene rubber with 5% styrene solution cannot be infinitely reduced, otherwise, the Mooney viscosity of the rubber can be reduced to the extent that the rubber cannot be processed. At present, the low cis polybutadiene rubber product with the lowest 5% styrene solution viscosity on the market is 720AX formed by Asahi Kasei, wherein the 5% styrene solution viscosity is in the range of 20-30 centipoise, but the Mooney viscosity at 100 ℃ is below 40, and the cold flow phenomenon is very serious during processing.
Therefore, there is a need to develop a low cis polybutadiene rubber product with a lower 5% styrene solution viscosity and a moderate Mooney viscosity to meet the upgrade requirements of high quality HIPS resin products.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a low cis-polybutadiene rubber, a preparation method and application thereof, wherein the low cis-polybutadiene rubber has high branching degree, low 5% styrene solution viscosity and high Mooney viscosity, and can be suitable for high-gloss HIPS resin.
In order to achieve the above object, the present invention provides a low cis-polybutadiene rubber characterized in that the molecular weight of the low cis-polybutadiene rubber is bimodal and the low cis-polybutadiene rubber has the following characteristics:
(1) The ratio of the number average molecular weight Mn2 of the bimodal high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component is from 5 to 6;
(2) The bimodal low molecular weight component has a number average molecular weight Mn1 in the range of 30,000 to 50,000 and a molecular weight distribution index Mw1/Mn1 in the range of 1 to 1.1;
(3) The number average molecular weight Mn2 of the bimodal high molecular weight component is in the range of 150,000-300,000 and the molecular weight distribution index Mw2/Mn2 is from 1 to 1.1;
(4) Mooney viscosity ML of the low cis-polybutadiene rubber at 100 DEG C 1+4 In the range of 45-65;
(5) The viscosity of the 5 wt.% styrene solution at 25℃of the low cis-polybutadiene rubber is in the range of 10 to 28 centipoise.
In a second aspect, the present invention provides a process for producing a low cis-polybutadiene rubber, comprising the steps of:
(1) In an organic solvent, carrying out anionic solution polymerization reaction on 1, 3-butadiene in the presence of an organolithium initiator and a structure regulator until the conversion rate of the 1, 3-butadiene is more than 99%, so as to obtain a polybutadiene active chain; wherein the molar ratio of the 1, 3-butadiene to the organolithium initiator is 550-950:1, a step of;
(2) Coupling the polybutadiene living chain in the presence of a 6-functional coupling agent; the molar ratio of the coupling agent to the organolithium initiator is 0.14-0.19:1, a step of;
(3) The product of the coupling reaction is terminated in the presence of a terminating agent.
In a third aspect, the present invention provides a low cis-polybutadiene rubber produced by the above-mentioned production method.
In a fourth aspect, the present invention provides the use of the low cis-polybutadiene rubber described above in HIPS resins.
The low cis-polybutadiene rubber provided by the invention and the preparation method and application thereof have the following beneficial effects:
the low cis-polybutadiene rubber provided by the invention has the advantages of higher Mooney viscosity, ultralow 5% styrene solution viscosity, low gel content and halogen content, good APHA chromaticity and proper molecular weight distribution, and can obviously improve the glossiness of HIPS resin when being used for toughening continuous bulk HIPS resin.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a low cis-polybutadiene rubber, characterized in that the molecular weight of the low cis-polybutadiene rubber is bimodal, and the low cis-polybutadiene rubber has the following characteristics:
(1) The ratio of the number average molecular weight Mn2 of the bimodal high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component is from 5 to 6;
(2) The bimodal low molecular weight component has a number average molecular weight Mn1 in the range of 30,000 to 50,000 and a molecular weight distribution index Mw1/Mn1 in the range of 1 to 1.1;
(3) The number average molecular weight Mn2 of the bimodal high molecular weight component is in the range of 150,000-300,000 and the molecular weight distribution index Mw2/Mn2 is from 1 to 1.1;
(4) Mooney viscosity ML of the low cis-polybutadiene rubber at 100 DEG C 1+4 In the range of 45-65;
(5) The viscosity of the 5 wt.% styrene solution at 25℃of the low cis-polybutadiene rubber is in the range of 10 to 28 centipoise.
The low cis-polybutadiene rubber provided by the invention has high Mooney viscosity and low 5% styrene solution viscosity, and when the molecular weight of the low cis-polybutadiene rubber has the characteristics, more small-particle-size rubber can be obtained, and when the low cis-polybutadiene rubber is used for toughening continuous bulk HIPS resin, the glossiness of the HIPS resin can be obviously improved.
In particular, in the present invention, controlling the number average molecular weight of the high molecular weight component in the bimodal distribution to satisfy the above range enables the Mooney viscosity ML of the low cis-polybutadiene rubber at 100 DEG C 1+4 In the range of 45-65. In the present invention, controlling the number average molecular weight of the low molecular weight component in the bimodal distribution to satisfy the above range enables the low cis-polybutadiene rubber to have a 5 wt% styrene solution viscosity in the range of 10 to 28 centipoise at 25 ℃.
