CN107722402B - Toughening agent composition, ABS resin and preparation method thereof - Google Patents
Toughening agent composition, ABS resin and preparation method thereof Download PDFInfo
- Publication number
- CN107722402B CN107722402B CN201610649835.9A CN201610649835A CN107722402B CN 107722402 B CN107722402 B CN 107722402B CN 201610649835 A CN201610649835 A CN 201610649835A CN 107722402 B CN107722402 B CN 107722402B
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- CN
- China
- Prior art keywords
- styrene
- composition
- polybutadiene rubber
- low
- butadiene
- 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.)
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000012745 toughening agent Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 177
- 239000005064 Low cis polybutadiene Substances 0.000 claims abstract description 166
- 238000000034 method Methods 0.000 claims abstract description 117
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 111
- 238000009826 distribution Methods 0.000 claims abstract description 84
- 230000002902 bimodal effect Effects 0.000 claims abstract description 48
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 257
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 224
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 156
- 238000006116 polymerization reaction Methods 0.000 claims description 76
- 150000002900 organolithium compounds Chemical class 0.000 claims description 62
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 53
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 42
- 239000003960 organic solvent Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 27
- 239000001569 carbon dioxide Substances 0.000 claims description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 26
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 25
- 239000007822 coupling agent Substances 0.000 claims description 21
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 16
- 150000003254 radicals Chemical class 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 15
- 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 claims description 13
- 239000005049 silicon tetrachloride Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 150000002642 lithium compounds Chemical class 0.000 claims description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 9
- 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 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 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
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 5
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 5
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 5
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 claims description 3
- BOGFHOWTVGAYFK-UHFFFAOYSA-N 1-[2-(2-propoxyethoxy)ethoxy]propane Chemical compound CCCOCCOCCOCCC BOGFHOWTVGAYFK-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- -1 alkyl peroxides Chemical class 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000012933 diacyl peroxide Substances 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
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 4
- 125000005634 peroxydicarbonate group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 34
- 239000003963 antioxidant agent Substances 0.000 description 33
- 230000003078 antioxidant effect Effects 0.000 description 31
- 239000011347 resin Substances 0.000 description 28
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 26
- 239000007787 solid Substances 0.000 description 20
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 17
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 17
- 239000012046 mixed solvent Substances 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000005060 rubber Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 241001550224 Apha Species 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- FARAXEAITGXHNY-UHFFFAOYSA-N CCCCCC.[Si](Cl)(Cl)(Cl)Cl Chemical compound CCCCCC.[Si](Cl)(Cl)(Cl)Cl FARAXEAITGXHNY-UHFFFAOYSA-N 0.000 description 2
- 239000005063 High cis polybutadiene Substances 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding 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
- 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
- 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
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The invention relates to the field of ABS resin, and discloses a toughening agent composition which contains low-cis polybutadiene rubber and a linear styrene-butadiene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber is in bimodal distribution, and the bimodal number average molecular weight is respectively in the range of 40000-75000 and the range of 125000-250000; the number average molecular weight of the linear butylbenzene copolymer is 70000-200000. The invention also discloses an ABS resin and a preparation method thereof. According to the method, the low cis-polybutadiene rubber with a specific molecular weight and bimodal distribution and the linear styrene-butadiene copolymer with a specific molecular weight are matched to be used as the toughening agent component for preparing the ABS resin, so that the ABS resin with higher impact resistance and higher glossiness is obtained.
Description
Technical Field
The invention relates to an ABS resin, in particular to a toughening agent composition, an ABS resin and a preparation method thereof.
Background
The traditional continuous bulk ABS resin (namely acrylonitrile-butadiene-styrene copolymer) is obtained by adding a toughening agent into styrene and acrylonitrile monomers according to a certain proportion and adopting thermal initiation or free radical initiator initiation in the presence of a small amount of ethylbenzene solvent. The toughening rubber selected for the ABS resin can be low cis-polybutadiene rubber, high cis-polybutadiene rubber, solution polymerized styrene-butadiene rubber, styrene-butadiene-styrene copolymer, and is especially preferably polybutadiene rubber (low cis-polybutadiene rubber and high cis-polybutadiene rubber).
Compared with other toughening rubbers, the low cis-polybutadiene rubber has the advantages of low ① gel content, pure ② product, no transition metal, good ③ color, 8-20% of vinyl structure in ④, and high grafting and crosslinking reactivity, but the single-component toughening system of the low cis-polybutadiene rubber has the following problems that ① has narrow molecular weight distribution and single particle size distribution of the single-component toughening rubber due to the inherent characteristics of an active polymerization product, the improvement of the impact resistance of ② ABS resin mainly depends on the improvement of the rubber content, but the excessive rubber content can reduce the glossiness of the product, and the problem of the rubber solubility is also solved.
Disclosure of Invention
The invention aims to provide a toughening agent composition capable of simply preparing ABS resin with higher impact resistance and higher glossiness, a preparation method of the ABS resin and the ABS resin prepared by the method, aiming at the defect that the ABS resin with high impact resistance and high glossiness is difficult to prepare in the prior art.
The inventors of the present invention have intensively studied to find that the molecular weight and molecular weight distribution of rubber as a toughening agent are closely related to the particle size of rubber particles formed by a phase inversion process, thereby affecting the impact resistance and gloss of ABS resin. The rubber has small molecular weight, is not beneficial to the termination of silver streaks and the induction of shear bands, and leads to poor impact resistance of the obtained ABS resin; the 5% styrene solution of the rubber with large molecular weight has high viscosity, the particle size of the rubber formed in the phase inversion process is large, and the induction and termination of crazing are facilitated, but the number of molecules of the rubber with the same weight is reduced, the improvement range of the impact resistance is small, and the glossiness of the ABS resin is influenced. The toughening agent contains the low cis-polybutadiene rubber with the specific molecular weight and bimodal distribution, and the linear styrene-butadiene copolymer with the specific molecular weight is matched, so that the defects of a single toughening agent can be overcome under the synergistic effect of the low cis-polybutadiene rubber and the linear styrene-butadiene copolymer, and the ABS resin with higher impact resistance and higher glossiness can be obtained. Thus, the present invention has been completed.
In order to achieve the above object, the present invention provides a toughening agent composition comprising a low-cis polybutadiene rubber and a linear styrene-butadiene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber is bimodal, and the bimodal number average molecular weights are respectively in the range of 40000-75000 and in the range of 125000-250000; the number average molecular weight of the linear butylbenzene copolymer is 70000-200000.
The invention provides a preparation method of ABS resin, which comprises the following steps:
(1) preparing low cis-polybutadiene rubber; wherein the molecular weight of the low-cis polybutadiene rubber is in bimodal distribution, and the bimodal number average molecular weight is respectively in the range of 40000-75000 and in the range of 125000-250000;
(2) preparing a linear styrene-butadiene copolymer; wherein the linear butylbenzene copolymer has a number average molecular weight of 70000-200000;
(3) carrying out polymerization reaction on styrene, acrylonitrile and a toughening agent in the presence of a free radical initiator; wherein the toughening agent is a solution containing the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer.
The invention also provides the ABS resin prepared by the method.
According to the method, the low cis-polybutadiene rubber with a specific molecular weight and bimodal distribution and the linear styrene-butadiene copolymer with a specific molecular weight are matched to be used as the toughening agent component for preparing the ABS resin, so that the toughening agent can keep proper solution viscosity and molecular weight distribution, the problem that the impact resistance and the glossiness of the ABS resin cannot be simultaneously achieved in the existing preparation method is solved, and the ABS resin with higher impact resistance and higher glossiness is obtained.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
In the present invention, the low cis-polybutadiene rubber means a polymer having a relatively low content of a structural unit obtained by polymerizing cis 1, 4-butadiene, and generally means a polybutadiene rubber having a content of a cis 1, 4-butadiene structural unit of 30 to 40% by weight. Coupled polymer means that the polymer has undergone a coupling reaction during formation.
The invention provides a toughening agent composition, which contains low-cis polybutadiene rubber and a linear styrene-butadiene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber is in bimodal distribution, and the bimodal number average molecular weight is respectively in the range of 40000-75000 and 125000-250000; the number average molecular weight of the linear butylbenzene copolymer is 70000-200000.
According to the invention, in order to enable the obtained toughening agent composition to be better used for preparing ABS resin and obtain ABS resin with better performance, the weight ratio of the low-cis polybutadiene rubber to the linear styrene-butadiene copolymer is preferably 0.4-5: 1, preferably 0.4 to 4: 1, more preferably 0.43 to 2.3: 1, more preferably 0.67 to 1.5: 1.
according to the invention, although the low-cis polybutadiene rubber with the molecular weight in bimodal distribution and the bimodal number average molecular weight respectively in the range of 40000-75000 and 125000-250000 can be used as the component of the toughening agent for preparing the ABS resin, in order to obtain the low-cis polybutadiene rubber with better improved glossiness and impact resistance and better processability, the low-cis polybutadiene rubber preferably has the bimodal number average molecular weight respectively in the range of 45000-65000 and 140000-210000 (preferably 145000-210000).
More preferably, in the low-cis polybutadiene rubber, the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number average molecular weight in the range of 40000-75000 (preferably 45000-65000), the molecular weight distribution coefficient of the segment can be 1-1.2, to the content of the low-cis polybutadiene rubber in the range of 125000-250000 (preferably 140000-210000, more preferably 145000-210000), the molecular weight distribution coefficient of the segment can be 1-1.2, is 100: 150-: 250-1900, more preferably 100: 280-1600 (e.g., 100: 300-1600), more preferably 100: 500-. More preferably, the low-cis polybutadiene rubber has a vinyl side group content of 10 to 20 weight percent (based on the total weight of the low-cis polybutadiene rubber).
Preferably, the low cis polybutadiene rubber is a coupled polymer with a branching area of 70-95%, more preferably 75-95%.
According to the present invention, since the 5% styrene solution viscosity has an important influence on the impact resistance and gloss of the ABS resin, controlling the low cis-polybutadiene rubber of the present invention within the above molecular weight and distribution range enables control of the 5% styrene solution viscosity and Mooney viscosity of the low cis-polybutadiene rubber, preferably 30 to 60 (preferably 35 to 55) Mooney viscosity of the low cis-polybutadiene rubber. Preferably, the low cis-polybutadiene rubber has a5 wt% styrene solution viscosity of 15-50cp (preferably 20-40 cp). The viscosity of a5 wt% styrene solution of the low-cis polybutadiene rubber is the viscosity of the resulting solution when the low-cis polybutadiene rubber is dissolved in styrene so that the concentration of the low-cis polybutadiene rubber is 5 wt% (the same is understood for the viscosity of a5 wt% styrene solution of the linear styrene-butadiene copolymer in the present invention).
According to the invention, the low-cis polybutadiene rubber has a low color and gel content, wherein the color is preferably 5 to 15APHA, preferably 5 to 10 APHA. The gel content is preferably 100ppm or less, more preferably 50ppm or less, for example, 20 to 50ppm, for example, 20 to 30ppm (the lower the gel content, the more advantageous the ABS resin having excellent properties can be obtained).
