CN113461857A - Low cis-polybutadiene rubber and preparation method thereof, and HIPS and preparation method thereof - Google Patents
Low cis-polybutadiene rubber and preparation method thereof, and HIPS and preparation method thereof Download PDFInfo
- Publication number
- CN113461857A CN113461857A CN202010244096.1A CN202010244096A CN113461857A CN 113461857 A CN113461857 A CN 113461857A CN 202010244096 A CN202010244096 A CN 202010244096A CN 113461857 A CN113461857 A CN 113461857A
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- CN
- China
- Prior art keywords
- polybutadiene rubber
- low
- cis
- solution
- low cis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000005064 Low cis polybutadiene Substances 0.000 title claims abstract description 126
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 125
- 229920005669 high impact polystyrene Polymers 0.000 title claims abstract description 65
- 239000004797 high-impact polystyrene Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 239000012745 toughening agent Substances 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 75
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 53
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 39
- 239000003999 initiator Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012442 inert solvent Substances 0.000 claims description 12
- 125000001979 organolithium group Chemical group 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 11
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium 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
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- -1 potassium alkoxide Chemical class 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012933 diacyl peroxide Substances 0.000 claims description 2
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- QCYIFDAFIXZTQO-UHFFFAOYSA-N lithium;diphenylmethylbenzene Chemical compound [Li+].C1=CC=CC=C1[C-](C=1C=CC=CC=1)C1=CC=CC=C1 QCYIFDAFIXZTQO-UHFFFAOYSA-N 0.000 claims description 2
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 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
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000003963 antioxidant agent Substances 0.000 description 17
- 230000003078 antioxidant effect Effects 0.000 description 16
- 238000005259 measurement Methods 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000004807 desolvation Methods 0.000 description 8
- 230000000379 polymerizing effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 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 5
- 239000005063 High cis polybutadiene Substances 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 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
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 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
- 239000004793 Polystyrene Substances 0.000 description 2
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FFHGJCBXRQUCED-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)peroxybenzene Chemical compound CC1=CC=CC=C1OOC1=CC=CC=C1C FFHGJCBXRQUCED-UHFFFAOYSA-N 0.000 description 1
- VQACZQDUDLKEOJ-UHFFFAOYSA-N 1-n-phenyl-4-n-(2-phenylpropan-2-yl)benzene-1,4-diamine Chemical compound C=1C=CC=CC=1C(C)(C)NC(C=C1)=CC=C1NC1=CC=CC=C1 VQACZQDUDLKEOJ-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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- 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 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100498537 Scheffersomyces stipitis (strain ATCC 58785 / CBS 6054 / NBRC 10063 / NRRL Y-11545) DPB7 gene Proteins 0.000 description 1
- 241001302210 Sida <water flea> Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers 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
- C08F236/04—Copolymers 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
- C08F236/10—Copolymers 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 with vinyl-aromatic monomers
-
- 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
- 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)
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Abstract
The invention relates to the field of HIPS (high impact polystyrene) resin, and discloses low cis-polybutadiene rubber and a preparation method thereof, and HIPS resin and a preparation method thereof. The content of 1, 2-polymerization structural unit in the low cis-polybutadiene rubber is 8-20 wt%; the number average molecular weight is 70,000-90,000 g/mol; the molecular weight distribution coefficient is 2.25-2.65; mooney viscosity ML at 100 ℃1+4Is 40 to 60; the 5 wt.% styrene solution at 25 ℃ had a viscosity of 40-66 cp. The low cis-polybutadiene rubber is used as a toughening agent, and HIPS resin with more balanced impact resistance and glossiness can be obtained.
Description
Technical Field
The invention relates to the field of synthetic rubber and resin, in particular to low cis-polybutadiene rubber and a preparation method thereof, and HIPS resin and a preparation method thereof.
Background
The use of different toughening rubbers can have a significant impact on the properties of HIPS resins. Theoretically, LCBR rubber, high cis-polybutadiene rubber, styrene-butadiene-styrene thermoplastic elastomer and the like are common rubber types for preparing HIPS resin by a continuous bulk method.
The toughened rubber cannot select a crosslinked structure because the crosslinked rubber cannot undergo a grafting reaction. In the traditional body process, high cis-polybutadiene rubber is adopted, the glass transition temperature of the high cis-polybutadiene rubber is lower, the high cis-polybutadiene rubber is easy to relax, the impact resistance effect is good, but the high cis-polybutadiene rubber has a low-temperature crystallization tendency and is not beneficial to improving the low-temperature toughness. For low-temperature toughness HIPS resin, LCBR is the best toughening agent because of the characteristics of moderate vinyl content, low gel content and random distribution of the cis-trans 1,4 molecular chain structure.
LCBR rubbers are classified into batch polymerization products and continuous polymerization products according to the process. The batch polymerization process is flexible, and after the polymerization is finished, a polyfunctional group coupling agent is generally adopted for coupling reaction so as to balance the Mooney viscosity of the product and the viscosity of 5 percent styrene. Continuous polymerization processes, due to the continuous transport of the material, cannot introduce a terminating coupling agent during the polymerization process when there is only one reactor, otherwise the living chains would be terminated by the coupling agent and the desired branched polymer product would not be obtained.
The continuous polymerization products on the market are classified into two types, i.e., a single-reactor continuous polymerization process and a three-reactor continuous polymerization process. The former is represented by Asahi chemical company of Japan, and does not add any branching agent during polymerization, and the product thereof has a linear structure, and cannot achieve a balance between Mooney viscosity and 5% styrene solution viscosity, and it is difficult to balance gloss and impact resistance at the same time in the modification of HIPS. The latter is represented by Arrangian-Neodylaceae, and the polymerization reaction is carried out in a first reactor, the coupling reaction is carried out in a second reactor, and the termination reaction is carried out in a third reactor; the process has long process flow, large investment and large occupied area, and the product adopts silane containing chlorine as a coupling agent, and chloride ions enter condensed water and colloidal particles in the post-treatment stage to corrode post-treatment equipment.
Disclosure of Invention
The invention aims to overcome the defect that HIPS resin obtained by toughening low cis-polybutadiene rubber prepared by a single-reactor continuous polymerization process in the prior art is difficult to obtain more balanced glossiness and impact resistance, and provides continuous star-shaped low cis-polybutadiene rubber serving as a toughening agent and capable of obtaining the HIPS resin with more balanced glossiness and impact resistance, a preparation method of the continuous star-shaped low cis-polybutadiene rubber, the HIPS resin and a preparation method of the HIPS resin.
In order to achieve the above object, a first aspect of the present invention provides a low cis-polybutadiene rubber, wherein the content of 1, 2-polymerized structural units in the low cis-polybutadiene rubber is 8 to 20% by weight; the number average molecular weight is 70,000-90,000 g/mol; the molecular weight distribution coefficient is 2.25-2.65; mooney viscosity ML at 100 ℃1+4Is 40 to 60; the 5 wt.% styrene solution at 25 ℃ had a viscosity of 40-66 cp.