Further, when the ratio (Mn 2/Mn 1) of the number average molecular weights of the low molecular weight component and the high molecular weight component in the bimodal distribution is controlled to satisfy the above range, the low cis-polybutadiene rubber can be made to have a higher branching arm number, and further, the Mooney viscosity can be kept in a proper range when the 5% styrene solution viscosity of the low cis-polybutadiene rubber at 25 ℃ is low, thereby having good processability.
Further, the bimodal distribution of low molecular weight components has a number average molecular weight Mn1 in the range of 35,000-45,000.
Further, the number average molecular weight Mn2 of the bimodal high molecular weight component is in the range of 180,000-270,000.
Further, the low cis-polybutadiene rubber has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 50-60.
Further, the low cis polybutadiene rubber has a 5 wt.% styrene solution viscosity in the range of 12 to 26 centipoise at 25 ℃, preferably in the range of 15 to 24 centipoise.
According to the invention, the low cis-polybutadiene rubber has a number average molecular weight Mn in the range of 140,000-260,000 and a molecular weight distribution index Mw/Mn of 1.1 to 1.5.
In the present invention, when the number average molecular weight and the molecular weight distribution index of the low cis-polybutadiene rubber satisfy the above ranges, the low cis-polybutadiene rubber can be made to have an appropriate particle size distribution and a styrene solution viscosity of 5 wt% at 25 ℃, and when the above low cis-polybutadiene rubber is used for toughening a continuous bulk HIPS resin, the overall performance of the HIPS resin can be made excellent.
Further, the low cis-polybutadiene rubber has a number average molecular weight Mn in the range of 160,000-240,000 and a molecular weight distribution index Mw/Mn of 1.15 to 1.45.
According to the invention, the weight ratio of the bimodal low molecular weight component to the high molecular weight component is from 0.01 to 0.25:1.
In the invention, when the weight ratio of the low molecular weight component and the high molecular weight component in bimodal distribution meets the above range, the control of the branching degree of the low cis-polybutadiene rubber can be realized, so that the control of the Mooney viscosity of the low cis-polybutadiene rubber is realized, the low cis-polybutadiene rubber has high branching degree and proper Mooney viscosity, good processability is obtained, the control of the gel content and chromaticity of the product is facilitated, and HIPS resin with better comprehensive performance can be prepared when the HIPS resin is used as a toughening agent.
In the present invention, the weight ratio of the bimodal low molecular weight component to the high molecular weight component is measured by GPC.
Further, the weight ratio of the bimodal low molecular weight component to the high molecular weight component is from 0.04 to 0.18:1.
According to the invention, the weight ratio of the 1, 2-structure content to the 1, 4-structure content in the low cis-polybutadiene rubber is 0.06-0.25:1.
In the present invention, the term "1, 2-structure" means a structural unit in which butadiene is formed in a1, 2-polymerization manner, and the term "1, 4-structure" means a structural unit in which butadiene is formed in a1, 4-polymerization manner. When the weight ratio of the 1, 2-structure content to the 1, 4-structure content in the low cis-polybutadiene rubber is controlled to satisfy the above range, the grafting ratio before the polymerization phase inversion of the continuous bulk HIPS resin and the crosslinking degree in the post-polymerization can be controlled when the low cis-polybutadiene rubber is used for preparing HIPS resin.
Further, the weight ratio of the 1, 2-structure content to the 1, 4-structure content in the low cis-polybutadiene rubber is 0.08-0.2:1.
According to the invention, the gel content of the low cis-polybutadiene rubber is 150mg/kg or less, preferably 100mg/kg or less, more preferably 50mg/kg or less. Gels in low cis polybutadiene rubber can create crystallization sites in HIPS resins, forming stress concentrations, leading to reduced mechanical properties and poor gloss of HIPS resins. The lower the gel content is, the less defects are generated in the HIPS resin prepared, and the better the comprehensive performance is.
According to the invention, the low cis-polybutadiene rubber has a metal content of 100mg/kg or less, preferably 50mg/kg or less, more preferably 30mg/kg or less. Metals, particularly variable metals, in low cis-polybutadiene rubber, which have a low metal content in the present invention, cause deterioration of the color of the product, so that HIPS resins prepared from the low cis-polybutadiene rubber have a low yellow index.
According to the invention, the low cis-polybutadiene rubber has a halogen content of 150mg/kg or less, preferably 100mg/kg or less, more preferably 50mg/kg or less. In the invention, the low cis-polybutadiene rubber has low halogen content, so that the increase of APHA color caused by the excessively high halogen content in the low cis-polybutadiene rubber can be avoided, and the increase of yellow index of HIPS resin can be avoided.