According to the present invention, the low-cis polybutadiene rubber is not particularly limited as long as the low-cis polybutadiene rubber having the above characteristics can be obtained, and preferably, the method for producing the low-cis polybutadiene rubber comprises:
(a) subjecting butadiene to a first polymerization reaction in a first organic solvent in the presence of an organolithium compound to a conversion of butadiene of 95 wt% or more (preferably 98 wt% or more, for example 99 wt% or more);
(b) carrying out a coupling reaction on the product of the first polymerization reaction in the presence of a coupling agent;
(c) and in the presence of a terminator, terminating the product of the coupling reaction, and coagulating and drying the terminated product to obtain the low cis-polybutadiene rubber.
According to the present invention, in the step (a) of the polymerization reaction of butadiene, the conditions of the first polymerization reaction are not particularly limited as long as the conversion rate of butadiene is 95 wt% or more, preferably, under the initiator using an organolithium compound, and the conditions of the first polymerization reaction include: the temperature is 50-100 deg.C (preferably 70 deg.C)-90 ℃, more preferably 80-90 ℃, for a period of 30-80min (preferably 40-60 min). According to the present invention, the organolithium compound is not particularly limited, and various organolithium initiators conventionally used in the preparation of polybutadiene rubber in the art may be used, and preferably, the organolithium compound is of the formula R1A compound represented by Li, wherein R1Alkyl selected from C1-C10; more preferably, the organolithium compound is one or more of n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium, more preferably n-butyllithium and/or sec-butyllithium, and still more preferably n-butyllithium.
According to the present invention, the amount of the organolithium compound is not particularly limited as long as the low-cis polybutadiene rubber of the present invention can be obtained, and it is preferable that the molar ratio of butadiene to the organolithium compound in the step (a) of the polymerization reaction of butadiene is 700-: 1 (e.g., 750-: 1, more preferably 830-: 1 (e.g., 830-1100: 1, 900-1050: 1). Wherein, the organic lithium compound is added into the polymerization system in the form of solution, the solvent of the organic lithium compound can be one or more of hexane, cyclohexane, heptane and the like, and the concentration is preferably 0.5-2 mol/L.
According to the present invention, in the step (a) of the process for preparing low-cis polybutadiene rubber, the first organic solvent is one or more of alkane solvents, more preferably one or more of alkane solvents of C5-C10 and cycloalkane solvents of C5-C10. The first organic solvent is one or more of hexane, cyclohexane, pentane, heptane and isooctane, in consideration of solubility of the resulting polybutadiene, solution viscosity and toxicity of the solvent. Particularly preferably, the weight ratio of 1: a combination of cyclohexane and hexane of 0.08 to 0.5 (e.g., 1: 0.1 to 0.42) as the first organic solvent makes the preparation of the low cis-polybutadiene rubber smoother and the low cis-polybutadiene rubber is more easily extracted from the polymerization solution to obtain the low cis-polybutadiene rubber.
The amount of the first organic solvent used may vary within wide limits, for example such that the butadiene content is from 10 to 15% by weight (based on the total weight of the first organic solvent and butadiene).
According to the present invention, in order to obtain a low-cis polybutadiene rubber more suitable as the toughening agent component, preferably, in step (a) of the process for producing a low-cis polybutadiene rubber, the first polymerization reaction is further carried out in the presence of a structure modifier which is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol C1-C4 alkyl ether and diethylene glycol di-C1-C4 alkyl ether, 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dipropyl ether, more preferably tetrahydrofuran. The amount of the structure-regulating agent is not particularly limited, and an amount conventionally used in the art can be used. Preferably, the molar ratio of the amount of the structure regulator to the amount of the organolithium compound is 0.05 to 5: 1, more preferably 0.1 to 4: 1 (e.g., 0.15-3: 1), more preferably 0.1-1: 1, more preferably 0.4 to 0.8: 1, more preferably 0.5 to 0.7: 1.
according to the present invention, in the step (b) of the polymerization reaction of butadiene, a low cis-polybutadiene rubber having a bimodal distribution of molecular weight can be obtained by subjecting the product of the second polymerization reaction to a coupling reaction, the present invention is not particularly limited as long as the low cis-polybutadiene rubber having a bimodal distribution of molecular weight of the present invention can be obtained, preferably, the coupling agent is one or more of silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, 1, 8-dibromooctane, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ - (methacryloyloxy) propyltrimethoxysilane and N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, more preferably, silicon tetrachloride and/or methyltrichlorosilane, the amount of the coupling agent is not particularly limited as long as the low cis-polybutadiene rubber having a molecular weight distribution of the bimodal number average molecular weight in the range of 40000-75000 and 125000-organic molecular weight distribution of the present invention can be obtained, but the low cis-polybutadiene rubber having a molecular weight distribution of the polybutadiene rubber in the range of preferably 0.95 to 0.5 mol% by adding the coupling agent to the low cis-polybutadiene rubber as a solution of a suitable branching agent (for example, the low cis-polybutadiene rubber having a suitable branching property of 0.1.95 to 5-0.1.5 mol ratio of polybutadiene to 1.1.5-1.5-1.1.1.1-95-0 mol of polybutadiene rubber), preferably, and the low-1.1.5-1-95-0-95-0-1-95-mol of the coupling agent to 5-1.35-mol of the organic branching-1-95-1-mol of the polybutadiene rubber, preferably to 1-95-mol of the polybutadiene rubber, respectively (preferably to 1-95-1-95-1-95-mol of the coupling agent of the butadiene-1-95.
According to the present invention, preferably, the coupling reaction conditions include: the temperature is 60-80 deg.C, and the time is 20-40 min.
According to the present invention, in the step (c) of the polymerization reaction of butadiene, the product of the coupling reaction is terminated, and the terminated product (in which the content of the low-cis polybutadiene rubber may be, for example, 10 to 15% by weight) is coagulated and dried to obtain the low-cis polybutadiene rubber (in a solid form). The terminator may be, for example, one or more of a C1-C4 alcohol, an organic acid, and carbon dioxide, preferably one or more of isopropyl alcohol, stearic acid, citric acid, and carbon dioxide, more preferably carbon dioxide. The carbon dioxide can form carbonate with metal ions (Li, Mg, Al and Fe) 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 0.5 to 2.0 mol/L).
The amount of carbon dioxide used is not particularly limited, and may be suitably larger than the amount of the organolithium compound. Preferably, the molar ratio of carbon dioxide to the amount of organolithium compound (in terms of Li element) is 0.6 to 5: 1 (e.g., 1-5: 1, 3-4: 1), preferably 0.6-3: 1, more preferably 0.9 to 1.5: 1.
preferably, the termination conditions include: the temperature is 50-80 deg.C, and the time is 10-30 min.
According to the present invention, step (c) of the above process for preparing a low-cis polybutadiene rubber may further comprise introducing an additive into the terminated product. The additive may be various additives conventional in the art, such as an antioxidant. The antioxidant is preferably a combination of 1520 and 1076 antioxidants, more preferably in a weight ratio of 1: 1-3 of 1520 and 1076 antioxidants. Wherein the weight ratio of the antioxidant to the butadiene is preferably 0.1-0.3: 100.
according to the present invention, the coagulation and drying in step (c) can be performed by a method conventional in the art, and will not be described herein.
According to the present invention, although a linear styrene-butadiene copolymer having a molecular weight within the range of 70000-. The molecular weight distribution coefficient of the linear styrene-butadiene copolymer may be, for example, 1 to 1.2.
Preferably, the weight ratio of the structural unit of styrene to the structural unit of butadiene in the linear styrene-butadiene copolymer is 1: 1-10, more preferably 1: 1.5 to 8, more preferably 1: 1.5-5, more preferably 1: 2.3-4. More preferably, the linear styrene-butadiene copolymer has a content of vinyl side groups of 8 to 10 wt% (based on the total weight of the linear styrene-butadiene copolymer).
According to the present invention, since the solution viscosity of the toughening agent has a relatively important effect on the preparation of the ABS resin, the linear styrene-butadiene copolymer of the present invention can be controlled within the above molecular weight and distribution range, so as to obtain a suitable viscosity to meet the preparation requirement of the ABS resin, preferably, the mooney viscosity of the linear styrene-butadiene copolymer is 45-160 (preferably 60-130), and the viscosity of the 5 wt% styrene solution is 8-40cp (preferably 15-30 cp).
According to the present invention, preferably, the linear styrene-butadiene copolymer obtained in the step (2) has a low chroma and gel content, wherein the chroma is preferably 5 to 15APHA, preferably 5 to 10 APHA. The gel content is preferably 100ppm or less, more preferably 50ppm or less, for example, 10 to 50ppm, for example, 15 to 25ppm (the lower the gel content, the more favorable the ABS resin having excellent properties can be obtained).
According to the present invention, the method for preparing the above-mentioned linear styrene-butadiene copolymer is not particularly limited as long as the linear styrene-butadiene copolymer having the above-mentioned characteristics can be obtained. Preferably, the preparation method of the linear styrene-butadiene copolymer comprises the following steps:
(A) carrying out second polymerization reaction on butadiene and styrene in a second organic solvent in the presence of an organic lithium compound;
(B) and (3) terminating the product of the second polymerization reaction in the presence of a terminating agent, and condensing and drying the terminated product to obtain the linear styrene-butadiene copolymer (in a solid form).
According to the invention, the second polymerization reaction will be such that butadiene and styrene are initiated by the organolithium compound to give a substantially linear polymer of butadiene and styrene. The organolithium compound is as described above and will not be described in detail herein. Preferably, in the step (A) of the polymerization reaction of butadiene and styrene, the molar ratio of the total amount of butadiene and styrene to the organolithium compound is 1000-3000: 1, more preferably 1100-: 1, more preferably 1190-: 1 (e.g., 1200-: 1, for example 1700-: 1. wherein, the organic lithium compound is added into the polymerization system in the form of solution, the solvent of the organic lithium compound can be one or more of hexane, cyclohexane, heptane and the like, and the concentration is preferably 0.5-2 mol/L.
According to the present invention, the second organic solvent is not particularly limited, and may be selected as described for the first organic solvent in the polymerization of butadiene, and will not be described in detail herein. Particularly preferably, the weight ratio of 1: a combination of cyclohexane and hexane of 0.08 to 0.42 (e.g., 1: 0.1 to 0.42) as the second organic solvent. The amount of the second organic solvent used may vary within wide limits, for example, such that the total content of butadiene and styrene is from 10 to 15% by weight (based on the total weight of the second organic solvent, butadiene and styrene).
According to the present invention, preferably, the conditions of the second polymerization reaction include: the temperature is 50-100 deg.C (such as 70-90 deg.C, preferably 80-90 deg.C), and the time is 40-80min (such as 50-60 min).
According to the present invention, the second polymerization may be carried out by initiating styrene and butadiene together with an organolithium compound, or by first initiating polymerization of styrene in the presence of an organolithium compound (for example, polymerization at a temperature of 40 to 70 ℃ C., for example, 40 to 60 ℃ C., preferably 50 to 70 ℃ C., for 10 to 300min, preferably 15 to 40min), and then adding butadiene to carry out polymerization (for example, polymerization at a temperature of 50 to 100 ℃ C., for 30 to 60 min). The present invention is not particularly limited thereto, but it is to be understood that the former way may give a linear styrene-butadiene random copolymer or a mixture of linear styrene-butadiene random copolymer and linear styrene-butadiene block copolymer, and the latter way will give a linear block styrene-butadiene copolymer.