The second aspect of the present invention provides a method for producing the low-cis polybutadiene rubber, wherein the method comprises:
(1) continuously feeding 1, 3-butadiene and a branched monomer into a reactor from the bottom of the reactor in an inert solvent in the presence of an organic lithium initiator, a gel inhibitor and a structure regulator to perform anionic solution polymerization reaction until the conversion rate of the 1, 3-butadiene reaches more than 99%;
(2) and (2) contacting the mixture obtained in the step (1) with a terminator to carry out termination reaction.
A third aspect of the present invention provides a process for preparing a HIPS resin, the process comprising:
(1) providing a low cis-polybutadiene rubber solution containing the low cis-polybutadiene rubber obtained by the method;
(2) in the presence of a free radical initiator, styrene and a toughening agent are subjected to polymerization reaction; wherein the toughening agent contains the low cis-polybutadiene rubber solution obtained in the step (1).
The fourth aspect of the present invention provides the HIPS resin prepared by the above-mentioned method.
The low cis-polybutadiene rubber realizes the balance control of Mooney viscosity and 5% styrene solution viscosity of single-reactor continuous polymerization low cis-polybutadiene rubber (LCBR), and the low cis-polybutadiene rubber serving as a toughening agent of the HIPS resin enables the HIPS resin to have more balanced glossiness and impact resistance. In particular, the low cis-polybutadiene rubber provided by the invention has the viscosity of a 5 wt% styrene solution at 25 ℃ of below 66cp, and the obtained HIPS resin has higher glossiness.
According to the preparation method of the low cis-polybutadiene rubber provided by the invention, the branched monomer is added from the bottom of the reaction container and copolymerized with the 1, 3-butadiene to prepare the star polymer, so that the mutual relation between the Mooney viscosity of the rubber and the viscosity of a 5 wt% styrene solution at 25 ℃ is balanced, the problem that the impact resistance and the glossiness of HIPS resin prepared from the low cis-polybutadiene rubber (LCBR) prepared by a single-reactor continuous polymerization process cannot be considered at the same time is solved, the non-halogenation of the process is realized, and the corrosion problem in the preparation process is solved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a low cis-polybutadiene rubber, wherein the content of 1, 2-polymerized structural units in the low cis-polybutadiene rubber is 8 to 20% by weight; number average molecular weight of 70,000-90,000; the molecular weight distribution coefficient is 2.25-2.65; mooney viscosity ML at 100 ℃1+4Is 40 to 60; the 5 wt.% styrene solution at 25 ℃ had a viscosity of 40-66 cp.
In the present invention, the butadiene monomer forming the low-cis polybutadiene rubber mainly refers to 1, 3-butadiene unless otherwise specified. Wherein the polymerized form of 1, 3-butadiene generally comprises a 1, 2-polymerized form, thereby forming said 1, 2-polymerized structural unit (- [ CH)2-CH2(CH＝CH2)]-) also includes a 1, 4-polymerized form, thereby forming a 1, 4-polymerized structural unit (- [ CH)2-CH＝CH-CH2]-). Wherein the content of said 1, 2-polymeric structural units is 8-20% by weight, which ensures the grafting reaction of the continuous bulk HIPS resin. When the content of the 1, 2-polymeric structural unit is less than 8% by weight, the progress of the subsequent grafting reaction in the preparation of the post HIPS resin will be unfavourable; when the content of the 1, 2-polymerized structural unit is more than 20% by weight, crosslinking points are easily formed, which is disadvantageous in improvement of impact resistance. Preferably, the low cis-polybutadiene rubber has a 1, 2-polymerized structural unit content of 9 to 18 wt%, more preferably 10 to 16 wt%.
In the case where the above-mentioned content range of the 1, 2-polymerized structural unit is satisfied, the content of the cis-1, 4-polymerized structural unit is preferably from 20 to 40% by weight, more preferably from 25 to 40% by weight, still more preferably from 30 to 40% by weight; the content of trans 1, 4-polymeric structural units is preferably 40 to 60% by weight, more preferably 45 to 60% by weight, still more preferably 50 to 60% by weight.
According to the present invention, the low-cis polybutadiene rubber is 70,000-90,000g/mol, which is provided for the purpose of controlling the Mooney viscosity and the viscosity of the 5% by weight styrene solution to be maintained in suitable ranges to better balance the correlation between the Mooney viscosity and the viscosity of the 5% by weight styrene solution; wherein, when the number average molecular weight of the low cis-polybutadiene rubber is less than 70,000g/mol, the requirement of Mooney viscosity of the low cis-polybutadiene rubber can not be met, the processability of the low cis-polybutadiene rubber is poor, and the impact strength of the HIPS resin is poor; when the number average molecular weight of the low cis-polybutadiene rubber is more than 90,000g/mol, the requirement of the product of low cis-polybutadiene rubber 5% styrene solution viscosity cannot be met, and the glossiness of the HIPS resin is poor. Preferably, the number average molecular weight of the low-cis polybutadiene rubber is 73,000-88,000g/mol, more preferably 75,000-85,000 g/mol.
The low cis-polybutadiene rubber of the present invention has a suitable molecular weight distribution coefficient, which facilitates control of the relative proportions of branched rubber and linear rubber to balance the relationship between Mooney viscosity and 5% styrene solution viscosity. When the molecular weight distribution coefficient of the low cis-polybutadiene rubber is less than 2.25, the branching of the product is insufficient, and the linear product accounts for a larger proportion, so that the Mooney viscosity of the low cis-polybutadiene rubber is lower; when the molecular weight distribution coefficient of the low cis-polybutadiene rubber is more than 2.65, the proportion of the branched product is higher, and the Mooney viscosity exceeds the upper limit of the low cis-polybutadiene rubber. Preferably, the molecular weight distribution coefficient is from 2.28 to 2.55, more preferably from 2.3 to 2.55.
In the invention, the molecular weight and the molecular weight distribution index of the low cis-polybutadiene rubber are measured by adopting a gel permeation chromatography, the gel permeation chromatography adopts an HLC-8320 type gel permeation chromatograph of Tosoh corporation of Japan, the chromatographic columns are TSKgel SuperMultiporeHZ-N and TSKgel SuperMultiporeHZ standard columns, the solvent is chromatographically pure Tetrahydrofuran (THF), narrow distribution polystyrene is used as a standard sample, a polymer sample is prepared into a tetrahydrofuran solution with the mass concentration of 1mg/mL, the sample feeding amount is 10.00 mu L, the flow rate is 0.35mL/min, and the test temperature is 40.0 ℃.