According to the invention, the low cis-polybutadiene rubber has an APHA color of 10 or less, preferably 7 or less, more preferably 5 or less. In the present invention, the low cis-polybutadiene rubber has a low APHA color, which indicates that the low cis-polybutadiene rubber solution has a high clarity, avoiding the increase of yellow index of HIPS resin due to the increase of APHA color of the low cis-polybutadiene rubber.
In a second aspect, the present invention provides a process for producing a low cis-polybutadiene rubber, comprising the steps of:
(1) In an organic solvent, carrying out anionic solution polymerization reaction on 1, 3-butadiene in the presence of an organolithium initiator and a structure regulator until the conversion rate of the 1, 3-butadiene is more than 99%, so as to obtain a polybutadiene active chain; wherein the molar ratio of the 1, 3-butadiene to the organolithium initiator is 550-950:1, a step of;
(2) Coupling the polybutadiene living chain in the presence of a 6-functional coupling agent; the molar ratio of the coupling agent to the organolithium initiator is 0.14-0.19:1, a step of;
(3) The product of the coupling reaction is terminated in the presence of a terminating agent.
In the present invention, the low cis-polybutadiene rubber of the first aspect of the present invention can be obtained by the above-mentioned production method. Particularly, in the invention, the polybutadiene active chain is coupled in the presence of the coupling agent with 6 functional groups, and when the molar ratio of the coupling agent to the organic lithium initiator is controlled to meet the range, the prepared low cis-polybutadiene rubber has higher Mooney viscosity, ultralow 5% styrene solution viscosity, low gel content and halogen content, good APHA chromaticity and proper molecular weight distribution, and can obviously improve the glossiness of HIPS resin when being used for toughening continuous bulk HIPS resin.
According to the invention, in step (1), the anionic solution polymerization will obtain a polymer living chain of 1, 3-butadiene, the reaction process being controlled such that the polymerization of 1, 3-butadiene results in a polybutadiene living chain with a number average molecular weight of 30,000-50,000, preferably a number average molecular weight of 35,000-45,000. In particular such that the molecular weight distribution index of the living chain of the polybutadiene is from 1.0 to 1.1.
In the present invention, in the step (1), the organic solvent may be an organic solvent commonly used in the art, such as an alkane solvent and/or a cycloalkane solvent. Wherein the alkane solvent is preferably at least one of C4-C8 alkane solvents, more preferably at least one of n-pentane, n-hexane, n-heptane and isooctane. Wherein the naphthenic hydrocarbon solvent is preferably at least one of C4-C8 naphthenic hydrocarbon solvents, more preferably cyclopentane and/or cyclohexane.
In the present invention, the amount of the organic solvent may vary within a wide range, and preferably, the content of 1, 3-butadiene is 10 to 20% by weight based on the total weight of the organic solvent and 1, 3-butadiene.
In the present invention, the kind of the organolithium initiator is not particularly limited, and various organolithium initiators conventionally used in the art for the preparation of polybutadiene rubber can be employed, preferably, the organolithium initiator is represented by the formula R 1 Li, wherein R 1 An alkyl group selected from C1-C10; more preferably, the organolithium initiator is one or more of n-butyllithium, sec-butyllithium, isobutyl lithium and tert-butyllithium, more preferably n-butyllithium and/or sec-butyllithium, still more preferably n-butyllithium. Wherein the organic lithium initiator is added into the polymerization system in the form of a solution, and the solvent of the organic lithium initiator can be one or more of hexane, cyclohexane, heptane and the like, and the concentration is preferably 0.1-1.0mol/L.
In the present invention, the amount of the organolithium initiator may be appropriately selected according to the amount of the monomer and the number average molecular weight of the low cis-polybutadiene rubber to be obtained, and may vary within a wide range, and preferably, the molar ratio of 1, 3-butadiene to the organolithium initiator is 550 to 950:1, more preferably 600-850:1, thereby controlling the polybutadiene active chain obtained in the step (1) to have the number average molecular weight as required by the present invention.
According to the invention, the anionic solution polymerization of step (1) will result in a conversion of 1, 3-butadiene of more than 99%, for example 99-100%; preferably, the conditions for the anionic solution polymerization reaction include: the temperature is 40-100deg.C, preferably 50-90deg.C; the time is 20-100min, preferably 30-60min; the gauge pressure is 0.1-1MPa, preferably 0.2-0.5MPa.
In the present invention, the anionic solution polymerization is performed in the presence of a structure-adjusting agent, and the type of the structure-adjusting agent is not particularly limited, and the structure-adjusting agent may be a structure-adjusting agent of a type generally known in the art, and preferably, the structure-adjusting agent is an ether compound structure-adjusting agent and/or an amine compound structure-adjusting agent.
Preferably, the ether compound structure regulator is one or more of aliphatic monoether, aliphatic polyether, aromatic ether and cyclic ether.
More preferably, the aliphatic monoether is one or more of an aliphatic symmetric monoether and an aliphatic asymmetric monoether, the aliphatic symmetric monoether is one or more of methyl ether, ethyl ether, propyl ether, and butyl ether, and the aliphatic asymmetric monoether is methyl ethyl ether.
