CN117070005A - Toughening agent composition, preparation method and application thereof, ABS resin and preparation method thereof - Google Patents
Toughening agent composition, preparation method and application thereof, ABS resin and preparation method thereof Download PDFInfo
- Publication number
- CN117070005A CN117070005A CN202210507036.3A CN202210507036A CN117070005A CN 117070005 A CN117070005 A CN 117070005A CN 202210507036 A CN202210507036 A CN 202210507036A CN 117070005 A CN117070005 A CN 117070005A
- Authority
- CN
- China
- Prior art keywords
- styrene
- molecular weight
- butadiene
- solution
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 239000012745 toughening agent Substances 0.000 title claims abstract description 99
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 198
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000005064 Low cis polybutadiene Substances 0.000 claims abstract description 103
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 97
- 238000009826 distribution Methods 0.000 claims abstract description 51
- 230000002902 bimodal effect Effects 0.000 claims abstract description 38
- 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 10
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 90
- 239000003999 initiator Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 30
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 28
- 239000003963 antioxidant agent Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 22
- 125000000129 anionic group Chemical group 0.000 claims description 21
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- 238000005859 coupling reaction Methods 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims description 6
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000002900 organolithium compounds Chemical class 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YTUUEOBZXXUZJL-UHFFFAOYSA-N 2,3-diethylpentane-1,2,3-triol Chemical compound CCC(O)(CC)C(O)(CC)CO YTUUEOBZXXUZJL-UHFFFAOYSA-N 0.000 claims description 2
- GFTPTQVIOIDDRL-UHFFFAOYSA-N 2,3-dimethylbutane-1,2,3-triol Chemical compound CC(C)(O)C(C)(O)CO GFTPTQVIOIDDRL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000000243 solution Substances 0.000 description 75
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 50
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 36
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 33
- 125000001931 aliphatic group Chemical group 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 16
- 239000005060 rubber Substances 0.000 description 16
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- 229920000570 polyether Polymers 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 101100014509 Arabidopsis thaliana GDU3 gene Proteins 0.000 description 9
- -1 ether compound Chemical group 0.000 description 9
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 8
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 8
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 4
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 150000008378 aryl ethers Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 150000004292 cyclic ethers Chemical class 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 125000001979 organolithium group Chemical group 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 2
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical group CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 description 2
- 101100272412 Arabidopsis thaliana BIA1 gene Proteins 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000008177 pharmaceutical agent Substances 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 101100064324 Arabidopsis thaliana DTX48 gene Proteins 0.000 description 1
- 101100388296 Arabidopsis thaliana DTX51 gene Proteins 0.000 description 1
- 101100022430 Arabidopsis thaliana MYB101 gene Proteins 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
-
- 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the field of styrene resin, and discloses a toughening agent composition, a preparation method and application thereof, ABS resin and a preparation method thereof. The toughening agent composition comprises low cis-polybutadiene rubber and linear butylbenzene copolymer, wherein the molecular weight of the low cis-polybutadiene rubber is in bimodal distribution, mn1 of a low molecular weight component in the bimodal distribution is 30,000-40,000, and the ratio Mn2/Mn1 of Mn2 of a high molecular weight component to Mn1 of the low molecular weight component is 5-6; the molecular weight of the linear butylbenzene copolymer is unimodal, the number average molecular weight is 100,000-140,000, and the weight ratio of the styrene chain segment to the butadiene chain segment in the linear butylbenzene copolymer is 0.53-0.82:1. The composition has extremely low viscosity of 5% styrene solution at 25 ℃, high Mooney viscosity and low gel content, and can obtain ABS resin with good impact resistance and higher glossiness and fluidity.
Description
Technical Field
The invention relates to the field of styrene resin, in particular to a toughening agent composition, a preparation method and application thereof, and an ABS resin and a preparation method thereof.