According to the present invention, in the step (B) of the process for preparing the linear styrene-butadiene copolymer, the product of the second polymerization reaction is terminated, and the terminated product (wherein the content of the linear styrene-butadiene copolymer may be, for example, 10 to 15 wt%) is coagulated and dried to obtain the linear styrene-butadiene copolymer (in a solid form). The termination, terminating agent, coagulation and drying are as described above and will not be described further herein.
The invention also provides a preparation method of the ABS resin, which comprises the following steps:
(1) preparing low cis-polybutadiene rubber; wherein the molecular weight of the low-cis polybutadiene rubber is in bimodal distribution, and the bimodal number average molecular weight is respectively in the range of 40000-75000 and in the range of 125000-250000;
(2) preparing a linear styrene-butadiene copolymer; wherein the number average molecular weight of the linear butylbenzene copolymer is 70000-200000;
(3) carrying out polymerization reaction on styrene, acrylonitrile and a toughening agent in the presence of a free radical initiator; wherein the toughening agent is a solution containing the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer.
According to the present invention, in step (1), the low-cis polybutadiene rubber is prepared, that is, after a polymerization solution of the low-cis polybutadiene rubber having a specific molecular weight and showing a bimodal distribution of the molecular weight is prepared by a conventional method in the art, the low-cis polybutadiene rubber is extracted (for example, by a coagulation method) and dried to obtain the low-cis polybutadiene rubber (in a solid form). Wherein, although the low-cis polybutadiene rubber with the molecular weight in the bimodal distribution prepared in the step (1) can be used as the component of the toughening agent for preparing the ABS resin, and the bimodal number average molecular weights are respectively in the range of 40000-75000 and 125000-250000, in order to obtain better improvement on the glossiness and the impact resistance of the ABS resin and better processing performance of the low-cis polybutadiene rubber in time, preferably, the bimodal number average molecular weight of the low-cis polybutadiene rubber is respectively in the range of 45000-65000 and 140000-210000 (more preferably 145000-210000).
More preferably, in the low-cis polybutadiene rubber, the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number average molecular weight in the range of 40000-75000 (preferably 45000-65000), the molecular weight distribution coefficient of the segment can be 1-1.2, to the content of the low-cis polybutadiene rubber in the range of 125000-250000 (preferably 140000-210000, more preferably 145000-210000), the molecular weight distribution coefficient of the segment can be 1-1.2, is 100: 150-: 250-1900, more preferably 100: 280-1600 (e.g., 100: 300-1600), more preferably 100: 500-. More preferably, the low-cis polybutadiene rubber has a vinyl side group content of 10 to 20 weight percent (based on the total weight of the low-cis polybutadiene rubber).
According to the present invention, although the low cis-polybutadiene rubber of the present invention is controlled within the above molecular weight and distribution range, a suitable 5% styrene solution viscosity and Mooney viscosity can be obtained, satisfying the requirements for the preparation of ABS resin. However, preferably, the Mooney viscosity of the low-cis polybutadiene rubber is 30 to 60 (preferably 35 to 55). Preferably, the low cis-polybutadiene rubber has a5 wt% styrene solution viscosity of 15-50cp (preferably 20-40 cp). The viscosity of a5 wt% styrene solution of the low-cis polybutadiene rubber is the viscosity of the resulting solution when the low-cis polybutadiene rubber is dissolved in styrene so that the concentration of the low-cis polybutadiene rubber is 5 wt% (the same is understood for the viscosity of a5 wt% styrene solution of the linear styrene-butadiene copolymer in the present invention).
According to the present invention, the low cis-polybutadiene rubber obtained in step (1) preferably has a low color and gel content, wherein the color is preferably 5 to 15APHA, preferably 5 to 10 APHA. The gel content is preferably 100ppm or less, more preferably 50ppm or less, for example, 20 to 50ppm, for example, 20 to 30ppm (the lower the gel content, the more advantageous the ABS resin having excellent properties can be obtained).
According to the present invention, the process for producing the low-cis polybutadiene rubber is not particularly limited as long as the low-cis polybutadiene rubber having the above characteristics can be obtained. Preferably, the process for preparing the low-cis polybutadiene rubber in the step (1) comprises:
(a) subjecting butadiene to a first polymerization reaction in a first organic solvent in the presence of an organolithium compound to a conversion of butadiene of 95 wt% or more (preferably 98 wt% or more, for example 99 wt% or more);
(b) carrying out a coupling reaction on the product of the first polymerization reaction in the presence of a coupling agent;
(c) and in the presence of a terminator, terminating the product of the coupling reaction, and coagulating and drying the terminated product to obtain the low cis-polybutadiene rubber.
According to the present invention, step (a), step (b) and step (c) of the polymerization reaction of butadiene are as described hereinbefore and will not be described herein again.
According to the present invention, in the step (2), a linear styrene-butadiene copolymer is prepared, that is, a polymerization solution of a linear styrene-butadiene copolymer having a specific molecular weight can be prepared by a conventional method in the art, and then the linear styrene-butadiene copolymer is extracted (for example, by a coagulation method) and dried to obtain a linear styrene-butadiene copolymer (in a solid form). Wherein, although the linear butylbenzene copolymer prepared in the step (2) and having a molecular weight within the range of 70000-. The molecular weight distribution coefficient of the linear styrene-butadiene copolymer may be, for example, 1 to 1.2.
Preferably, the weight ratio of the structural unit of styrene to the structural unit of butadiene in the linear styrene-butadiene copolymer is 1: 1-10, more preferably 1: 1.5 to 8, more preferably 1: 1.5-5, more preferably 1: 2.3-4. More preferably, the linear styrene-butadiene copolymer has a content of vinyl side groups of 8 to 10 wt% (based on the total weight of the linear styrene-butadiene copolymer).
According to the present invention, although the linear styrene-butadiene copolymer of the present invention is controlled within the above molecular weight and distribution range, a suitable 5% styrene solution viscosity can be obtained, satisfying the need for the preparation of ABS resin. However, it is preferable that the Mooney viscosity of the linear styrene-butadiene copolymer is 45 to 160 (preferably 60 to 130) and the viscosity of a5 wt% styrene solution thereof is 8 to 40cp (preferably 15 to 30 cp).
According to the present invention, preferably, the linear styrene-butadiene copolymer obtained in the step (2) has a low chroma and gel content, wherein the chroma is preferably 5 to 15APHA, preferably 5 to 10 APHA. The gel content is preferably 100ppm or less, more preferably 50ppm or less, for example, 10 to 50ppm, for example, 15 to 25ppm (the lower the gel content, the more favorable the ABS resin having excellent properties can be obtained).
According to the present invention, the process for preparing the above-mentioned linear styrene-butadiene copolymer is not particularly limited as long as the linear styrene-butadiene copolymer having the above-mentioned characteristics can be obtained. Preferably, the process for preparing the linear styrene-butadiene copolymer in the step (2) comprises:
(A) carrying out second polymerization reaction on butadiene and styrene in a second organic solvent in the presence of an organic lithium compound;
(B) and (3) terminating the product of the second polymerization reaction in the presence of a terminating agent, and condensing and drying the terminated product to obtain the linear styrene-butadiene copolymer (in a solid form).
According to the present invention, the steps (a) and (B) of the process for preparing the linear styrene-butadiene copolymer in the step (2) are as described above and will not be described herein again.
According to the invention, in the step (3) of the preparation method of the ABS resin, the toughening agent is a solution containing the low cis-polybutadiene rubber and the linear styrene-butadiene copolymer, so that the ABS resin is obtained by further free radical polymerization by using the toughening agent and matching with styrene and acrylonitrile. Preferably, in the toughening agent, the weight ratio of the low-cis polybutadiene rubber to the linear styrene-butadiene copolymer is 0.4-5: 1 (e.g., 0.4-4: 1), more preferably 0.43-2.3: 1, more preferably 0.67 to 1.5: 1.
in order to realize bulk polymerization of the ABS resin, the solvent content in the toughening agent needs to be relatively low, and the toughening agent is preferably used in an amount such that the solvent content is 18 wt% or less, more preferably 9 to 18 wt%, based on the total weight of styrene, acrylonitrile and the toughening agent. The solvent in the toughening agent is not particularly limited, and may be any of various solvents used in the art for preparing ABS resins, and preferably, the solvent is one or more benzene solvents selected from unsubstituted or C1-C4 alkyl substituted benzene. Among them, the C1-C4 alkyl group may be one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, etc., and the C1-C4 alkyl-substituted benzene as the benzene solvent may be one or more of single-point substituted or multi-point substituted, and preferably, the benzene solvent is one or more of toluene, ethylbenzene and xylene.
Under the condition that this condition is satisfied, preferably, the total content of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer in the solution containing the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer is 40 to 65 wt% (e.g., 40 to 55 wt%, 45 to 50 wt%, 45 to 60 wt%).
Under the condition that this condition is satisfied, the weight ratio of styrene, acrylonitrile and the toughening agent on a dry weight basis is preferably 400-1000: 100-400: 100, more preferably 500-: 140-350: 100 (e.g., 550-: 150-200: 100, more preferably 550-: 180-200: 100.
according to the present invention, the radical initiator may be various initiators conventionally used in the art for preparing ABS 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 of diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl peroxide and azobisnitrile type compounds, and still more preferably one or more of dibenzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, di-o-methylbenzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile. Preferably, the weight ratio of the total amount of styrene and acrylonitrile to the amount of the radical initiator is 2500-: 1, more preferably 3000-: 1 (e.g., 3000 + 10000: 1), more preferably 4000 + 10000: 1 (e.g., 5000-: 1.
according to the present invention, preferably, in the step (3), the polymerization conditions include: the temperature is 100-.
In another preferred embodiment of the present invention, in step (3), the polymerization conditions include: first reacting at 100-110 deg.C for 1-3h (such as 1.5-2.5h), then reacting at 115-125 deg.C for 1-3h (such as 1.5-2.5h), then reacting at 130-140 deg.C for 1-3h (such as 1.5-2.5h), and finally reacting at 145-155 deg.C for 1-3h (such as 1.5-2.5 h). More preferably, in step (3), the polymerization conditions include: firstly reacting at 110 ℃ for 1-2h, then reacting at 125 ℃ for 1-2h, then reacting at 135 ℃ for 1-2h, and finally reacting at 155 ℃ for 1-2 h.
The invention also provides the ABS resin prepared by the method.
Preferably, in the ABS resin of the present invention, the content of structural units of styrene is 60 to 72 wt.% (preferably 61 to 71.5 wt.%, more preferably 63 to 69 wt.%), the content of structural units of acrylonitrile is 15 to 30 wt.% (preferably 18 to 27 wt.%, more preferably 20 to 27 wt.%) (it is understood that the remaining content is mainly structural units provided by butadiene, for example 7 to 35 wt.%, preferably 8 to 20 wt.%), and the weight average molecular weight of the ABS resin is 150000-350000g/mol, more preferably 180000-300000g/mol, still more preferably 190000-295000 g/mol. The molecular weight distribution coefficient of the obtained ABS resin may be, for example, 2 to 3.