More preferably, the aliphatic polyether is one or more of an aliphatic symmetric polyether and an aliphatic asymmetric polyether, the aliphatic symmetric polyether is one or more of ethylene glycol di-C1-C4 alkyl ether, diethylene glycol di-C1-C4 alkyl ether and diethylene glycol di-C1-C4 alkyl ether, preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, and the aliphatic asymmetric polyether is ethylene glycol methyl ethyl ether and/or diethylene glycol methyl ethyl ether.
Preferably, the aromatic ether is anisole and/or diphenyl ether.
Preferably, the cyclic ether is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol C1-C4 alkyl ether and 1, 4-dioxane, preferably one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether and 1, 4-dioxane.
Preferably, the amine compound structure regulator is one or more of N, N, N ', N' -tetramethyl ethylenediamine, N, N-dimethyl tetrahydrofurfuryl amine, triethylamine and tripropylamine.
In a preferred embodiment of the present invention, the structure-modifying agent is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, more preferably one or more of tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether and tetrahydrofurfuryl alcohol propyl ether, particularly preferably tetrahydrofurfuryl alcohol ethyl ether.
According to the invention, the molar ratio of the structure-modifying agent to the organolithium initiator is between 0.02 and 2:1. when the molar ratio of the structure regulator to the organolithium initiator satisfies the above range, it is possible to ensure that the vinyl content of the prepared low cis-polybutadiene rubber satisfies the range defined in the present invention while simultaneously improving the reaction rate.
According to the invention, in step (2), the obtained polymer is made to exhibit a bimodal distribution by a coupling reaction, which is controlled to obtain a bimodal distribution polybutadiene rubber, the number average molecular weight of the low molecular weight component in the bimodal is in the range of 30,000-50,000, and the molecular weight distribution index is 1-1.1; the number average molecular weight of the high molecular weight component in the double peak is in the range of 150,000-300,000, and the molecular weight distribution index is 1-1.1; the ratio of the number average molecular weight of the high molecular weight component to the low molecular weight component in the double peak is 5-6; the weight ratio of the low molecular weight component to the high molecular weight component in the double peak is 0.01-0.25:1; the molecular weight distribution of the low cis-polybutadiene rubber is 1.1 to 1.5.
According to the present invention, the 6-functional coupling agent is selected from at least one of hexachlorodisilane, hexachloroethane, 1, 3-hexachloropropane, triethyl glycerol and trimethyl glycerol. Further, in order to further improve the stability and reproducibility of the coupling reaction, the 6-functional coupling agent is preferably hexachlorodisilane and/or hexachloroethane.
According to the invention, in step (2), the molar ratio of the coupling agent to the organolithium initiator is between 0.15 and 0.18:1.
in the present invention, when the molar ratio of the coupling agent to the organolithium initiator satisfies the above range, the low cis-polybutadiene rubber thus produced has a better branching degree to obtain a desired Mooney viscosity.
According to the invention, the conditions of the coupling reaction include: the reaction temperature is 40-100 ℃, the reaction time is 15-40min, and the gauge pressure is 0.1-1MPa.
Further, the conditions of the coupling reaction include: the reaction temperature is 60-100 ℃, the reaction time is 20-40min, and the gauge pressure is 0.1-0.5MPa.
In the present invention, it is preferable that the steps (1) and (2) are performed in a protective atmosphere provided by an inert gas selected from one or more of nitrogen, neon and argon.
In the present invention, in the step (3), the coupling reaction can be terminated and the polymerization reaction can be initiated by using a terminator, and a polymerization solution containing a low cis-polybutadiene rubber can be obtained.
According to the invention, the terminator is one or more of C1-C4 alcohol, organic acid and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid and carbon dioxide, more preferably carbon dioxide. Carbon dioxide is adopted for termination reaction, and can form carbonate with metal ions in a polymerization system to be separated from a polymer, so that the color reaction of the metal ions is avoided, and the product has lower chromaticity. The carbon dioxide may be introduced into the reaction system in the form of a gas (for example, a carbon dioxide gas having a gauge pressure of 0.2 to 1MPa (for example, may be 0.3 to 0.6 MPa)), or may be introduced into the reaction system in the form of an aqueous dry ice solution (for example, a concentration of 0.1 to 5% by weight).
According to the invention, the terminator is used in an amount of 0.1 to 0.2 parts by weight relative to 100 parts by weight of the 1, 3-butadiene monomer.
In order to improve the antioxidant properties of the low cis-polybutadiene rubber according to the present invention, the method preferably further comprises: and (3) mixing the product obtained by terminating the step (3) with an antioxidant.
In the present invention, the kind of the antioxidant is not particularly limited, and may be one or more selected from the group consisting of 4, 6-bis (octylthiomethyl) orthocresol (trade name: antioxidant 1520), N-octadecyl beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: antioxidant 1076), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (trade name: antioxidant 4020), N-isopropyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010 NA) and N-phenyl-2-naphthylamine (trade name: antioxidant D), preferably a mixture of antioxidant 1520 and antioxidant 1076, particularly a combination of antioxidant 1520 and antioxidant 1076 in a weight ratio of 0.5 to 5:1, preferably 1:1.