According to the invention, the Mooney viscosity ML of the low-cis polybutadiene rubber of the invention at 100 ℃1+440 to 60 in order to ensure processability of the low cis polybutadiene rubber while better balancing gloss and impact strength of the HIPS. Mooney viscosity ML of low cis-polybutadiene rubber at 100 ℃1+4Less than 40, the low cis-polybutadiene rubber has poor processability and simultaneously influences the impact resistance of HIPS; mooney viscosity ML at 100 ℃1+4Above 60, the low cis-polybutadiene rubber is easy to plasticize in the drying stage, and the product quality is influenced. Preferably, the Mooney viscosity ML of the low-cis polybutadiene rubber at 100 ℃1+4From 40 to 58, more preferably from 45 to 55.
In the invention, the Mooney viscosity is measured according to GB/T1232.1 standard by adopting a GT-7080-S2 Mooney viscometer manufactured by Gotech company of Taiwan, wherein the preheating time is 1min, the rotating time is 4min, and the testing temperature is 100 ℃.
According to the present invention, the low cis-polybutadiene rubber of the present invention has a 5 wt% styrene solution viscosity at 25 ℃ of 40-66cp, preferably 42-66cp, more preferably 44-58 cp. Controlling the viscosity of the 5 wt.% styrene solution of the low-cis polybutadiene rubber at 25 ℃ within the above-described range and preferred range balances the correlation between gloss and impact resistance of the resulting HIPS resin.
The viscosity of the 5 wt% styrene solution at 25 ℃ was measured using a Fengshan petrochemical company, Beijing, standard Q/SH3155.SXL. C26-2019, and using a Fin's viscometer at 25 ℃.
According to the present invention, the low cis-polybutadiene rubber of the present invention can obtain a low gel content, and preferably, the gel content of the low cis-polybutadiene rubber is 400ppm or less, preferably 200ppm or less, more preferably 150ppm or less. The solvent system and the gel inhibitor adopted by the invention can effectively avoid the accumulation of active macromolecular chains in the reactor and the generation of gel in the polymerization stage, and the gel content is extremely low.
In the invention, the gel content is determined by a gravimetric method of a standard Q/SH3155.SXL.C27-2019 test of Beijing Yanshan petrochemical company enterprise. The specific process is as follows: adding a polymer sample into styrene, shaking the mixture in a shaker at the temperature of 25 ℃ for 16 hours to completely dissolve soluble substances, preparing a styrene solution containing 5 weight percent of polymer, and recording the mass of the polymer sample as C (in grams); weighing a 400-mesh clean nickel screen, and recording the mass of the clean nickel screen as B (in grams); then filtering the solution by using a nickel screen; washing the nickel screen with styrene after filtering, drying the nickel screen for 30 minutes at 150 ℃ under normal pressure, weighing, and recording the mass of the nickel screen as A (in grams); the gel content was calculated according to the following formula:
gel content [ (% a-B)/C ] × 100%.
According to the present invention, the low cis-polybutadiene rubber of the present invention can obtain a lower color, and preferably the color of the low cis-polybutadiene rubber in a 5 wt% styrene solution is less than 5, preferably 0 or less, more preferably-2 or less.
The chromaticity is tested by adopting a Hunter Lab ColorFlex desktop color difference meter of Hunter company in America according to the standard Q/SH3155.SXL. C29-2019; and (3) testing conditions are as follows: the color system adopts CIELAB, the optical geometry structure is 45 degrees/0 degrees, the light source is C light source, the observation angle is 2 degrees, and the thickness of the sample is about 15 mm.
The second aspect of the present invention provides a method for producing the low-cis polybutadiene rubber, wherein the method comprises:
(1) continuously feeding 1, 3-butadiene and a branched monomer into a reactor from the bottom of the reactor in an inert solvent in the presence of an organic lithium initiator, a gel inhibitor and a structure regulator to perform anionic solution polymerization reaction until the conversion rate of the 1, 3-butadiene reaches more than 99%;
(2) and (2) contacting the mixture obtained in the step (1) with a terminator to carry out termination reaction.
According to the present invention, the above-mentioned process for producing a low cis-polybutadiene rubber is carried out by a continuous reaction. The process may be carried out in a reactor as is conventional in the art, the volume of which may be reasonably selected depending on the yield of the desired product and the amount of raw material used, and generally the volume of the reactor may be 10 to 10000L.
The inventors of the present invention have found in their studies that an aromatic vinyl monomer can be copolymerized with 1, 3-butadiene as a branched monomer to prepare a star-shaped polymer, thereby balancing the rubber Mooney viscosity and the viscosity of a 5 wt% styrene solution at 25 ℃. Further, the inventors of the present invention have found that the location of the addition of the branching monomer affects the molecular weight and molecular weight distribution of the low-cis polybutadiene rubber of the final product, thereby affecting the mooney viscosity of the product and the viscosity of the 5 wt% styrene solution at 25 ℃, and further affecting the impact resistance and gloss of the HIPS product.
According to the present invention, 1, 3-butadiene and a branched monomer are each continuously fed into a reactor from the bottom of the reactor to carry out an anionic solution polymerization reaction. The shape of the reactor may be a shape conventional in the art as long as the branching reaction of the branching monomer with 1, 3-butadiene is allowed to occur.
According to the invention, the inert solvent refers to an inert solvent which does not participate in the polymerization reaction, and the inert solvent can be C5-C8 cycloalkane and/or C5-C9 alkane, and is preferably one or more of cyclohexane, methyl cyclopentane, methyl cyclohexane, methyl pentane, n-hexane, n-heptane and isooctane.
The amount of the inert solvent used in the present invention can be reasonably selected according to the amount of the monomer and the control requirement of the polymerization temperature, and can vary within a wide range, and the amount of the inert solvent used can be 400-900g based on 100g of the total weight of the 1, 3-butadiene monomer.
According to the invention, the inert solvent is preferably added from the bottom of the reactor together with the 1, 3-butadiene. Therefore, the method avoids the excessive concentration of local monomers to form gel, ensures the quality of LCBR rubber, and further ensures that the final HIPS product has better comprehensive performance.
According to the present invention, the organolithium initiator is not particularly limited, and various organolithium initiators conventionally used in polybutadiene rubber preparation in the art can be used, preferably, the organolithium initiator is a compound represented by formula RLi, wherein R is selected from alkyl groups of C1-C20, cycloalkyl groups of C6-C20, or aryl groups of C6-C20, preferably alkyl groups of C1-C10, cycloalkyl groups of C6-C8, or aryl groups of C6-C8; more preferably, the organolithium initiator is one or more of methyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium, cyclohexyllithium, 4-cyclohexylbutyllithium, phenyllithium, triphenylmethyllithium and 2-naphthyllithium, more preferably n-butyllithium and/or sec-butyllithium, still more preferably n-butyllithium in view of solubility and storage stability of the initiator in an inert solvent. Wherein the organic lithium initiator is added into a polymerization system in the form of solution, and the solvent of the organic lithium initiatorFor example, the solvent may be one or more selected from hexane, cyclohexane, heptane, etc., and the concentration is preferably 0.04 to 0.2 mol.L-1。
The amount of the initiator used in the present invention can be reasonably selected according to the amount of the monomer and the molecular weight of the low cis-polybutadiene rubber to be obtained, and the amount can be varied within a wide range, preferably, the molar ratio of 1, 3-butadiene to the organolithium initiator is 750-: 1, preferably 850-: 1, more preferably 900-: 1.
according to the invention, the anionic solution polymerization is carried out in the presence of a structure-modifying agent, the type of which may be conventional in the art, preferably potassium alkoxide and/or sodium alkoxide. In order to obtain a better balance between the Mooney viscosity of the low-cis polybutadiene rubber and the viscosity of the 5 wt.% styrene solution, it is preferred that the structure-regulating agent is potassium tert-pentoxy and/or potassium 2-hexoxide, which has good solubility in hydrocarbon solvents.