The method can prepare the ABS resin in a bulk polymerization mode, and the obtained ABS resin has high impact resistance and high glossiness. Preferably, I of the ABS resinzodThe impact strength is more than 200J/m, preferably more than 205J/m, more preferably more than 207J/m, more preferably more than 216J/m, still more preferably 250-400J/m, most preferably 280-390J/m, for example, can reach 314-382J/m; the 60 DEG gloss is 80 or more, preferably 81 or more, more preferably 83 or more, andpreferably 88 or more, most preferably 90 to 99.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the molecular weight and the molecular weight distribution coefficient were measured by the use of a gel permeation chromatograph, model HLC-8320 from Tosoh corporation, Japan. Wherein the ABS weight average molecular weight is obtained by dissolving ABS resin in toluene, centrifuging, collecting supernatant with ethanol, and measuring with HLC-8320 gel permeation chromatograph.
The content of each structural unit is determined by means of an AVANCEDRX model 400MHz nuclear magnetic resonance apparatus manufactured by BRUKER.
The branching area is the coupling peak area and is determined by HLC-8320 gel permeation chromatography. Izod impact strength is an Izod impact strength (23 ℃ C.), measured in accordance with ASTM D256 (J/m).
The 60 ℃ gloss is measured according to ASTM D526(60 ℃).
Mooney viscosity was measured by means of a Mooney viscometer without a rotor, model SMV-201SK-160, manufactured by Shimadzu corporation, Japan.
The viscosity of a 5% by weight solution of the polymer in styrene was measured thermostatically at 25 ℃ using a capillary viscometer; the chroma of the polymer is measured by a platinum-cobalt standard colorimetric method; the gel content of the polymer was determined gravimetrically (ratio of the weight of the residue after filtration through a 360 mesh screen to the amount of rubber used).
Example 1
This example is intended to illustrate the ABS resin of the present invention and the process for its preparation.
(1) 528g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 0.06g of tetrahydrofuran and 72g of butadiene were mixed, and 1.6mL of a hexane solution of n-butyllithium (1mol/L, the same applies hereinafter) was added at 50 ℃ and then reacted at 80 ℃ for 40min (conversion of butadiene was 99% by weight); then adding 2.1mL of hexane solution of silicon tetrachloride (0.2mol/L, the same applies below) to react for 20min at 70 ℃; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then, 0.1g of 1520 antioxidant (available from Ciba chemical Co., Ltd., Switzerland, the same shall apply hereinafter) and 0.1g of 1076 antioxidant (available from Ciba chemical Co., Ltd., the same shall apply hereinafter) were added, and the resultant polymer product was coagulated and dried; to give low cis polybutadiene rubber A1 (in solid form); wherein the low-cis polybutadiene rubber has a molecular weight bimodal distribution in which a portion having a number average molecular weight of 47000 accounts for 7% by weight, a molecular weight distribution coefficient of 1.04, a portion having a number average molecular weight of 150000 accounts for 93% by weight, a molecular weight distribution coefficient of 1.10, a vinyl side group content of 12.8% by weight, a Mooney viscosity of 39, a 5% by weight styrene solution thereof has a viscosity of 24.6cp, a color of 10APHA, a gel content of 45ppm, a branching area of 93%, and a cis 1, 4-polymerized butadiene structural unit content of 34.6% by weight;
(2) 516g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 25.2g of styrene and 58.8g of butadiene were mixed, and 0.7mL of an n-butyllithium hexane solution was added at 50 ℃ and then reacted at 80 ℃ for 60 min; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; linear butylbenzene copolymer B1 (solid form) is obtained; wherein the linear styrene-butadiene copolymer has a number average molecular weight of 144000, a molecular weight distribution coefficient of 1.06, a content of styrene structural units of 30.1 wt%, a content of butadiene structural units of 69.9 wt%, a content of vinyl side groups of 8.6 wt%, a Mooney viscosity of 126, a viscosity of a5 wt% styrene solution of 22.4cp, a chroma of 10APHA and a gel content of 38 ppm;
(3) 10.8g of low cis-polybutadiene rubber A1 and 10.8g of linear styrene-butadiene copolymer B1 are dissolved in 20g of ethylbenzene to obtain a toughening agent C1; the toughening agent C1 is mixed with 150g of styrene, 50g of acrylonitrile and 0.02g of dibenzoyl peroxide, and polymerized for 2 hours at 105 ℃, 2 hours at 120 ℃, 2 hours at 135 ℃ and 2 hours at 150 ℃, and the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvent, so that the ABS resin P1 is obtained.
Wherein the resin has a butadiene structural unit content of about 11.8 wt%, a styrene structural unit content of about 68.2 wt%, and an acrylonitrile structural unit content of about 20% by weight, the weight average molecular weight of the ABS resin is 265000g/mol, and the molecular weight distribution coefficient is 2.36; i of the ABS resinzodThe impact strength was 314J/m and the (60 ℃) gloss was 96.
Example 2
This example illustrates the ABS resin and the method of preparing the same according to the present invention.
(1) 528g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 0.06g of tetrahydrofuran and 72g of butadiene were mixed, and 1.3mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 90 ℃ for 40min (conversion of butadiene is 99% by weight); then adding 1.6mL of hexane solution of silicon tetrachloride to react for 20min at 70 ℃; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; to give low cis polybutadiene rubber A2 (in solid form); wherein the molecular weight of the low cis-polybutadiene rubber is bimodal, wherein the part with the number average molecular weight of 61000 accounts for 16 wt%, the molecular weight distribution coefficient is 1.06, the part with the number average molecular weight of 195000 accounts for 84 wt%, the molecular weight distribution coefficient is 1.11, the vinyl side group content is 12.9 wt%, the Mooney viscosity is 52, the viscosity of a5 wt% styrene solution thereof is 33.4cp, the chroma is 10APHA, the gel content is 37ppm, the branching area is 84%, and the content of cis-1, 4-polymerized butadiene structural units is 34.2 wt%;
(2) 516g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 21g of styrene and 63g of butadiene were mixed, and 0.7mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 80 ℃ for 60 min; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.5MPa for 15 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; linear butylbenzene copolymer B2 (solid form) is obtained; wherein the linear styrene-butadiene copolymer has a number average molecular weight of 151000, a molecular weight distribution coefficient of 1.07, a styrene structural unit content of 25.2 wt%, a butadiene structural unit content of 74.8 wt%, a vinyl side group content of 8.8 wt%, a Mooney viscosity of 103, a5 wt% styrene solution viscosity of 26.7cp, a chroma of 10APHA, and a gel content of 26 ppm;
(3) 9g of low cis-polybutadiene rubber A2 and 12g of linear styrene-butadiene copolymer B2 are dissolved in 20g of ethylbenzene to obtain a toughening agent C2; the toughening agent C2 is mixed with 150g of styrene, 60g of acrylonitrile and 0.02g of dibenzoyl peroxide, and polymerized for 2 hours at 105 ℃, 2 hours at 120 ℃, 2 hours at 135 ℃ and 2 hours at 150 ℃, and the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvents, so that the ABS resin P2 is obtained.
Wherein, in the resin, the content of the structural unit of butadiene is about 10.1 weight percent, the content of the structural unit of styrene is about 63.8 weight percent, the content of the structural unit of acrylonitrile is about 26.1 weight percent, the weight average molecular weight of the ABS resin is 294000g/mol, and the molecular weight distribution coefficient is 2.48; i of the ABS resinzodThe impact strength was 284J/m, and the gloss at 60 ℃ was 97.
Example 3
This example is intended to illustrate the ABS resin of the present invention and the process for its preparation.
(1) 528g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 0.06g of tetrahydrofuran and 72g of butadiene were mixed, and 1.4mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 80 ℃ for 40min (conversion of butadiene 98% by weight); then adding 1.8mL of hexane solution of silicon tetrachloride to react for 20min at 80 ℃; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.5MPa for 15 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; to give low cis polybutadiene rubber A3 (in solid form); wherein the molecular weight of the low cis-polybutadiene rubber is bimodal distribution, wherein the fraction with a number average molecular weight of 56000 accounts for 10 wt%, the molecular weight distribution coefficient is 1.06, the fraction with a number average molecular weight of 179000 accounts for 90 wt%, the molecular weight distribution coefficient is 1.09, the vinyl side group content is 12.4 wt%, the Mooney viscosity is 43, the viscosity of a5 wt% styrene solution thereof is 28.7cp, the chroma is 10APHA, the gel content is 34ppm, the branching area is 90%, and the content of cis 1, 4-polymerized butadiene structural units is 34.2 wt%;
(2) 516g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 17.5g of styrene and 66.5g of butadiene were mixed, and 0.65mL of an n-butyllithium hexane solution was added at 50 ℃ and then reacted at 90 ℃ for 60 min; introducing carbon dioxide into the reaction system at 60 deg.C under 0.2MPa for 20 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; linear butylbenzene copolymer B3 (solid form) is obtained; wherein the linear styrene-butadiene copolymer has a number average molecular weight of 158000, a molecular weight distribution coefficient of 1.06, a content of a styrene structural unit of 20.9 wt%, a content of a butadiene structural unit of 79.1 wt%, a content of a vinyl side group of 8.7 wt%, a Mooney viscosity of 84, a viscosity of a5 wt% styrene solution of 29.1cp, a chroma of 10APHA and a gel content of 17 ppm;
(3) dissolving 13.5g of low cis-polybutadiene rubber A3 and 13.5g of linear styrene-butadiene copolymer B3 in 20g of ethylbenzene to obtain a toughening agent C3; the toughening agent C3 is mixed with 150g of styrene, 50g of acrylonitrile and 0.02g of dibenzoyl peroxide, and polymerized for 1.5h at 105 ℃, 2.5h at 125 ℃, 2.5h at 135 ℃ and 1.5h at 155 ℃, and the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvent, so that the ABS resin P3 is obtained.
Wherein the resin has a butadiene structural unit content of about 13.5 wt%, a styrene structural unit content of about 66.1 wt%, an acrylonitrile structural unit content of about 20.4 wt%, an ABS resin weight average molecular weight of 225000g/mol, and a molecular weight distribution coefficient of 2.51; i of the ABS resinzodThe impact strength was 382J/m, and the (60 ℃) gloss was 90.
Example 4
This example is intended to illustrate the ABS resin of the present invention and the process for its preparation.