According to the invention, the amount of antioxidant used can vary within wide limits, preferably the weight ratio of antioxidant to 1, 3-butadiene used is between 0.1 and 0.3:100.
in the present invention, in order to extract the low cis-polybutadiene rubber from the reaction product in which the antioxidant is terminated or introduced, such a reaction product may also be subjected to steam coagulation treatment to remove the solvent and dried to remove the water, and then the dried low cis-polybutadiene rubber is obtained.
In a third aspect, the present invention provides a low cis-polybutadiene rubber prepared by the above-mentioned preparation method.
In a fourth aspect, the invention provides the use of a low cis-polybutadiene rubber in HIPS resins.
In the invention, the low cis-polybutadiene rubber is used as a toughening agent in HIPS resin.
In the present invention, although the toughening agent contains the low cis-polybutadiene rubber obtained by the above method of the present invention to obtain a HIPS resin with high gloss, in order to obtain a HIPS resin with more excellent overall properties, it is preferable that the weight ratio of styrene and the toughening agent in terms of dry weight is 550 to 1900:100, more preferably 800-1600:100. the toughening agent is preferably a low cis polybutadiene rubber.
The HIPS resin prepared by the method has excellent mechanical properties, particularly impact strength, and higher glossiness; preferably, the HIPS resin has a surface gloss of 60 ° of 90 or more, preferably 92 or more, more preferably 95 or more.
The present invention will be described in detail by examples. In the following examples of the present invention,
molecular structure: the contents of 1, 2-and 1, 4-polymeric structural units in the low cis polybutadiene rubber were measured by Bruker AVANCE400 type superconducting nuclear magnetic resonance apparatus (1H-NMR), the resonance frequency of the 1H core was 300.13MHz, the spectral width was 2747.253Hz, the pulse width was 5.0 μs, the data point was 16K, the diameter of the sample tube was 5mm, the solvent was deuterated chloroform CDCl3, the sample concentration was 15% (W/V), the measurement temperature was normal temperature, the number of scans was 16 times, and the chemical shift of tetramethylsilane was 0 ppm.
Molecular weight and molecular weight distribution: the polymer sample is prepared into tetrahydrofuran solution with the mass concentration of 1mg/mL, the sample injection amount is 10.00 mu L, the flow rate is 0.35mL/min, and the test temperature is 40.0 ℃ by adopting a HLC-8320 gel permeation chromatograph of Tosoh corporation of Japan to measure, preparing a TSKgelSuperMultipore HZ-N, TSKgelSuperMultiporeHZ standard column, taking chromatographic pure THF as a solvent and narrow-distribution polystyrene as a standard sample.
Styrene solution viscosity of 5 wt.% rubber at 25 ℃): the measurement is carried out by adopting the enterprise standard Q/SH3155.SXL.C26-2019 of Beijing Yanshan petrochemical industry company and adopting a Fender viscometer at a constant temperature of 25 ℃. The viscosity of the rubber at 25℃in styrene (5% strength by weight of solution) was determined by means of the flow resistance of the fluid through the capillary tube over a certain period of time. Accurately preparing a styrene solution with the rubber content of 5%, filling the solution into a viscometer ball, starting a timer when the liquid level of the solution reaches an upper dividing line of the ball, stopping the timer when the liquid level of the solution reaches a lower dividing line of the ball, and recording the time when the solution just flows from the upper dividing line to the lower dividing line to be accurate to 0.1 second. Instrument: thermostatic water bath and viscometer; test conditions: constant temperature of 25 ℃.
Gel content: measured by a gravimetric method. The specific process is as follows: adding a rubber sample into styrene, oscillating in an oscillator at 25 ℃ for 16 hours to completely dissolve soluble matters, preparing a styrene solution containing 5 weight percent of rubber, and recording the mass of the rubber sample as C (in grams); weigh the 360 mesh clean nickel screen and record the mass of the clean nickel screen as B (in grams); then filtering the solution by using a nickel screen; washing nickel screen with styrene after filtering, drying nickel screen at 150 ℃ and normal pressure for 30 minutes, weighing, and recording the weight of the nickel screen as A (in grams); the gel content was calculated according to the following formula: gel content% = [ (a-B)/C ] ×100%.
The Mooney viscosity was measured according to GB/T1232.1 standard using a GT-7080-S2 Mooney viscometer manufactured by Gotech company of Taiwan, wherein the preheating time was 1min, the rotation time was 4min, and the test temperature was 100deg.C.