According to the invention, the dosage of the structure regulator can be reasonably selected according to various performance indexes of a target product, the dosage of the structure regulator is too low, the reactivity ratio of 1, 3-butadiene and a branched monomer is high, the branched monomer is more prone to homopolymerization, so that the gel is easier to produce, more gel inhibitor is required to be added for inhibiting the gel content, and the addition amount of the gel inhibitor has an upper limit. The use amount of the structure regulator is too high, molecular chains are easily inactivated, and the conversion rate of 1, 3-butadiene is reduced. Preferably, the molar ratio of the amount of the structure modifier to the organolithium initiator is 0.1 to 1: 1, more preferably 0.1 to 0.8: 1, more preferably 0.1 to 0.5: 1. this makes it possible to adjust the reactivity ratio of 1, 3-butadiene to the branching monomer so that 1, 3-butadiene and the branching monomer are more likely to be copolymerized ideally in step (2) to control the degree of branching and gel content of the product without seriously deactivating the living chain.
According to the invention, the gel inhibitor is a substance which has a certain chain transfer effect and can inhibit gel generation in a polymerization process, the gel inhibitor is one or more of tetramethylethylenediamine/1, 2-butadiene, carbon four raffinate and 1, 2-butadiene, 1, 2-butadiene is preferred, the 1, 2-butadiene can be pure 1, 2-butadiene or 1, 2-butadiene containing a part of inert components, and the gel inhibitor can be prepared into a certain concentration for use according to the requirements of equipment.
According to the invention, the dosage of the gel inhibitor can be reasonably selected according to the gel content index of a target product, so as to meet the requirements of the product. Preferably, the weight ratio of the gel inhibitor to 1, 3-butadiene is 1-10: 10000, more preferably 5 to 8: 10000.
according to the present invention, the conditions of the anionic solution polymerization reaction of step (1) are such that the conversion of 1, 3-butadiene is 99% or more. The polymerization temperature is too low, the conversion rate of the monomer in unit time is low, and the retention time needs to be prolonged; the polymerization temperature is too high, gel is easy to generate, and the quality of the product is influenced.
Preferably, the anionic solution polymerization conditions include: the temperature is 0-120 deg.C, preferably 40-115 deg.C (e.g. 80-110 deg.C), more preferably 50-110 deg.C; the time (i.e. residence time) is 30-90min, preferably 40-80 min; the gauge pressure is 0.1 to 2MPa, preferably 0.5 to 1 MPa. The anionic solution polymerization reaction of the invention has higher controllability, and the polymerization temperature is easy to control, thereby obtaining the product with easy-to-control performance.
According to the present invention, the branching monomer is not particularly limited as long as the low-cis polybutadiene rubber of the present invention can be obtained. Preferably, the branched monomer is an aromatic vinyl monomer of C10-C16, more preferably one or more of divinylbenzene, dipropenylbenzene and diallylbenzene, and further preferably divinylbenzene. Aromatic vinyl monomers and 1, 3-butadiene are copolymerized to prepare a star polymer, so that the relationship between the Mooney viscosity of low cis-polybutadiene rubber and the viscosity of a 5% styrene solution is balanced, HIPS resin with more balanced glossiness and impact resistance can be obtained, non-halogenation of the process is realized, and the corrosion problem in the post-treatment process is solved.
The amount of the branching monomer used in the present invention is not particularly limited as long as the low-cis polybutadiene rubber of the present invention having a number average molecular weight in the range of 70,000-90,000g/mol (preferably 73,000-88,000g/mol, more preferably 75,000-85,000g/mol) and in the range of the molecular weight distribution coefficient can be obtained, respectively. But in order to enable the resulting low cis polybutadiene rubber to have a more suitable branching area to enable HIPS to have higher impact properties. Preferably, the molar ratio of the branched monomer to the organolithium initiator is from 0.4 to 1: 1, preferably 0.4 to 0.8: 1.
wherein the branched monomer is added to the polymerization system in the form of a solution. Preferably, the solvent of the solution containing the branching monomer is selected as the same as the inert solvent previously described, which may be a C5-C8 cycloalkane and/or a C5-C9 alkane, preferably one or more of cyclohexane, methylcyclopentane, methylcyclohexane, methylpentane, n-hexane, n-heptane and isooctane. The concentration of the branching monomer can be adjusted within a wide range depending on the metering range of the branching monomer.
Preferably, steps (1) and (2) are carried out in an inert atmosphere provided by a non-reactive gas selected from one or more of nitrogen, neon and argon.
According to the present invention, in the step (2), the branching reaction can be terminated by using a terminator, and a polymerization solution of low cis-polybutadiene rubber can be obtained.
According to the present invention, the process for producing a low cis-polybutadiene rubber of the present invention comprises the step of subjecting the mixed solution obtained in the step (2) to solvent removal for the purpose of extracting a low cis-polybutadiene rubber. The solvent removal method may be a method conventional in the art, for example, a method of extracting the low cis-polybutadiene rubber from the mixed solution by vapor condensation desolventizing treatment.
Preferably, the terminating agent is one or more of a C1-C4 alcohol, an organic acid, and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid, and carbon dioxide, more preferably carbon dioxide. The carbon dioxide is adopted for termination reaction, and the carbon dioxide can form carbonate with metal ions (Li, Mg, Al, Fe and Zn) in a polymerization system, so that the color development reaction of the metal ions is avoided, and the product has lower chroma. The carbon dioxide herein may be introduced into the reaction system in the form of a gas (for example, carbon dioxide gas having a gauge pressure of 0.2 to 1MPa (for example, 0.3 to 0.6MPa) or may be introduced into the reaction system in the form of an aqueous dry ice solution (for example, having a concentration of 0.1 to 5% by weight).
The amount of carbon dioxide used is not particularly limited, but the molar ratio of carbon dioxide to initiator is preferably 0.5 to 5:1, preferably 0.6 to 2: 1. can ensure the pH value of a polymerization system and remove metal ions in the low cis-polybutadiene rubber.