(1) 528g of a cyclohexane/hexane (weight ratio of 1: 0.2) mixed solvent, 0.05g of tetrahydrofuran and 72g of butadiene were mixed, and 1.5mL of a hexane solution of n-butyllithium was added at 40 ℃ and then reacted at 90 ℃ for 60min (conversion of butadiene is 99% by weight); then 2.6mL of a hexane solution of methyl silicon trichloride (0.2mol/L, the same applies below) was added and reacted at 80 ℃ for 30 min; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; to give low cis polybutadiene rubber A4 (in solid form); wherein the low-cis polybutadiene rubber has a bimodal distribution of molecular weight, wherein 6% by weight of a portion having a number average molecular weight of 51000, a molecular weight distribution coefficient of 1.05, 94% by weight of a portion having a number average molecular weight of 133000, a molecular weight distribution coefficient of 1.08, a vinyl side group content of 13.1% by weight, a Mooney viscosity of 42, a 5% by weight styrene solution thereof having a viscosity of 29.1cp, a chroma of 10APHA, a gel content of 46ppm, a branching area of 94%, and a cis-1, 4-polymerized butadiene structural unit content of 34.7% by weight;
(2) 516g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 28g of styrene and 56g of butadiene were mixed, and 0.7mL of a hexane solution of n-butyllithium was added at 40 ℃ and then reacted at 90 ℃ for 60 min; introducing carbon dioxide into the reaction system at 60 deg.C under 0.3MPa for 20 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; linear butylbenzene copolymer B4 (solid form) is obtained; wherein the linear styrene-butadiene copolymer has a number average molecular weight of 141000, a molecular weight distribution coefficient of 1.06, a styrene structural unit content of 33.5 wt%, a butadiene structural unit content of 66.5 wt%, a vinyl side group content of 8.6 wt%, a Mooney viscosity of 129, a5 wt% styrene solution viscosity of 29.7cp, a chroma of 10APHA, and a gel content of 23 ppm;
(3) 9g of low cis-polybutadiene rubber A4 and 10g of linear styrene-butadiene copolymer B4 are dissolved in 20g of ethylbenzene to obtain a toughening agent C4; the toughening agent C4 is mixed with 150g of styrene, 50g of acrylonitrile and 0.03g of tert-butyl peroxybenzoate, polymerized for 2 hours at 105 ℃, polymerized for 2 hours at 120 ℃ and polymerized for 4 hours at 150 ℃, and the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvent, so that the ABS resin P4 is obtained.
Wherein the resin has a butadiene structural unit content of about 8.6 wt%, a styrene structural unit content of about 67.2 wt%, an acrylonitrile structural unit content of about 24.2 wt%, an ABS resin weight average molecular weight of 194000g/mol, and a molecular weight distribution coefficient of 2.57; i of the ABS resinzodThe impact strength was 216J/m and the (60 ℃) gloss was 88.
Example 5
This example is intended to illustrate the ABS resin of the present invention and the process for its preparation.
(1) 528g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 0.06g of tetrahydrofuran and 72g of butadiene were mixed, and 1.3mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 80 ℃ for 40min (conversion of butadiene 98% by weight); then adding 1.5mL of hexane solution of silicon tetrachloride to react for 20min at 80 ℃; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; to give low cis polybutadiene rubber A5 (in solid form); wherein the molecular weight of the low-cis polybutadiene rubber is bimodal, wherein the proportion of 59000 number average molecular weight accounts for 16 wt%, the molecular weight distribution coefficient is 1.07, the proportion of 189000 number average molecular weight accounts for 84 wt%, the molecular weight distribution coefficient is 1.12, the content of vinyl side group is 13.6 wt%, the Mooney viscosity is 54, the viscosity of 5 wt% styrene solution is 34.7cp, the chroma is 10APHA, the gel content is 32ppm, the branching area is 84%, and the content of cis 1, 4-polymerized butadiene structural unit is 34.4 wt%;
(2) 516g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent and 17g of styrene were mixed, and 1mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 70 ℃ for 40 min; adding 67g of butadiene and continuing to react for 40 min; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; linear butylbenzene copolymer B5 (solid form) is obtained; wherein the linear styrene-butadiene copolymer has a number average molecular weight of 84000, a molecular weight distribution coefficient of 1.08, a content of styrene structural units of 20.3 wt%, a content of butadiene structural units of 79.7 wt%, a content of vinyl side groups of 8.3 wt%, a Mooney viscosity of 66, a viscosity of a5 wt% styrene solution of 15.3cp, a chroma of 10APHA and a gel content of 37 ppm;
(3) 9g of low cis-polybutadiene rubber A5 and 10g of linear styrene-butadiene copolymer B5 are dissolved in 20g of ethylbenzene to obtain a toughening agent C5; the toughening agent C5 is mixed with 150g of styrene, 55g of acrylonitrile and 0.02g of dibenzoyl peroxide, and polymerized for 2 hours at 105 ℃, 2 hours at 120 ℃, 2 hours at 135 ℃ and 2 hours at 150 ℃, and the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvents, so that the ABS resin P5 is obtained.
Wherein, in the resin, the content of the structural unit of butadiene is about 9.1 weight percent, the content of the structural unit of styrene is about 65.1 weight percent, the content of the structural unit of acrylonitrile is about 25.8 weight percent, the weight average molecular weight of the ABS resin is 242000g/mol, and the molecular weight distribution coefficient is 2.44; i of the ABS resinzodThe impact strength was 207J/m, and the (60 ℃) gloss was 88.
Example 6
This example is intended to illustrate the ABS resin of the present invention and the process for its preparation.
(1) 528g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 0.06g of tetrahydrofuran and 72g of butadiene were mixed, and 1.1mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 80 ℃ for 40min (conversion of butadiene 98% by weight); then adding 1.2mL of hexane solution of silicon tetrachloride to react for 20min at 80 ℃; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; to give low cis polybutadiene rubber A6 (in solid form); wherein the low-cis polybutadiene rubber has a bimodal distribution of molecular weight, wherein the fraction having a number average molecular weight of 69000 accounts for 26 wt%, the molecular weight distribution coefficient is 1.05, the fraction having a number average molecular weight of 221000 accounts for 74 wt%, the molecular weight distribution coefficient is 1.08, the vinyl side group content is 13.8 wt%, the Mooney viscosity is 54, the viscosity of a5 wt% styrene solution thereof is 42.8cp, the chroma is 15APHA, the gel content is 48ppm, the branching area is 74%, and the content of cis-1, 4-polymerized butadiene structural units is 35.1 wt%;
(2) mixing 516g of cyclohexane/hexane (weight ratio is 1: 0.2) mixed solvent, 14g of styrene and 70g of butadiene, adding 1.2mL of n-butyllithium hexane solution at 50 ℃, reacting for 60min at 80 ℃, and introducing carbon dioxide into the reaction system at 60 ℃, wherein the pressure is 0.3MPa and the time is 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; linear butylbenzene copolymer B6 (solid form) is obtained; wherein the linear styrene-butadiene copolymer has a number average molecular weight of 75000, a molecular weight distribution coefficient of 1.07, a styrene structural unit content of 16.8 wt%, a butadiene structural unit content of 83.2 wt%, a vinyl side group content of 8.5 wt%, a Mooney viscosity of 46, a5 wt% styrene solution viscosity of 8.3cp, a chroma of 15APHA, and a gel content of 88 ppm;
(3) dissolving 20g of low cis-polybutadiene rubber A6 and 15g of linear styrene-butadiene copolymer B6 in 20g of ethylbenzene to obtain a toughening agent C6; mixing the toughening agent C6 with 140g of styrene, 50g of acrylonitrile and 0.02g of dibenzoyl peroxide, polymerizing at 105 ℃ for 2h, 120 ℃ for 2h, 135 ℃ for 2h and 150 ℃ for 2h, and carrying out vacuum flash evaporation on a reaction product to remove unreacted monomers and a solvent to obtain the ABS resin P5.
Wherein the resin has a butadiene structural unit content of about 17.6 wt%, a styrene structural unit content of about 61.8 wt%, and an acrylonitrile structural unit content of about 20.6 wt%, and the ABS resin has a weight average molecular weight of 339000g/mol and a molecular weight distribution coefficient of 2.68; i of the ABS resinzodThe impact strength was 374J/m and the (60 ℃) gloss was 81.
Example 7
This example is intended to illustrate the ABS resin of the present invention and the process for its preparation.
(1) 528g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 0.06g of tetrahydrofuran and 72g of butadiene were mixed, and 1.8mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 80 ℃ for 40min (conversion of butadiene is 99% by weight); then adding 2.3mL of silicon tetrachloride hexane solution to react for 20min at 80 ℃; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; to give low cis polybutadiene rubber A7 (in solid form); wherein the low cis-polybutadiene rubber has a bimodal distribution of molecular weight, wherein the fraction having a number average molecular weight of 41000 accounts for 4 wt%, the molecular weight distribution coefficient is 1.05, the fraction having a number average molecular weight of 131000 accounts for 96 wt%, the molecular weight distribution coefficient is 1.08, the vinyl side group content is 12.4 wt%, the Mooney viscosity is 36, the viscosity of a5 wt% styrene solution thereof is 42.8cp, the chroma is 15APHA, the gel content is 48ppm, the branching area is 96%, and the content of cis 1, 4-polymerized butadiene structural units is 34.8 wt%;
(2) 516g of a cyclohexane/hexane (weight ratio: 1: 0.2) mixed solvent, 32g of styrene and 52g of butadiene were mixed, and 0.5mL of a hexane solution of n-butyllithium was added at 50 ℃ and then reacted at 80 ℃ for 60 min; introducing carbon dioxide into the reaction system at 60 ℃ under the pressure of 0.3MPa for 10 min; then 0.1g of 1520 antioxidant and 0.1g of 1076 antioxidant were added, and the resultant polymerization product was coagulated and dried; linear butylbenzene copolymer B7 (solid form) is obtained; wherein the linear styrene-butadiene copolymer has a number average molecular weight of 179000, a molecular weight distribution coefficient of 1.06, a styrene structural unit content of 38.3 wt%, a butadiene structural unit content of 61.7 wt%, a vinyl side group content of 9.1 wt%, a Mooney viscosity of 155, a5 wt% styrene solution viscosity of 36.8cp, a chroma of 15APHA and a gel content of 88 ppm;
(3) 9g of low cis-polybutadiene rubber A7 and 9g of linear styrene-butadiene copolymer B7 are dissolved in 20g of ethylbenzene to obtain a toughening agent C7; the toughening agent C7 is mixed with 160g of styrene, 50g of acrylonitrile and 0.04g of dibenzoyl peroxide, and polymerized for 2 hours at 105 ℃, 3 hours at 135 ℃ and 3 hours at 150 ℃, and the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvent, so that the ABS resin P5 is obtained.
Wherein the resin has a butadiene structural unit content of about 9.2 wt%, a styrene structural unit content of about 71.1 wt%, an acrylonitrile structural unit content of about 19.7 wt%, an ABS resin weight average molecular weight of 186000g/mol, and a molecular weight distribution coefficient of 2.72; i of the ABS resinzodThe impact strength was 205J/m, and the gloss at 60 ℃ was 83.
Comparative example 1
The process of example 1 was followed except that the toughening agent used was only an ethylbenzene solution of low cis polybutadiene rubber A1, i.e., 21.6g of low cis polybutadiene rubber A1 was dissolved in 20g of ethylbenzene as the toughening agent, and the amount of styrene used in step (3) was increased to 155g, thereby obtaining an ABS resin DP1 after vacuum flash evaporation to remove unreacted monomers and solvents, the resin having a butadiene structural unit content of about 12.3 wt%, a styrene structural unit content of about 68.1 wt%, an acrylonitrile structural unit content of about 19.6 wt%, a weight average molecular weight of 297000g/mol, and a molecular weight distribution coefficient of 2.48; i of the ABS resinzodThe impact strength was 268J/m and the (60 ℃) gloss was 78.