The metal content is tested by adopting an Optima 8300 full-spectrum direct-reading ICP spectrometer of the American Perkin Elmer (PE) company, and the lowest argon consumption of the instrument is ensured by adopting a flat plasma technology through an echelle grating, a solid detector, an ultraviolet light region and a visible light region double-light-path double-solid detector. Instrument operating parameters: high-frequency power 1300W, plasma air flow 15L/min, atomization air flow 0.55L/min, auxiliary air flow 0.2L/min, peristaltic pump speed 1.50mL/min, integration time 10s, and plasma axial observation. Analysis of spectral lines: ni 231.604nm,Al308.215nm,Li670.784nm,Fe 238.204nm,Ca 317.933nm,Mg 285.213nm. Reagent: nitric acid: high-grade pure, national medicine group chemical reagent Co., ltd, content 65% -68%; ni, al, li, fe, ca, mg base stock solution: 100 μg/mL, national institute of metrology science; the water used was deionized water. Sample preparation: accurately weighing 2.000g of a sample in a porcelain crucible, placing in a high-temperature resistance furnace, gradually heating to 500 ℃, taking out after ashing is completed, adding 5mL of 10% (V%) dilute nitric acid, slowly heating on an electric plate until the sample is completely dissolved, steaming the solution to dryness, adding 1mL of concentrated nitric acid, transferring into a 50mL volumetric flask, fixing the volume by distilled water, and simultaneously preparing a reagent blank solution.
Halogen content: the combustion ion chromatography was performed according to EN 14582-2016.
APHA color: LCBR samples were prepared as 5% styrene solutions and measured using LICO620 colorimeter with a cuvette diameter of 11mm.
The notched Izod impact strength of HIPS was measured according to GB/T1843-1996 (kJ/m) 2 ) 60 gloss is measured according to ASTM D526 (60).
The pressure of carbon dioxide is hereinafter referred to as gauge pressure.
Cyclohexane and hexane are supplied by national pharmaceutical agents, polymeric grades, molecular sieves soaked to a water content below 10ppm; butadiene, supplied by the petrification, polymerization grade; THF is provided by the national medicine reagent company, is chromatographically pure, and is soaked for more than 15 days by adopting a molecular sieve after hexane is diluted by 10 times, and the dosage in the system is calculated according to pure substances; tetrahydrofurfuryl alcohol diethyl ether is provided by national drug reagent company, analytically pure, hexane is diluted 20 times and soaked by molecular sieve for more than 15 days, and the dosage in the system is calculated according to pure substances; n-butyllithium is supplied by the reagent Co.Ltd.of carbofuran, 1.6mol.L -1 Diluted to 0.4mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the Hexachloroethane and hexachlorodisilane were supplied by Inonoka reagent Co., ltd., analytically pure, diluted to 0.1mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The anti-aging agents 1520 and 1076 are provided by the national pharmaceutical agents company and are diluted to the mass concentration of 10%, and the dosage in the system is calculated according to pure substances;
polybutadiene rubber 720AX, available from Asahi Karaku chemical, having molecular structure parameters as shown in Table 3;
polybutadiene rubber 730A, available from Asahi Karakui chemical, has molecular structure parameters as shown in Table 3.
Example 1
This example illustrates the LCBR rubber of the present invention and its preparation method.
(1) Adding nonpolar hydrocarbon solvent, 1, 3-butadiene monomer and structure regulator (the types and the amounts are shown in table 1 and are all metered by pure compounds) into a reactor under the protection of nitrogen, heating to a specified temperature, adding organolithium initiator (the types and the amounts are shown in table 1 and are all metered by pure compounds), and then carrying out anionic solution polymerization reaction at the specified temperature and the specified reaction pressure (the conditions are shown in table 1) until the conversion rate of 1, 3-butadiene is 100%;
(2) Then adding a coupling agent (the types and the amounts of which are shown in Table 2 and are all measured by pure compounds) into the product of the anionic solution polymerization reaction to perform the coupling reaction at the specified temperature and pressure (the conditions are shown in Table 2);
(3) Terminating the coupling reaction by using a terminating agent (the types and the amounts of the terminating agent are shown in Table 2), adding an antioxidant (1.2 g of a combined antioxidant of 1520 and 1076 in a weight ratio of 1:1), mixing to finally obtain a polymerization solution of the LCBR rubber, performing steam coagulation desolventizing treatment on the obtained polymerization solution, and drying to obtain the LCBR rubber PB1. The structure and properties of the obtained polymer were measured, and the results are shown in Table 3.
Examples 2 to 9
This example illustrates the LCBR rubber of the present invention and its preparation method.
According to the method of example 1, except that the reaction was conducted using the parameters shown in tables 1 and 2, thereby obtaining LCBR rubbers PB2-PB9, respectively, the resulting polymers were subjected to the structure and property measurements, and the results are shown in Table 3.
Comparative example 1
The process of example 1, except that the coupling agent of step (2) is silicon tetrachloride; thus, LCBR rubber DPB1 was obtained, and the structure and properties of the obtained polymer were measured, and the results are shown in Table 3.
Comparative example 2
According to the method of example 1, except that the coupling agent in step (2) was silicon tetrachloride and the amount thereof was 2.28mmol, LCBR rubber DPB2 was obtained, and the structure and properties of the obtained polymer were measured, and the results are shown in Table 3.