In order to achieve the oxidation resistance of the low cis-polybutadiene rubber obtained, an antioxidant may be further introduced into the low cis-polybutadiene rubber, and preferably, after the termination in the step (2), an antioxidant is introduced into the reaction system obtained by the termination, whereby the polymerization solution of the low cis-polybutadiene rubber obtained may contain an antioxidant, and the solvent removal step is performed after the introduction of the antioxidant. The antioxidant of the present invention is not particularly limited, and may be any of various antioxidants conventionally used in the art. For example, the antioxidant is one or more of 4, 6-bis (octylthiomethyl) o-cresol (trade name: antioxidant 1520), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: antioxidant 1076), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (trade name: antioxidant 4020), N-cumyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010NA), and N-phenyl-2-naphthylamine (trade name: antioxidant D), and generally, since the antioxidant 1520 has two sulfide substituents at the 2,4 positions, it has a bifunctional function (having both a primary antioxidant function and a secondary antioxidant function), and thus, it can exert an intramolecular synergistic effect, the use of the antioxidant 1520 as an antioxidant system can reduce the amount of the antioxidant system. In addition, the addition of the anti-aging agent 1076 can significantly prevent the cleavage of the polymer molecular chain. Preferably a combination of anti-aging agent 1520 and anti-aging agent 1076, the weight ratio of anti-aging agent 1520 to anti-aging agent 1076 may be 0.5 to 5:1, more preferably 1 to 3: 1, 1520 antioxidant and 1076 antioxidant.
Preferably, the weight ratio of the antioxidant to the 1, 3-butadiene is 0.1-0.6: 100, preferably 0.2 to 0.4: 100.
in a third aspect, the present invention provides a method for preparing a HIPS resin, wherein the method comprises:
(1) providing a low cis-polybutadiene rubber solution, wherein the low cis-polybutadiene rubber solution contains the low cis-polybutadiene rubber obtained by the method;
(2) in the presence of a free radical initiator, styrene and a toughening agent are subjected to polymerization reaction; wherein the toughening agent contains the low cis-polybutadiene solution obtained in the step (1).
According to the invention, the solvent in the low cis-polybutadiene polymerization solution is a benzene solvent, the benzene solvent is one or more of unsubstituted or C1-C4 alkyl substituted benzene, C1-C4 alkyl can be one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl and the like, C1-C4 alkyl substituted benzene as the benzene solvent can be single-point substituted or multi-point substituted, preferably, the benzene solvent is one or more of benzene, toluene, ethylbenzene and xylene, preferably ethylbenzene.
The benzene-based solvent may be used in such an amount that the content of the low-cis polybutadiene rubber in the solution of the low-cis polybutadiene rubber is 25 to 55 wt% or more, and the benzene-based solvent is preferably used in such an amount that the content of butadiene is 30 to 45 wt% under the condition that the benzene-based solvent satisfies the above conditions.
The manner of providing the low cis-polybutadiene solution in the step (1) is preferably to form a solution of the above-mentioned low cis-polybutadiene rubber and a benzene-based solvent. The low cis-polybutadiene rubber is obtained by subjecting a mixed solution obtained after termination reaction to a solvent removal step.
According to the invention, in the step (2) of the preparation method of the HIPS resin, the low cis-polybutadiene rubber is used as a toughening agent and is polymerized together with styrene to obtain the HIPS resin. The toughening agent contains a solvent brought by the solution in the step (1), preferably, in the step (2), the toughening agent is used in an amount such that the benzene-based solvent content is 18 wt% or less, more preferably 6-18 wt%, based on the total weight of the styrene and the toughening agent. Preferably, the weight ratio of styrene to the toughening agent on a dry basis is 550-2500: 100, more preferably 600-: 100, more preferably 900-: 100.
according to the present invention, the radical initiator may be various initiators conventionally used in the art for preparing HIPS resins, for example, the radical initiator may be one or more of thermal decomposition type initiators, preferably one or more selected from peroxide type initiators and azobisnitrile type compound initiators, more preferably one or more selected from t-butyl peroxy-2-ethylhexyl tert-carbonate, diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl peroxide and azobisnitrile type compounds, still more preferably one or more selected from dibenzoyl peroxide, di-o-toluyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile. Preferably, the weight ratio of the styrene to the free radical initiator is 2500-: 1, more preferably 3000-: 1, more preferably 4000-: 1, more preferably 5000-: 1.
according to the present invention, preferably, in the step (2), the polymerization conditions include: the polymerization conditions include: the temperature is 100 ℃ and 150 ℃, and the time is 7-9 h. The polymerization reaction may be carried out with stirring, for example, with stirring at 100-400 rpm.
In another preferred embodiment of the present invention, in step (2), the polymerization conditions include: first reacting at 100-110 ℃ for 1-3h, then reacting at 115-125 ℃ for 1-3h (e.g. 1-2h), then reacting at 130-140 ℃ for 1-3h (e.g. 1-2h), and finally reacting at 145-155 ℃ for 1-3h (e.g. 1-2.5 h). More preferably, in step (2), the polymerization conditions include: firstly reacting at 110 ℃ for 1.5-2.5h, then reacting at 125 ℃ for 1.5-2.5h, then reacting at 135 ℃ for 1.5-2.5h, and finally reacting at 155 ℃ for 1.5-2.5 h. The polymerization reaction may be carried out with stirring, for example, with stirring at 100-400 rpm.
The invention also provides the HIPS resin prepared by the method.
Preferably, in the HIPS resin of the present invention, the content of structural units of styrene is from 85 to 95% by weight, preferably from 90 to 95% by weight (it is understood that the remaining content is mainly structural units provided for butadiene, i.e., the content of structural units of butadiene is from 5 to 15% by weight, preferably from 5 to 10% by weight), and the number average molecular weight is from 60,000 to 150,000, more preferably from 80,000 to 120,000; the molecular weight distribution coefficient is 2-3.
The method of the present invention enables to obtain a HIPS resin product having more balanced gloss and impact properties, preferably, the HIPS resin has an Izod impact strength of 10kJ/m2Above, preferably 10.5kJ/m2The above; the 60 ℃ surface gloss is 70 or more, preferably 80 or more. HIPS mechanical properties were tested using an INSTRON 5567 Universal Material testing machine, UK. Wherein the notched Izod impact Strength is measured in accordance with GB/T1843-1996 (kJ/m)2) (ii) a The 60 ℃ surface gloss is measured according to ASTM D526(60 ℃).
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the measurement methods involved include:
(1) the monomer conversion is determined gravimetrically, i.e.as the weight percentage of polymer after removal of solvent to the theoretical polymer yield.
(2) The Mooney viscosity was measured according to GB/T1232.1 using a Mooney viscometer model GT-7080-S2 manufactured by Gotech corporation of Taiwan, China, wherein the preheating time was 1min, the rotation time was 4min, and the measurement temperature was 100 ℃.