Comparative example 2
The method of example 1, except that the toughening agent used was only an ethylbenzene solution of the linear styrene-butadiene copolymer B1, i.e., 21.6g of the linear styrene-butadiene copolymer B1 was dissolved in 20g of ethylbenzene as the toughening agent, and the amount of styrene used in step (3) was reduced to 145g, thereby obtaining an ABS resin DP2 by vacuum flash evaporation and removal of unreacted monomers and solvents, in which the content of butadiene structural units was about 11.4 wt%, the content of styrene structural units was about 68.8 wt%, the content of acrylonitrile structural units was about 19.8 wt%, the weight average molecular weight of the ABS resin was 235000g/mol, and the molecular weight distribution coefficient was 2.51; i of the ABS resinzodThe impact strength was 184J/m, and the (60 ℃) gloss was 89.
Comparative example 3
According to the method of example 1, except that no silicon tetrachloride is added in the step (1), the coupling reaction is carried out, so that low cis-polybutadiene rubber DA1 is obtained; the molecular weight of the low cis-polybutadiene rubber in the solution is unimodal distribution, wherein the number average molecular weight is 47000, and the molecular weight distribution coefficient is 1.07;
DA1 is adopted to replace A1 in the preparation of the toughening agent; thus, the ABS resin DP3 was finally obtained. In the resin, the content of a structural unit of butadiene is about 11.6 wt%, the content of a structural unit of styrene is about 68.1 wt%, the content of a structural unit of acrylonitrile is about 20.3 wt%, the weight average molecular weight of the ABS resin is 308000g/mol, and the molecular weight distribution coefficient is 2.58; i of the ABS resinzodThe impact strength was 196J/m and the (60 ℃) gloss was 92.
Comparative example 4
The process as described in example 1, except that, in the step (1), the amount of the n-butyllithium solution added in hexane was 2.5mL, and the amount of the silicon tetrachloride solution added in hexane was 3.1 mL; wherein the molecular weight of the low-cis polybutadiene rubber is bimodal, wherein the part with the number average molecular weight of 31000 accounts for 8 wt%, the molecular weight distribution coefficient is 1.05, the part with the number average molecular weight of 99000 accounts for 92 wt%, the molecular weight distribution coefficient is 1.08, the vinyl side group content is 12.4 wt%, the Mooney viscosity is 17, the viscosity of a5 wt% styrene solution thereof is 8cp, the chroma is 10APHA, the gel content is 134ppm, the branching area is 92%, and the content of cis 1, 4-polymerized butadiene structural units is 34.6 wt%;
DA2 is adopted to replace A1 in the preparation of the toughening agent; thus, the ABS resin DP4 was finally obtained. In the resin, the content of a structural unit of butadiene was about 11.2% by weight, the content of a structural unit of styrene was about 68.4% by weight, the content of a structural unit of acrylonitrile was about 20.4% by weight, the weight average molecular weight of the ABS resin was 247000g/mol, and the molecular weight distribution coefficient was 2.49; i of the ABS resinzodThe impact strength was 188J/m and the (60 ℃) gloss was 84.
Comparative example 5
The process as described in example 1, except that, in the step (1), the amount of the n-butyllithium hexane solution added was 1mL, and the amount of the silicon tetrachloride hexane solution added was 1.3 mL; wherein the low-cis polybutadiene rubber has a bimodal distribution of molecular weight, wherein the fraction having a number average molecular weight of 91000 constitutes 7% by weight, the molecular weight distribution coefficient is 1.09, the fraction having a number average molecular weight of 291000 constitutes 93% by weight, the molecular weight distribution coefficient is 1.12, the vinyl side group content is 13.1% by weight, the Mooney viscosity is 84, the viscosity of a 5% by weight styrene solution thereof is 144cp, the chroma is 10APHA, the gel content is 146ppm, the branching area is 93%, and the cis-1, 4-polymerized butadiene structural unit content is 34.5% by weight;
DA3 is adopted to replace A1 in the preparation of the toughening agent; thus, the ABS resin DP5 was finally obtained. The resin had a butadiene structural unit content of about 11.3 wt%, a styrene structural unit content of about 68.5 wt%, and an acrylonitrile structural unit content of about 20.2 wt%, and the ABS resin had a weight average molecular weight of 188000g/mol and a molecular weight distribution coefficient of 2.48; i of the ABS resinzodThe impact strength was 268J/m and the (60 ℃) gloss was 78.
Comparative example 6
The process as described in example 1, except that, in the step (2), 1.9mL of a hexane solution of n-butyllithium was added, the number average molecular weight of the linear styrene-butadiene copolymer was 49000, the molecular weight distribution coefficient was 1.05, the content of styrene structural units was 30.1% by weight, the content of butadiene structural units was 69.9% by weight, the content of vinyl side groups was 8.8% by weight, the Mooney viscosity was 44, and a 5% by weight styrene solution thereof had a viscosity of 11cp, a color of 10APHA and a gel content of 136 ppm;
DB1 is adopted to replace B1 in the preparation of the toughening agent; thus, the ABS resin DP6 was finally obtained. In the resin, the content of a butadiene structural unit is about 11.6 weight percent, the content of a styrene structural unit is about 68.1 weight percent, the content of an acrylonitrile structural unit is about 20.3 weight percent, the weight average molecular weight of the ABS resin is 273000g/mol, and the molecular weight distribution coefficient is 2.66; i of the ABS resinzodThe impact strength was 194J/m and the (60 ℃) gloss was 83.
Comparative example 7
The process of example 1, except that, in the step (2), 0.5mL of a hexane solution of n-butyllithium was added, the linear styrene-butadiene copolymer had a number average molecular weight of 246000 and a molecular weight distribution coefficient of 1.10, the content of styrene structural units was 30.1% by weight, the content of butadiene structural units was 69.9% by weight, the content of vinyl side groups was 8.2% by weight, the Mooney viscosity exceeded the Mooney test upper limit and could not be detected, and the 5% by weight styrene solution had a viscosity of 54cp, a color of 15APHA and a gel content of 228 ppm;
DB2 is adopted to replace B1 in the preparation of the toughening agent; thus, the ABS resin DP7 was finally obtained. The resin had a butadiene structural unit content of about 11.7 wt%, a styrene structural unit content of about 68.4 wt%, and an acrylonitrile structural unit content of about 19.9 wt%, and the ABS resin had a weight average molecular weight of 224000g/mol and a molecular weight distribution coefficient of 2.78; i of the ABS resinzodThe impact strength was 174J/m, and the gloss at 60 ℃ was 86.
It can be seen from the comparison between the above examples and comparative examples that, in the method of the present invention, the low cis-polybutadiene rubber with a specific molecular weight and bimodal distribution and the linear styrene-butadiene copolymer with a specific molecular weight are used in combination as the toughening agent component for preparing the ABS resin, so that the toughening agent can maintain appropriate solution viscosity and molecular weight distribution, the problem that the impact resistance and the gloss of the existing preparation method of the ABS resin cannot be considered at the same time is overcome, and the ABS resin with higher impact resistance and higher gloss is obtained. For example, as can be seen from a comparison of example 1 with comparative examples 1 and 2, the toughening agent composition of the present invention requires a coordination between the low cis polybutadiene rubber and the linear styrene-butadiene copolymer to obtain an ABS resin with higher impact resistance and higher gloss; as can be seen from the comparison of example 1 with comparative examples 3 to 7, ABS resins having both higher impact properties and gloss can be obtained only when the molecular weights of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer satisfy the requirements of the toughening agent composition of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (159)
1. A toughening agent composition, which is characterized by comprising low-cis polybutadiene rubber and a linear styrene-butadiene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber is in bimodal distribution, and the bimodal number average molecular weight is respectively in the range of 40000-75000 and 125000-250000; the number average molecular weight of the linear butylbenzene copolymer is 70000-200000.
2. The composition of claim 1 wherein the weight ratio of low-cis polybutadiene rubber to linear styrene-butadiene copolymer is 0.4-5: 1.
3. the composition of claim 2 wherein the weight ratio of low-cis polybutadiene rubber to linear styrene-butadiene copolymer is 0.4-4: 1.
4. the composition of claim 3, wherein the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer is 0.43-2.3: 1.
5. the composition of claim 4, wherein the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer is 0.67-1.5: 1.
6. the composition as claimed in any one of claims 2 to 5, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 40000-75000 to the content of the low-cis polybutadiene rubber in the range of 125000-250000 is 100: 150-2000.
7. The composition as claimed in claim 6, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 45000-65000 to the content of the low-cis polybutadiene rubber in the range of 140000-210000 is 100: 200-2000.
8. The composition as claimed in claim 6, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 40000-75000 to the content of the low-cis polybutadiene rubber in the range of 125000-250000 is 100: 250-1900.
9. The composition as claimed in claim 8, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 40000-75000 to the content of the low-cis polybutadiene rubber in the range of 125000-250000 is 100: 280-1600.
10. The composition as claimed in claim 9, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 40000-75000 to the content of the low-cis polybutadiene rubber in the range of 125000-250000 is 100: 500-1570.
11. The composition of any of claims 2-5 and 7-10, wherein the low-cis polybutadiene rubber has a vinyl side group content of 10-20 wt%.
12. The composition of any of claims 2-5, 7-10, wherein the low-cis polybutadiene rubber is a coupled polymer with a branching area of 70-95%.
13. The composition of claim 12, wherein the branching area is 75-95%.
14. The composition of any of claims 2-5 and 7-10, wherein the low cis polybutadiene rubber has a5 wt% styrene solution viscosity of 15-50 cp.
15. The composition of claim 14 wherein the low cis polybutadiene rubber has a5 wt% styrene solution viscosity of 20-40 cp.
16. The composition as claimed in any one of claims 2-5 and 7-10, wherein the number average molecular weight of the linear styrene-butadiene copolymer is 80000-: 1-10.
17. The composition of claim 16, wherein the weight ratio of structural units of styrene and structural units of butadiene in the linear styrene-butadiene copolymer is 1: 1.5-8.
18. The composition of claim 17, wherein the weight ratio of structural units of styrene and structural units of butadiene in the linear styrene-butadiene copolymer is 1: 1.5-5.
19. The composition of claim 18, wherein the weight ratio of structural units of styrene and structural units of butadiene in the linear styrene-butadiene copolymer is 1: 2.3-4.
20. The composition of any of claims 2-5 and 7-10, wherein the linear styrene-butadiene copolymer has a vinyl side group content of 8-10 wt%.
21. The composition of any of claims 2-5 and 7-10, wherein the linear styrene-butadiene copolymer has a5 wt% styrene solution viscosity of 8-40 cp.
22. The composition of claim 21, wherein the viscosity of a5 wt% styrene solution of the linear styrene-butadiene copolymer is 15-30 cp.