Comparative example 3
According to the method of example 1, except that the amount of butyllithium used in step (1) was 6mmol and that of hexachlorosilane used in step (2) was 1mmol, thereby obtaining LCBR rubber DPB3, and the obtained polymer was subjected to structural and performance measurements, and the results are shown in Table 3.
Comparative example 4
According to the method of example 1, except that the amount of n-butyllithium used in step (1) was 15mmol and the amount of hexachlorosilane used in step (2) was 2.55mmol, thereby obtaining LCBR rubber DPB4, the resulting polymer was subjected to the structure and property measurement, and the results are shown in Table 3.
Comparative example 5
According to the method of example 1, except that hexachlorosilane was used in an amount of 1.23mmol in step (2), thereby obtaining LCBR rubber DPB5, the resultant polymer was subjected to structure and property measurement, and the results are shown in Table 3.
Comparative example 6
According to the method of example 1, except that hexachlorosilane was used in an amount of 1.9mmol in step (2), thereby obtaining LCBR rubber DPB6 having a molecular weight of a monomodal distribution, the resulting polymer was subjected to structural and performance measurements, and the results are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
Note that: area1/Area2 is the weight ratio of the bimodal low molecular weight component to the high molecular weight component.
Table 3 (subsequent)
As can be seen from Table 3, the low cis-polybutadiene rubber prepared by the invention has extremely low viscosity of 5% styrene solution, higher Mooney viscosity, moderate molecular weight distribution, low gel content, halogen content and metal content, and is particularly suitable for being used as a toughening agent of high-gloss HIPS.
Application example 1
This example is a description of HIPS resin and method of preparing the same of the present invention.
100g of low cis-polybutadiene rubber PB1, 120g of ethylbenzene and 900g of styrene monomer are mixed, 40g of mineral oil (supplied by chemical industry A of Beijing Yanshan petrochemical company, density 0.85-0.88g/ml, the same applies below) and 0.2g of tert-butyl peroxy-2-ethylhexyl carbonate are added, and mixed, polymerized for 2h at a stirring rate of 400rpm and a polymerization temperature of 110 ℃, and then heated to 120 ℃ for polymerization for 2h; and (3) heating to 140 ℃ for polymerization for 2 hours under the stirring speed of 150rpm, heating to 150 ℃ for polymerization for 2 hours, and carrying out vacuum flash evaporation on the reaction product to remove unreacted monomers and solvent to obtain HIPS resin P1.
The HIPS resin was dried and then subjected to structural and performance measurements, the results of which are shown in Table 4.
Application examples 2 to 9
This example is a description of HIPS resin and method of preparing the same of the present invention.
According to the method of application example 1, except that low cis-polybutadiene rubbers PB2 to PB9 were used in place of low cis-polybutadiene rubber PB1, respectively, the reaction products were subjected to vacuum flash evaporation to remove unreacted monomers and solvents, respectively, to obtain HIPS resins P2 to P9.
The HIPS resin was dried and then subjected to structural and performance measurements, the results of which are shown in Table 4.
Comparative application examples 1 to 6
According to the method of application example 1, except that low cis-polybutadiene rubbers DPB1 to DPB6 were used in place of low cis-polybutadiene rubber PB1, respectively, the reaction products were subjected to vacuum flash evaporation to remove unreacted monomers and solvents, thereby obtaining HIPS resins DP1 to DP6, respectively.
The HIPS resin was dried and then subjected to structural and performance measurements, the results of which are shown in Table 4.
Comparative application examples 7 to 8
According to the method of application example 1, except that the low cis-polybutadiene rubber PB1 was replaced with the respective Japanese Asahi chemical products 720AX and 730A, thereby obtaining HIPS resins DP7-DP8 after the reaction products were subjected to vacuum flash evaporation to remove unreacted monomers and solvents, respectively.
The HIPS resin was dried and then subjected to structural and performance measurements, the results of which are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, by using the low cis-polybutadiene rubber of the present invention as a toughening agent, HIPS resins excellent in gloss can be obtained while ensuring the impact strength of HIPS resins, and the HIPS resins obtained by the present invention have a significant improvement in gloss as compared with HIPS resins obtained by using toughening agents which are popular in the market.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A low cis-polybutadiene rubber characterized in that the molecular weight of the low cis-polybutadiene rubber is bimodal and the low cis-polybutadiene rubber has the following characteristics:
(1) The ratio of the number average molecular weight Mn2 of the bimodal high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component is from 5 to 6;
(2) The bimodal low molecular weight component has a number average molecular weight Mn1 in the range of 30,000 to 50,000 and a molecular weight distribution index Mw1/Mn1 in the range of 1 to 1.1;
(3) The number average molecular weight Mn2 of the bimodal high molecular weight component is in the range of 150,000-300,000 and the molecular weight distribution index Mw2/Mn2 is from 1 to 1.1;
(4) Mooney viscosity ML of the low cis-polybutadiene rubber at 100 DEG C 1+4 In the range of 45-65;
(5) The viscosity of the 5 wt.% styrene solution at 25℃of the low cis-polybutadiene rubber is in the range of 10 to 28 centipoise.