(3) The content of 1, 2-polymerized structural units in the low-cis polybutadiene rubber is measured by using an AVANCEDRX400MHz type nuclear magnetic resonance apparatus (manufactured by BRUKER)1H-NMR), wherein,1the resonance frequency of the H-nuclei is 300.13MHz,spectrum width 2747.253Hz, pulse width 5.0 μ s, data point 16K, sample tube diameter 5mm, solvent deuterated chloroform CDCl3The sample concentration is 15% (W/V), the test temperature is normal temperature, the scanning times are 16 times, and the calibration is carried out by taking the chemical displacement of tetramethylsilane as 0 ppm.
(4) The molecular weight and the molecular weight distribution were measured by using a gel permeation chromatograph model HLC-8320 from Tosoh corporation, Japan, wherein the test conditions included: the chromatographic column was TSKgel SuperMultiporeHZ-N, the standard column was TSKgel SuperMultiporeHZ, the solvent was chromatographically pure THF, the calibration standard was polystyrene, the sample mass concentration was 1mg/ml, the sample amount was 10.00. mu.l, the flow rate was 0.35ml/min, and the test temperature was 40.0 ℃.
(5) The viscosity of the styrene solution of 5 wt% rubber at 25 ℃ is measured by adopting the standard Q/SH3155.SXL.C26-2019 of Beijing Yanshan petrochemical company enterprise, and is measured at constant temperature at 25 ℃ by adopting a Fin viscometer.
(6) In the invention, the gel content is determined by a gravimetric method of a standard Q/SH3155.SXL.C27-2019 test of Beijing Yanshan petrochemical company enterprise. The specific process is as follows: adding a polymer sample into styrene, shaking the mixture in a shaker at the temperature of 25 ℃ for 16 hours to completely dissolve soluble substances, preparing a styrene solution containing 5 weight percent of polymer, and recording the mass of the polymer sample as C (in grams); weighing a 400-mesh clean nickel screen, and recording the mass of the clean nickel screen as B (in grams); then filtering the solution by using a nickel screen; washing the nickel screen with styrene after filtering, drying the nickel screen for 30 minutes at 150 ℃ under normal pressure, weighing, and recording the mass of the nickel screen as A (in grams); the gel content was calculated according to the following formula:
gel content [ (% a-B)/C ] × 100%.
(7) The chromaticity is tested by adopting a Hunter Lab ColorFlex desktop color difference meter of Hunter company in America according to the standard Q/SH3155.SXL. C29-2019; and (3) testing conditions are as follows: the color system adopts CIELAB, the optical geometry structure is 45 degrees/0 degrees, the light source is C light source, the observation angle is 2 degrees, and the thickness of the sample is about 15 mm.
(8) HIPS mechanical properties were tested using an INSTRON 5567 Universal Material testing machine, UK. Wherein, the cantilever beam notch is towardsImpact Strength measured according to GB/T1843-1996 Standard (kJ/m)2) (ii) a The 60 ℃ surface gloss is measured according to ASTM D526(60 ℃).
Experimental device and process: the experiment was carried out in a 16L polymerization reactor (manufactured by sida corporation, with a reactor internal diameter of 20cm) operated at full load with a bottom-in-top-out feed. Solvent, butadiene monomer, branched monomer, gel inhibitor, initiator and structure regulator are added separately from the bottom of the reactor, and terminator and antioxidant are added into the pipeline at the outlet of the reactor to obtain polymer glue solution.
The experimental pressures are both gauge pressures.
Antioxidant 1520 was purchased from national pharmaceutical agents; antioxidant 1076 was purchased from enokay reagent.
The organolithium initiators were purchased from carbofuran reagent and diluted to 0.07 mol.L with hexane-1。
1,2 butadiene was purchased from Inokay reagent and diluted to 1 wt% concentration with hexane.
Potassium tert-pentoxy purchased from carbofuran reagent company and diluted to 0.02 mol.L with hexane-1。
Divinylbenzene (DVB) was purchased from Inokay reagent and diluted to 0.04 mol.L with hexane-1。
Example 1
This example illustrates the low cis polybutadiene rubber of the present invention and its preparation.
(1) Under the protection of nitrogen, continuously adding an n-hexane solvent, a 1, 3-butadiene monomer, a DVB monomer, 1, 2-butadiene (a gel inhibitor), an organic lithium initiator and a structure regulator into a 16L reactor from the bottom of the reactor respectively (the type and the amount of the organic lithium initiator are shown in Table 1, and the flow rates listed in the table are measured by pure compounds); and an anionic solution polymerization was carried out at the specified temperature and reaction pressure (conditions are shown in Table 1),
(2) a terminator and an antioxidant (the type and amount are shown in Table 2, and the flow rates are all measured as pure compounds) were sequentially added to the line at the upper outlet of the polymerization to finally obtain a polymerization solution PB1 of low cis-polybutadiene rubber, wherein the content of the low cis-polybutadiene rubber was 15.8 wt%.
A sample of the finally obtained polymerization solution was taken out to conduct a vapor condensation desolvation treatment, and the resulting polymer C1 was subjected to the structure and property measurement, and the results are shown in Table 3.
Examples 2 to 5
This example illustrates the low cis polybutadiene rubber of the present invention and its preparation.
According to the method described in example 1, except that the reactions were carried out using the materials and amounts shown in Table 1, to obtain polymerization solutions of low cis-polybutadiene rubber PB2-PB5, respectively, wherein the contents of the respective low cis-polybutadiene rubbers were: PB 2: 15.8 wt%; PB 3: 15.8 wt%; PB 4: 15.8 wt%; PB 5: 15.8% by weight.
A sample of the finally obtained polymerization solution was taken out and subjected to steam coagulation and desolvation treatment, and the resulting polymers C2-C5 were subjected to structure and property measurements, the results of which are shown in Table 3.
Example 6
This example illustrates the low cis polybutadiene rubber of the present invention and its preparation.
According to the method described in example 1, except that isopropanol was used as a terminator in place of the aqueous carbon dioxide solution and in an amount of 0.15g of isopropanol per 100g of 1, 3-butadiene, a polymerization solution PB6 of low cis-polybutadiene rubber was obtained, wherein the content of low cis-polybutadiene rubber was 15.8 wt%.
A sample of the final polymerization solution was taken out and subjected to a vapor condensation desolvation treatment, and the resulting polymer C6 was subjected to the structure and property measurement, and the results are shown in Table 3.
Comparative example 1
According to the process described in example 1, except that no DVB was added as a comonomer at the bottom of the reactor, a polymerization solution DPB1 of low cis-polybutadiene rubber was obtained, wherein the content of low cis-polybutadiene rubber was 15.7% by weight.
A sample of the final polymerization solution was taken out and subjected to a vapor condensation desolvation treatment, and the resulting polymer DC1 was subjected to the structure and property measurement, and the results are shown in Table 3.
Comparative example 2
The procedure of example 1 was followed, except that the DVB flow rate was 1.94g/h, to thereby obtain a polymerization solution DPB2 of low cis-polybutadiene rubber, wherein the content of low cis-polybutadiene rubber was 15.8% by weight.
A sample of the final polymerization solution was taken out and subjected to a vapor condensation desolvation treatment, and the resulting polymer DC2 was subjected to the structure and property measurement, and the results are shown in Table 3.