23. The composition of claim 1 or 2, wherein the process for preparing the low-cis polybutadiene rubber comprises:
(a) subjecting butadiene to a first polymerization reaction in a first organic solvent in the presence of an organolithium compound until the conversion of butadiene is 95 wt% or more;
(b) carrying out a coupling reaction on the product of the first polymerization reaction in the presence of a coupling agent;
(c) and in the presence of a terminator, terminating the product of the coupling reaction, and coagulating and drying the terminated product to obtain the low cis-polybutadiene rubber.
24. The composition of claim 23, wherein the coupling agent is one or more of silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, 1, 8-dibromooctane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane.
25. The composition of claim 24, wherein the coupling agent is silicon tetrachloride and/or methyltrichlorosilane.
26. The composition of claim 23Wherein, in step (a), the organolithium compound is of formula R1A compound represented by Li, wherein R1Selected from C1-C10 alkyl groups.
27. The composition of claim 26, wherein the organolithium compound is one or more of n-butyllithium, sec-butyllithium, iso-butyllithium, and tert-butyllithium.
28. The composition of claim 27, wherein the organolithium compound is n-butyllithium and/or sec-butyllithium.
29. The composition of claim 23, wherein in step (a), the first organic solvent is one or more of an alkane solvent.
30. The composition of claim 29, wherein the first organic solvent is one or more of a C5-C10 paraffinic solvent and a C5-C10 naphthenic solvent.
31. The composition of claim 30, wherein the first organic solvent is one or more of hexane, cyclohexane, pentane, heptane, and isooctane.
32. The composition of claim 23, wherein in step (a), the conditions of the first polymerization reaction comprise: the temperature is 50-100 ℃; the time is 30-80 min.
33. The composition of claim 32, wherein the conditions of the first polymerization reaction comprise: the temperature is 70-90 ℃; the time is 40-60 min.
34. The composition of claim 23, wherein in step (b), the conditions of the coupling reaction comprise: the temperature is 60-80 deg.C, and the time is 20-40 min.
35. The composition as claimed in claim 23, wherein, in step (a) of the process for preparing low-cis polybutadiene rubber, the molar ratio of butadiene to the organolithium compound is 700-: 1.
36. the composition as claimed in claim 35, wherein the molar ratio of butadiene to the organolithium compound is 740-1250: 1.
37. the composition as claimed in claim 36, wherein the molar ratio of butadiene to the organolithium compound is 830-1200: 1.
38. the composition of claim 35, wherein the first organic solvent is present in a weight ratio of 1: a combination of cyclohexane and hexane of 0.08-0.5.
39. The composition of claim 35, wherein the first organic solvent is used in an amount such that the butadiene content is 10-15 wt%.
40. The composition according to claim 35, wherein in step (a) of the process for preparing low-cis polybutadiene rubber, the first polymerization reaction is further carried out in the presence of a structure-modifying agent, the structure-modifying agent being one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol C1-C4 alkyl ether and diethylene glycol di-C1-C4 alkyl ether.
41. A composition according to claim 40, wherein the structure modifier 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl ether.
42. The composition of claim 41, wherein the structure modulator is tetrahydrofuran.
43. The composition of claim 35, wherein the molar ratio of the amount of the structure-modifying agent to the amount of the organolithium compound is from 0.05 to 5: 1.
44. the composition of claim 43, wherein the molar ratio of the amount of the structure-modifying agent to the amount of the organolithium compound is from 0.1 to 4: 1.
45. the composition of claim 44, wherein the molar ratio of the amount of the structure-modifying agent to the amount of the organolithium compound is from 0.1 to 1: 1.
46. the composition of claim 45, wherein the molar ratio of the amount of the structure-modifying agent to the amount of the organolithium compound is from 0.4 to 0.8: 1.
47. the composition of claim 46, wherein the molar ratio of the amount of the structure-modifying agent to the amount of the organolithium compound is from 0.5 to 0.7: 1.
48. the composition as claimed in claim 35, wherein, in step (b) of the process for preparing a low-cis polybutadiene rubber, the molar ratio between the amount of the coupling agent and the amount of the organolithium compound is from 0.15 to 0.5: 1.
49. the composition of claim 48, wherein the molar ratio of the amount of coupling agent to the amount of organolithium compound is from 0.16 to 0.4: 1.
50. the composition of claim 49, wherein the molar ratio of the amount of coupling agent to the amount of organolithium compound is from 0.2 to 0.4: 1.
51. the composition of claim 50, wherein the molar ratio of the amount of coupling agent to the amount of organolithium compound is from 0.2 to 0.35: 1.
52. the composition of claim 1 or 2, wherein the preparation method of the linear styrene-butadiene copolymer comprises:
(A) carrying out second polymerization reaction on butadiene and styrene in a second organic solvent in the presence of an organic lithium compound;
(B) and in the presence of a terminator, terminating the product of the second polymerization reaction, and condensing and drying the terminated product to obtain the linear styrene-butadiene copolymer.
53. The composition of claim 52, wherein in step (A), the organolithium compound is of formula R1A compound represented by Li, wherein R1Selected from C1-C10 alkyl groups.
54. The composition of claim 53, wherein the organolithium compound is one or more of n-butyllithium, sec-butyllithium, iso-butyllithium, and tert-butyllithium.
55. The composition of claim 54, wherein the organolithium compound is n-butyllithium and/or sec-butyllithium.
56. The composition of claim 52, wherein in step (A), the second organic solvent is one or more of an alkane solvent.
57. The composition of claim 56, wherein the second organic solvent is one or more of a C5-C10 paraffinic solvent and a C5-C10 naphthenic solvent.
58. The composition of claim 57, wherein the second organic solvent is one or more of hexane, cyclohexane, pentane, heptane, and isooctane.
59. The composition of claim 52, wherein in step (A), the conditions of the second polymerization reaction comprise: the temperature is 50-100 ℃; the time is 40-80 min.
60. The composition of claim 59, wherein the conditions of the second polymerization reaction comprise: the temperature is 70-90 ℃; the time is 50-60 min.
61. The composition as claimed in claim 52, wherein, in the step (A) of the process for preparing a linear styrene-butadiene copolymer, the molar ratio of the total amount of butadiene and styrene to the organolithium compound is 1000-3000: 1.
62. the composition of claim 61, wherein the molar ratio of the total amount of butadiene and styrene used to the organolithium compound is 1100-2800: 1.
63. the composition as claimed in claim 62, wherein the molar ratio of the total amount of butadiene and styrene used to the organolithium compound is 1190-: 1.
64. the composition as claimed in claim 63, wherein the molar ratio of the total amount of butadiene and styrene used to the organolithium compound is 1400-2200: 1.
65. the composition of claim 61, wherein the second organic solvent is present in a weight ratio of 1: a combination of cyclohexane and hexane of 0.08-0.42.
66. The composition of claim 61, wherein the second organic solvent is used in an amount such that the total content of butadiene and styrene is from 10 to 15 wt%.
67. A method for preparing an ABS resin, which is characterized by comprising the following steps:
(1) preparing low cis-polybutadiene rubber; wherein the molecular weight of the low-cis polybutadiene rubber is in bimodal distribution, and the bimodal number average molecular weight is respectively in the range of 40000-75000 and in the range of 125000-250000;
(2) preparing a linear styrene-butadiene copolymer; wherein the number average molecular weight of the linear butylbenzene copolymer is 70000-200000;
(3) carrying out polymerization reaction on styrene, acrylonitrile and a toughening agent in the presence of a free radical initiator; wherein the toughening agent is a solution containing the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer.
68. The process as claimed in claim 67, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 40000-75000 to the content of the low-cis polybutadiene rubber in the range of 125000-250000 is 100: 200-2000.
69. The process as claimed in claim 68, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 45000-65000 to the content of the low-cis polybutadiene rubber in the range of 140000-210000 is 100: 250-1900.
70. The process as claimed in claim 68, wherein the weight ratio of the content of the low-cis polybutadiene rubber with bimodal number-average molecular weight in the range of 40000-75000 to the content of the low-cis polybutadiene rubber in the range of 125000-250000 is 100: 280-1600.
71. The process as claimed in claim 70, wherein the weight ratio of the content of the low-cis polybutadiene rubber with a bimodal number-average molecular weight in the range of 40000-75000 to the content of the low-cis polybutadiene rubber in the range of 125000-250000 is 100: 500-1570.
72. The method of claim 68 wherein the low-cis polybutadiene rubber has a vinyl side group content of 10-20 wt%.
73. The method of claim 68, wherein said low-cis polybutadiene rubber has a Mooney viscosity of 30-60 and a5 wt.% styrene solution viscosity of 15-50 cp.
74. The method of claim 73, wherein the 5 wt.% styrene solution has a viscosity of 20-40 cp.
75. The process of any one of claims 67-74, wherein the process for preparing low-cis polybutadiene rubber in step (1) comprises:
(a) subjecting butadiene to a first polymerization reaction in a first organic solvent in the presence of an organolithium compound until the conversion of butadiene is 95 wt% or more;
(b) carrying out a coupling reaction on the product of the first polymerization reaction in the presence of a coupling agent;
(c) and in the presence of a terminator, terminating the product of the coupling reaction, and coagulating and drying the terminated product to obtain the low cis-polybutadiene rubber.
76. The method as claimed in claim 75, wherein, in step (a) of the process for preparing low-cis polybutadiene rubber, the molar ratio of butadiene to the organolithium compound is 700-: 1.
77. the process as claimed in claim 76, wherein the molar ratio of butadiene to the organolithium compound is 740-1250: 1.
78. the method as claimed in claim 77, wherein the molar ratio of butadiene to the organolithium compound is 830-1200: 1.
79. the method of claim 76, wherein the organolithium compound is of formula R1Shown as LiWherein R is1Selected from C1-C10 alkyl groups.
80. The method of claim 79, wherein the organolithium compound is one or more of n-butyllithium, sec-butyllithium, iso-butyllithium, and tert-butyllithium.
81. The method of claim 80, wherein the organolithium compound is n-butyllithium and/or sec-butyllithium.
82. The process of claim 75, wherein in step (a) of the process for preparing low-cis polybutadiene rubber, the first organic solvent is one or more of an alkane solvent.
83. The method of claim 82, wherein the first organic solvent is one or more of a C5-C10 paraffinic solvent and a C5-C10 naphthenic solvent.
84. The method of claim 83, wherein the first organic solvent is one or more of hexane, cyclohexane, pentane, heptane, and isooctane.
85. The method of claim 84, wherein the first organic solvent is present in a weight ratio of 1: a combination of cyclohexane and hexane of 0.08-0.5.
86. A process as claimed in claim 82, in which the first organic solvent is used in an amount such that the butadiene content is from 10 to 15% by weight.
87. The method of claim 82, wherein the conditions of the first polymerization reaction comprise: the temperature is 50-100 ℃; the time is 30-80 min.
88. The method of claim 87, wherein the conditions of the first polymerization reaction comprise: the temperature is 70-90 ℃; the time is 40-60 min.
89. The process of claim 82, wherein in step (a) of the process for preparing low-cis polybutadiene rubber, the first polymerization reaction is further carried out in the presence of a structural regulator, the structural regulator being one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol C1-C4 alkyl ether, and diethylene glycol di-C1-C4 alkyl ether.