2. The low cis-polybutadiene rubber of claim 1, wherein the bimodal distribution of low molecular weight components has a number average molecular weight Mn1 in the range of 35,000-45,000;
preferably, the bimodal distribution of the high molecular weight component has a number average molecular weight Mn2 in the range of 180,000-270,000;
preferably, the low cis polybutadiene rubber has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 50-60;
preferably, the low cis polybutadiene rubber has a viscosity in the range of 12 to 26 centipoise, preferably 15 to 24 centipoise, in a 5 wt.% styrene solution at 25 ℃.
3. The low cis polybutadiene rubber according to claim 1 or 2, wherein the number average molecular weight Mn of the low cis polybutadiene rubber is in the range of 140,000-260,000, preferably in the range of 160,000-240,000; a molecular weight distribution index Mw/Mn of from 1.1 to 1.5, preferably from 1.15 to 1.45;
preferably, the weight ratio of bimodal low molecular weight component to high molecular weight component is from 0.01 to 0.25:1, preferably from 0.04 to 0.18:1;
preferably, the weight ratio of 1, 2-structure content to 1, 4-structure content in the low cis-polybutadiene rubber is 0.06-0.25:1; preferably 0.08-0.2:1.
4. The low cis polybutadiene rubber according to any of claims 1 to 3, wherein the gel content of the low cis polybutadiene rubber is equal to or less than 150mg/kg, preferably equal to or less than 100mg/kg, more preferably equal to or less than 50mg/kg;
preferably, the low cis polybutadiene rubber has a metal content of 100mg/kg or less, preferably 50mg/kg or less, more preferably 30mg/kg or less;
preferably, the low cis polybutadiene rubber has a halogen content of 150mg/kg or less, preferably 100mg/kg or less, more preferably 50mg/kg or less;
preferably, the low cis polybutadiene rubber has an APHA color of 10 or less, preferably 7 or less, more preferably 5 or less.
5. A process for the preparation of low cis-polybutadiene rubber, comprising the steps of:
(1) In an organic solvent, carrying out anionic solution polymerization reaction on 1, 3-butadiene in the presence of an organolithium initiator and a structure regulator until the conversion rate of the 1, 3-butadiene is more than 99%, so as to obtain a polybutadiene active chain; wherein the molar ratio of the 1, 3-butadiene to the organolithium initiator is 550-950:1, a step of;
(2) Coupling the polybutadiene living chain in the presence of a 6-functional coupling agent; the molar ratio of the coupling agent to the organolithium initiator is 0.14-0.19:1, a step of;
(3) The product of the coupling reaction is terminated in the presence of a terminating agent.
6. The process according to claim 5, wherein in step (1), the polybutadiene active chain has a number average molecular weight of 30,000-50,000, preferably 35,000-45,000;
preferably, the molar ratio of the 1, 3-butadiene to the organolithium initiator is 600-850:1;
preferably, the conditions of the anionic solution polymerization reaction include: the reaction temperature is 40-100 ℃, preferably 50-90 ℃; the reaction time is 20-100min, preferably 30-60min; the gauge pressure is 0.1-1MPa, preferably 0.2-0.5MPa;
preferably, the molar ratio of the structure modifier to the organolithium initiator is from 0.02 to 2:1.
7. the production method according to claim 5 or 6, wherein in the step (2), a molar ratio of the coupling agent to the organolithium initiator is 0.15 to 0.18:1, a step of;
preferably, the 6-functional coupling agent is selected from at least one of hexachlorodisilane, hexachloroethane, 1, 3-hexachloropropane, triethyl glycerol and trimethyl glycerol, preferably hexachlorodisilane and/or hexachloroethane;
preferably, the conditions of the coupling reaction include: the reaction temperature is 40-100 ℃, the reaction time is 15-40min, and the gauge pressure is 0.1-1MPa.
8. The preparation method according to any one of claims 5 to 7, wherein the terminator is selected from at least one of C1-C4 alcohol, organic acid and carbon dioxide, preferably at least one of isopropanol, stearic acid, citric acid and carbon dioxide, more preferably carbon dioxide;
preferably, the terminator is used in an amount of 0.1 to 0.2 parts by weight with respect to 100 parts by weight of the 1, 3-butadiene monomer.
9. The production method according to any one of claims 5 to 8, wherein the method further comprises: mixing the product obtained by terminating the step (3) with an antioxidant;
preferably, the weight ratio of the antioxidant to the 1, 3-butadiene is 0.1-0.3:100.
10. a low cis-polybutadiene rubber produced by the production process according to any one of claims 5 to 9.
11. Use of the low cis polybutadiene rubber of any one of claims 1-4 and 10 in HIPS resins.
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