Comparative example 3
According to the process described in example 1, except that the flow rate of n-butyllithium during the polymerization was 2.66g/h, a polymerization solution DPB3 of a low cis-polybutadiene rubber was obtained, wherein the content of the low cis-polybutadiene rubber was 15.8% by weight.
A sample of the final polymerization solution was taken out and subjected to a vapor condensation desolvation treatment, and the resulting polymer DC3 was subjected to the structure and property measurement, and the results are shown in Table 3.
Comparative example 4
According to the method described in example 1, except that 1, 2-butadiene is not added in the polymerization process, after 6 hours, the polymerization kettle is full of gel, and normal polymerization cannot be carried out; a polymerization solution DPB4 of low cis-polybutadiene rubber was obtained, in which the content of low cis-polybutadiene rubber was 15.8% by weight.
A part of the finally obtained polymerization solution sample was taken out to be subjected to steam coagulation and solvent removal treatment, and the obtained polymer DC4 was subjected to the structure and property measurement, and the results are shown in Table 3.
Comparative example 5
According to the method described in example 1, except that potassium tert-pentoxy was not added during the polymerization, a large amount of gel was formed in the polymerization vessel after 24 hours; a polymerization solution DPB5 of low cis-polybutadiene rubber was obtained, in which the content of low cis-polybutadiene rubber was 15.8% by weight.
A sample of the finally obtained polymerization solution was taken out to conduct vapor condensation solvent removal treatment, and the structure and properties of the obtained polymer DC5 were measured, and the results are shown in Table 3.
Comparative example 6
The process of example 1 was followed except that the n-hexane solution containing the branching monomer DVB was continuously fed into the reactor at a distance from the bottom 1/2 of the reactor. Thus, a polymerization solution DPB6 of low cis-polybutadiene rubber was obtained, in which the content of low cis-polybutadiene rubber was 15.7% by weight.
A sample of the finally obtained polymerization solution was taken out and subjected to steam coagulation and desolvation treatment to obtain polymer DC6, and the results of the structural and performance measurements were found to be shown in Table 3.
Comparative example 7
According to the method of example 1, except that a solution of n-hexane containing the branching monomer DVB was continuously fed into the reactor at a distance from the bottom 5/8 of the reactor to obtain a polymerization solution DPB7 of low cis-polybutadiene rubber with a content of 15.7% by weight of low cis-polybutadiene rubber.
A sample of the finally obtained polymerization solution was taken out and subjected to steam coagulation and desolvation treatment to obtain polymer DC7, and the results of the structural and performance measurements were found to be shown in Table 3.
TABLE 1
TABLE 2
TABLE 3
As can be seen from Table 3, the low cis-polybutadiene rubber prepared by the invention has moderate 5% styrene solution viscosity and Mooney viscosity, low chroma and gel content, and is particularly suitable for serving as a HIPS (or ABS) toughening agent.
Example 7
This example illustrates the HIPS resin of the present invention and the preparation method thereof
(1) 96g of the low cis-polybutadiene rubber C1 obtained in example 1 was mixed with 234g of ethylbenzene to form a low cis-polybutadiene polymerization solution;
(2) mixing 330g of the polymerization solution of the low cis-polybutadiene rubber obtained in the step (1) with 1100g of styrene monomer, adding 45g of mineral oil (provided by Beijing Yanshan petrochemical company, chemical industry and factories, the density of which is 0.85-0.88g/ml, the same applies below) and 0.1g of tert-butyl peroxy-2-ethylhexyl carbonate, mixing, polymerizing for 2 hours at the stirring speed of 300rpm and the polymerization temperature of 105 ℃, and then heating to 120 ℃ for polymerizing for 2 hours; heating to 135 ℃ at the stirring speed of 100rpm, polymerizing for 2h, finally heating to 150 ℃, polymerizing for 2h, and carrying out vacuum flash evaporation on the reaction product to remove unreacted monomers and solvent to obtain the HIPS resin P1.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
Example 8
This example illustrates the HIPS resin of the present invention and the method of preparing the same.
(1) 90g of the low cis-polybutadiene rubber C2 obtained in example 2 was mixed with 210g of ethylbenzene to form a low cis-polybutadiene polymerization solution;
(2) mixing 300g of the polymerization solution of the low cis-polybutadiene rubber obtained in the step (1) with 1100g of styrene monomer, adding 50g of mineral oil and 0.2g of azobisisobutyronitrile, mixing, polymerizing for 1.5h at a stirring speed of 350rpm and a polymerization temperature of 110 ℃, and then heating to 120 ℃ for polymerizing for 2.5 h; heating to 130 ℃ under the stirring speed of 200rpm, polymerizing for 1.5h, finally heating to 155 ℃ for polymerizing for 2h, and carrying out vacuum flash evaporation on the reaction product to remove unreacted monomers and solvent to obtain the HIPS resin P2.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
Examples 9 to 12
This example illustrates the HIPS resin of the present invention and the method of preparing the same.
According to the method described in example 7, except that low cis-polybutadiene rubber C3-C6 was used instead of low cis-polybutadiene rubber C1, respectively, the reaction product was subjected to vacuum flash evaporation to remove unreacted monomers and solvent, thereby obtaining HIPS resins P3-P6, respectively.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
Comparative example 6
According to the method described in example 7, except that the low cis-polybutadiene rubber described in DC1-DC5 was used in place of the low cis-polybutadiene rubber C1, respectively, the reaction product was subjected to vacuum flash evaporation to remove the unreacted monomers and solvent, thereby obtaining HIPS resins DP1-DP5, respectively.
Comparative examples 7 to 8
According to the method described in example 7, except that the low cis-polybutadiene rubber described in DC6-DC7 was used in place of the low cis-polybutadiene rubber C1, respectively, the reaction product was subjected to vacuum flash evaporation to remove the unreacted monomers and solvent, thereby obtaining HIPS resins DP6-DP7, respectively.
Comparative examples 9 to 10
HIPS resins DP8-DP9 were obtained according to the method of example 7, except that Japanese Asahi-formulated products 720A and 730A (solvent-removed) were used, respectively, instead of low cis-polybutadiene rubber C1.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
TABLE 4
As can be seen from Table 4, by using the low cis-polybutadiene of the present invention as a toughening agent, HIPS resins with more balanced impact resistance and gloss can be obtained, and the HIPS resins obtained by the present invention have better overall properties than HIPS resins obtained by using a toughening agent which is popular in the market.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A low cis-polybutadiene rubber, characterized in that the content of 1, 2-polymerized structural units in the low cis-polybutadiene rubber is 8-20 wt%; the number average molecular weight is 70,000-90,000 g/mol; the molecular weight distribution coefficient is 2.25-2.65; mooney viscosity ML at 100 ℃1+4Is 40 to 60; the 5 wt.% styrene solution at 25 ℃ had a viscosity of 40-66 cp.