90. A process according to claim 89, wherein the structure modifier 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl ether.
91. The method of claim 90, wherein the structure modulator is tetrahydrofuran.
92. The method of claim 89, wherein the molar ratio of the amount of the structure modifier to the amount of the organolithium compound is from 0.05 to 5: 1.
93. the method of claim 92, wherein the molar ratio of the amount of the structure modifier to the amount of the organolithium compound is from 0.1 to 4: 1.
94. the method of claim 93, wherein the molar ratio of the amount of the structure modifier to the amount of the organolithium compound is from 0.1 to 1: 1.
95. the method of claim 94, wherein the molar ratio of the amount of the structure-modifying agent to the amount of the organolithium compound is from 0.4 to 0.8: 1.
96. the method of claim 95, wherein the molar ratio of the amount of the structure modifier to the amount of the organolithium compound is from 0.5 to 0.7: 1.
97. the method according to claim 75, wherein in step (b) of the process of preparing the low-cis polybutadiene rubber, the coupling agent is one or more of silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, 1, 8-dibromooctane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane.
98. The method of claim 97, wherein the coupling agent is silicon tetrachloride and/or methyltrichlorosilane.
99. The process of claim 97, wherein the molar ratio of the amount of coupling agent to the amount of organolithium compound is from 0.15 to 0.5: 1.
100. the process of claim 99, wherein the molar ratio of the amount of coupling agent to the amount of organolithium compound is from 0.16 to 0.4: 1.
101. the process of claim 100, wherein the molar ratio of the amount of coupling agent to the amount of organolithium compound is from 0.2 to 0.4: 1.
102. the process of claim 101, wherein the molar ratio of the amount of coupling agent to the amount of organolithium compound is from 0.2 to 0.35: 1.
103. the method of claim 97, wherein the conditions of the coupling reaction comprise: the temperature is 60-80 deg.C, and the time is 20-40 min.
104. The method of any of claims 67-74 and 76-103 wherein the linear styrene-butadiene copolymer has a number average molecular weight of 80000-: 1-10.
105. The method of claim 104, wherein the weight ratio of structural units of styrene to structural units of butadiene in the linear styrene-butadiene copolymer is 1: 1.5-8.
106. The method of claim 105, wherein the weight ratio of structural units of styrene to structural units of butadiene in the linear styrene-butadiene copolymer is 1: 1.5-5.
107. The method of claim 106, wherein the weight ratio of structural units of styrene to structural units of butadiene in the linear styrene-butadiene copolymer is 1: 2.3-4.
108. The method of claim 104, wherein the linear styrene-butadiene copolymer has a vinyl pendant group content of 8-10 wt%.
109. The method of claim 104, wherein the linear styrene-butadiene copolymer has a5 wt% styrene solution viscosity of 8-40 cp.
110. The method of claim 109, wherein the linear styrene-butadiene copolymer has a5 wt% styrene solution viscosity of 15-30 cp.
111. The method of claim 67, wherein the step (2) of preparing the linear styrene-butadiene copolymer comprises:
(A) carrying out second polymerization reaction on butadiene and styrene in a second organic solvent in the presence of an organic lithium compound;
(B) and in the presence of a terminator, terminating the product of the second polymerization reaction, and condensing and drying the terminated product to obtain the linear styrene-butadiene copolymer.
112. The method of claim 104, wherein the preparing of the linear styrene-butadiene copolymer in step (2) comprises:
(A) carrying out second polymerization reaction on butadiene and styrene in a second organic solvent in the presence of an organic lithium compound;
(B) and in the presence of a terminator, terminating the product of the second polymerization reaction, and condensing and drying the terminated product to obtain the linear styrene-butadiene copolymer.
113. The process of claim 111 or 112, wherein the conditions of the second polymerization reaction comprise: the temperature is 50-100 ℃; the time is 40-80 min.
114. The process of claim 113, wherein the conditions of the second polymerization reaction comprise: the temperature is 70-90 ℃; the time is 50-60 min.
115. The method as claimed in claim 111 or 112, wherein, in the step (a) of the process for preparing the linear styrene-butadiene copolymer, the molar ratio of the total amount of butadiene and styrene to the organolithium compound is 1000-3000: 1.
116. the process as claimed in claim 115, wherein the molar ratio of the total amount of butadiene and styrene used to the organolithium compound is 1100-2800: 1.
117. the process as claimed in claim 116, wherein the molar ratio of the total amount of butadiene and styrene to the organolithium compound is 1190-: 1.
118. the process as claimed in claim 117, wherein the molar ratio of the total amount of butadiene and styrene used to the organolithium compound is 1400-2200: 1.
119. the method of claim 115 wherein the organolithium compound is of formula R1A compound represented by Li, wherein R1Selected from C1-C10 alkyl groups.
120. The method of claim 119, wherein the organolithium compound is one or more of n-butyllithium, sec-butyllithium, iso-butyllithium, and tert-butyllithium.
121. The process of claim 120, wherein the organolithium compound is n-butyllithium and/or sec-butyllithium.
122. The method of claim 111 or 112, wherein in step (a) of the process of preparing the linear styrene-butadiene copolymer, the second organic solvent is one or more of an alkane solvent.
123. The process of claim 122, wherein the second organic solvent is one or more of a paraffinic solvent from C5 to C10 and a naphthenic solvent from C5 to C10.
124. The method of claim 123, wherein the second organic solvent is one or more of hexane, cyclohexane, pentane, heptane, and isooctane.
125. The method of claim 124, wherein the second organic solvent is present in a weight ratio of 1: a combination of cyclohexane and hexane of 0.08-0.42.
126. The method of claim 122, wherein the second organic solvent is used in an amount such that the total content of butadiene and styrene is 10-15 wt%.
127. The method of claim 75, wherein the terminating agent is one or more of a C1-C4 alcohol, an organic acid, and carbon dioxide.
128. The method of claim 111 or 112, wherein the terminating agent is one or more of a C1-C4 alcohol, an organic acid, and carbon dioxide.
129. The method of claim 127, wherein the terminating agent is one or more of isopropanol, stearic acid, citric acid, and carbon dioxide.
130. The method of claim 129, wherein the terminating agent is carbon dioxide.
131. The method as claimed in any one of claims 67-74, 76-103, 105-112, 114, 116-121, 123-127 and 130, wherein the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer in the toughening agent is 0.4-5: 1.
132. the method of claim 131 wherein the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer is 0.4-4: 1.
133. the method of claim 132 wherein the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer is 0.43-2.3: 1.
134. the method of claim 133, wherein the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer is 0.67-1.5: 1.
135. the method of claim 131 wherein the total content of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer in the solution containing the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer is 40-65 wt%.
136. The method as claimed in claim 131, wherein in step (3), the weight ratio of styrene, acrylonitrile and the toughening agent on a dry weight basis is 400-1000: 100-400: 100.
137. the method as recited in claim 136, wherein the weight ratio of styrene, acrylonitrile, and dry weight basis toughener is 500-900: 140-350: 100.
138. the method as recited in claim 137, wherein the weight ratio of styrene, acrylonitrile, and dry weight basis toughener is 500-800: 150-200: 100.
139. the method as set forth in claim 138 wherein the weight ratio of styrene, acrylonitrile and dry weight basis toughener is 550-750: 180-200: 100.
140. the method as set forth in any one of claims 67-74, 76-103, 105-112, 114, 116-121, 123-127, 130 and 132-139, wherein the radical initiator is a thermal decomposition type initiator in the step (3).
141. The method as claimed in claim 140, wherein the free radical initiator is selected from one or more of peroxide-based initiators and azobisnitrile-based initiators.
142. The method of claim 141, wherein the free radical initiator is selected from one or more of diacyl peroxides, peroxydicarbonates, peroxycarboxylates, alkyl peroxides, and azobisnitrile compounds.
143. The process of claim 142 wherein the free radical initiator is selected from one or more of dibenzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, di-o-methylbenzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile.
144. The process as set forth in claim 140 wherein the weight ratio of the total amount of styrene and acrylonitrile to the amount of the free radical initiator is 2500-: 1.
145. the process as set forth in claim 144 wherein the weight ratio of the total amount of styrene and acrylonitrile to the amount of the free radical initiator is 3000-10500: 1.
146. the method as recited in claim 145, wherein the weight ratio of the total amount of styrene and acrylonitrile to the amount of free radical initiator is 3000-10000: 1.
147. the method as recited in claim 146, wherein the weight ratio of the total amount of styrene and acrylonitrile to the amount of the free radical initiator is 4000-10000: 1.
148. the method as recited in claim 147, wherein the weight ratio of the total amount of styrene and acrylonitrile to the amount of the free radical initiator is 6000-: 1.
149. the method as set forth in any one of claims 67-74, 76-103, 105-112, 114, 116-121, 123-127, 130, 132-139 and 141-148, wherein in the step (3), the polymerization conditions comprise: the temperature is 100-155 ℃, and the time is 4-12 h.
150. The method as set forth in any one of claims 67-74, 76-103, 105-112, 114, 116-121, 123-127, 130, 132-139 and 141-148, wherein in the step (3), the polymerization conditions comprise: firstly reacting at 110 ℃ for 1-3h, then reacting at 125 ℃ for 1-3h, at 115 ℃ for 1-3h, then reacting at 140 ℃ for 1-3h, and finally reacting at 155 ℃ for 1-3 h.
151. The process of claim 150 wherein in step (3), the polymerization conditions comprise: firstly reacting at 110 ℃ for 1-2h, then reacting at 125 ℃ for 1-2h, then reacting at 135 ℃ for 1-2h, and finally reacting at 155 ℃ for 1-2 h.
152. An ABS resin produced by the method of any one of claims 67-151.
153. The ABS resin of claim 152, wherein the content of structural units of styrene is 60-72 wt%; the content of acrylonitrile structural units is 15 to 30 wt%; the weight average molecular weight of the ABS resin was 150000-350000 g/mol.
154. The ABS resin of claim 153 wherein the structural units of styrene are present in an amount of 61-71.5 wt%.
155. The ABS resin of claim 154 wherein the structural unit of styrene is present in an amount of 63-69 wt%.
156. The ABS resin of claim 153, wherein the acrylonitrile has a structural unit content of 18-27 wt%.
157. The ABS resin of claim 156, wherein the acrylonitrile has a structural unit content of 20-27 wt%.
158. The ABS resin of claim 153, wherein the weight average molecular weight of the ABS resin is 180000-300000 g/mol.
159. The ABS resin of claim 158 wherein the ABS resin has a weight average molecular weight of 190000-295000 g/mol.
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| CN111978445B (en) * | 2019-05-21 | 2023-05-12 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber, preparation method and application thereof, and aromatic vinyl resin and preparation method |
| CN112646083B (en) * | 2019-10-12 | 2022-08-12 | 中国石油化工股份有限公司 | Preparation method of toughening agent of polystyrene |
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| CN113698558A (en) * | 2020-05-20 | 2021-11-26 | 中国石油化工股份有限公司 | Butylbenzene copolymer and preparation method and application thereof |
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