2. The low-cis polybutadiene rubber according to claim 1, wherein the content of 1, 2-polymerized structural units in the low-cis polybutadiene rubber is 9 to 18% by weight, preferably 10 to 16% by weight;
preferably, the number average molecular weight is 73,000-88,000g/mol, more preferably 75,000-85,000 g/mol;
preferably, the molecular weight distribution coefficient is from 2.28 to 2.55, more preferably from 2.3 to 2.55;
preferably, the Mooney viscosity ML at 100 ℃1+4From 40 to 58, preferably from 45 to 55;
preferably, the 5 wt% styrene solution has a viscosity of 42-66cp, more preferably 44-58cp, at 25 ℃.
3. A process for preparing a low-cis polybutadiene rubber as described in claim 1 or 2, wherein the process comprises:
(1) continuously feeding 1, 3-butadiene and a branched monomer into a reactor from the bottom of the reactor in an inert solvent in the presence of an organic lithium initiator, a gel inhibitor and a structure regulator to perform anionic solution polymerization reaction until the conversion rate of the 1, 3-butadiene reaches more than 99%;
(2) and (2) contacting the mixture obtained in the step (1) with a terminator to carry out termination reaction.
4. The preparation method according to claim 3, wherein the organolithium initiator is a compound represented by the formula RLi, wherein R is selected from an alkyl group of C1-C20, a cycloalkyl group of C6-C20, or an aryl group of C6-C20; preferably, the organolithium initiator is one or more of methyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium, cyclohexyllithium, 4-cyclohexylbutyllithium, phenyllithium, triphenylmethyllithium and 2-naphthyllithium, more preferably n-butyllithium and/or sec-butyllithium;
preferably, the molar ratio of 1, 3-butadiene to the organolithium initiator is 750-1300: 1, preferably 850-: 1, more preferably 900-: 1,
preferably, the inert solvent is C5-C8 cycloalkane and/or C5-C9 alkane, preferably one or more of cyclohexane, methylcyclopentane, methylcyclohexane, methylpentane, n-hexane, n-heptane and isooctane.
5. The method of claim 3, wherein the anionic solution polymerization conditions comprise: the temperature is 0-120 ℃, preferably 40-115 ℃, and more preferably 50-110 ℃; the time is 30-90min, preferably 40-80 min; the gauge pressure is 0.1 to 2MPa, preferably 0.5 to 1 MPa.
6. The production method according to any one of claims 3 to 5, wherein the structure-regulating agent is potassium alkoxide, preferably potassium tert-pentylate and/or potassium 2-hexanoate,
preferably, the molar ratio of the structure regulator to the initiator is from 0.05 to 0.5:1, preferably from 0.1 to 0.2: 1.
7. The production method according to any one of claims 3 to 6, wherein the gel inhibitor is one or more of tetramethylethylenediamine/1, 2-butadiene, a carbon tetrakisraffinate, and 1, 2-butadiene,
preferably, the weight ratio of the gel inhibitor to 1, 3-butadiene is 1-10: 10000, preferably 5 to 8: 10000.
8. the production method according to any one of claims 3 to 7, wherein the branched monomer is an aromatic vinyl monomer of C10 to C16, preferably one or more of divinylbenzene, diallylbenzene and diallylbenzene,
preferably, the molar ratio of the branched monomer to the organolithium initiator is from 0.4 to 1: 1, preferably 0.4 to 0.8: 1.
9. the method according to any one of claims 3-8, wherein the terminating agent is one or more of a C1-C4 alcohol, an organic acid, and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid, and carbon dioxide, more preferably carbon dioxide.
10. The method according to any one of claims 3 to 9, wherein the method comprises a step of subjecting the mixed solution obtained in step (2) to solvent removal.
11. A method of preparing a HIPS resin, the method comprising:
(1) providing a low-cis polybutadiene rubber solution containing a low-cis polybutadiene rubber obtained by the method of any one of claims 3 to 10;
(2) in the presence of a free radical initiator, styrene and a toughening agent are subjected to polymerization reaction; wherein the toughening agent contains the low cis-polybutadiene rubber solution obtained in the step (1).
12. The preparation method of claim 11, wherein the solvent in the low-cis polybutadiene solution is a benzene-based solvent, the benzene-based solvent being one or more of unsubstituted or C1-C4 alkyl-substituted benzene;
preferably, the benzene solvent is used in an amount of 6 to 18 wt% based on the total weight of the styrene, the benzene solvent and the toughening agent;
preferably, the weight ratio of styrene to the toughening agent on a dry basis is 550-2500: 100, preferably 600-: 100, more preferably 900-: 100.
13. the production method according to claim 11 or 12, wherein the radical initiator is one or more of diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl peroxide, and azobisnitrile compounds, preferably one or more of t-butyl peroxy-2-ethylhexyl tert-carbonate, dibenzoyl peroxide, di-o-methylbenzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile, more preferably one or more of t-butyl peroxy-2-ethylhexyl tert-carbonate, dibenzoyl peroxide, di-o-methylbenzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile;
preferably, the weight ratio of the amount of the styrene to the amount of the radical initiator is 2500-: 1, more preferably 3000-: 1, more preferably 4000-: 1, more preferably 5000-: 1.
14. the production method according to any one of claims 11 to 13, wherein the conditions of the polymerization reaction include: the temperature is 100-150 ℃, and the time is 7-9 h;
alternatively, the polymerization conditions include: firstly reacting at the temperature of 100-110 ℃ for 1-3h, then reacting at the temperature of 115-125 ℃ for 1-3h, then reacting at the temperature of 130-140 ℃ for 1-3h, and finally reacting at the temperature of 145-155 ℃ for 1-3 h;
preferably, the polymerization conditions include: firstly reacting at 110 ℃ for 1.5-2.5h, then reacting at 125 ℃ for 1.5-2.5h, then reacting at 135 ℃ for 1.5-2.5h, and finally reacting at 155 ℃ for 1.5-2.5 h.
15. HIPS resin obtained by the production method according to any one of claims 11 to 14.
16. The HIPS resin of claim 15, wherein the content of the structural units of styrene in the HIPS resin is 85 to 95% by weight, preferably 90 to 95% by weight; the HIPS resin has a number average molecular weight of 60,000-150,000, more preferably 80,000-120,000;
preferably, the HIPS resin has a surface gloss of 70 or more at 60 ℃ and a notched Izod impact strength of 10kJ/m measured according to GB/T18432The above.
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| CN1519269A (en) * | 2003-01-31 | 2004-08-11 | 宇部兴产株式会社 | Rubber modified and impact preventing polystyrene resin compsns. |
| CN106589247A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber and preparing method and application thereof |
| CN109251263A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1519269A (en) * | 2003-01-31 | 2004-08-11 | 宇部兴产株式会社 | Rubber modified and impact preventing polystyrene resin compsns. |
| CN106589247A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber and preparing method and application thereof |
| CN109251263A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof |
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