Background
The continuous bulk ABS resin is obtained by adding a toughening agent into styrene and acrylonitrile monomers according to a certain proportion and adopting thermal initiation or free radical initiation in the presence of a small amount of ethylbenzene solvent. The low cis-polybutadiene rubber and the linear block styrene-butadiene copolymer have low gel content, no transition metal, good color, random cis-trans distribution, no crystallization tendency, good low-temperature impact resistance, freely adjustable molecular weight, moderate content of 1, 2-structural units and high grafting and crosslinking reaction activity, and are the preferred toughening rubber for continuous bulk ABS resin modification. ABS resin prepared by adopting single low cis-polybutadiene rubber component as a toughening agent has poor interfacial compatibility between rubber particles and styrene-acrylonitrile matrix resin, and has unsatisfactory impact resistance and glossiness; the ABS resin prepared by adopting the single component of the linear styrene-butadiene copolymer as the toughening agent has good interfacial compatibility between rubber particles and styrene-acrylonitrile matrix resin and good glossiness, but the high styrene content limits the impact resistance of the ABS resin; in order to achieve both impact resistance and glossiness of the ABS resin, the low cis-polybutadiene rubber and linear styrene-butadiene copolymer dual components are generally adopted for toughening so as to improve the interfacial compatibility of the rubber and matrix resin and increase the particle size distribution of the rubber.
The low cis polybutadiene rubber employs branching techniques to reduce its 5% styrene solution viscosity at 25 ℃, in the prior art the low cis polybutadiene rubber has a 5% styrene solution viscosity lower limit of 20 centipoise at 25 ℃, otherwise the Mooney viscosity is too low to process. In order to obtain an ABS resin having high gloss, it is generally required to make the 5% styrene solution viscosity of the low cis-polybutadiene rubber and the linear styrene-butadiene copolymer as low as possible. In order to control the viscosity of the 5% styrene solution of the linear styrene-butadiene copolymer at 25 ℃, the styrene content of the linear styrene-butadiene copolymer is generally higher, but too high styrene content leads to too high Mooney viscosity of the linear styrene-butadiene copolymer, so that the linear styrene-butadiene copolymer is difficult to feed in the processes of extrusion dehydration and expansion drying, has long retention time and gel content rise, is difficult to form in a briquetting stage, is seriously pulverized, and cannot guarantee the quality of products.
CN109503900a discloses a toughening agent composition, a preparation method thereof, a styrene resin and a preparation method thereof, wherein the viscosity of a 5 wt% styrene solution of the composition at 25 ℃ is 15-35 centipoise, the mooney viscosity at 100 ℃ is 60-90, the viscosity of a 5 wt% styrene solution of low cis-polybutadiene rubber in the composition at 25 ℃ is 20-30 centipoise, and the viscosity of a 5% styrene solution of a linear styrene-butadiene copolymer in the composition is 15-35 centipoise.
CN107722402a discloses a toughening agent composition and ABS resin and a preparation method thereof, the composition contains low cis-polybutadiene rubber and 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 in the range of 40000-75000 and 125000-250000 respectively; the number average molecular weight of the linear butylbenzene copolymer is 70000-200000.
The ratio of the number average molecular weight of the high molecular weight component to the low molecular weight component in the low cis polybutadiene rubber double peaks in the toughening agent compositions disclosed in CN109503900a and CN107722402a is less than 4, and in order to achieve balanced control of the mooney viscosity and the solution viscosity, the viscosity of the 5 wt% styrene solution is kept above 20 centipoise at 25 ℃, and still the requirement of the high performance ABS resin on fluidity cannot be met.
Disclosure of Invention
The invention aims to overcome the defects that in the prior art, the 5 weight percent styrene solution of a toughening agent at 25 ℃ has higher viscosity, the balance control of solution viscosity and Mooney viscosity cannot be realized, and the ABS resin with higher fluidity and high glossiness is difficult to prepare, and provides a toughening agent composition, a preparation method and application thereof and the ABS resin. The toughening agent composition has the characteristics of extremely low viscosity of 5% styrene solution at 25 ℃, high Mooney viscosity and low gel content, and when the toughening agent composition is used for preparing ABS resin, ABS resin with good impact resistance and higher glossiness and fluidity can be obtained.
The inventors of the present invention have intensively studied and found that the 5% styrene solution viscosity of the toughening agent at 25 ℃ is closely related to the particle size of rubber particles formed during the phase inversion process, thereby affecting the impact resistance, gloss and melt index of ABS resin. The 5% styrene solution viscosity of the low cis-polybutadiene rubber at 25℃is closely related to the molecular weight, the degree of branching and the number of branched arms, and the 5% styrene solution viscosity of the linear styrene-butadiene copolymer at 25℃is closely related to the molecular weight, the bound styrene content and the styrene sequence distribution. The particle size of the toughening rubber is too small, which is not beneficial to the termination of silver lines and the induction of shear bands, so that the prepared ABS resin has poor impact resistance. The particle size of the toughening rubber is too large, the molecular number of the rubber with the same weight is reduced, the probability of meeting cracks is low, the improvement range of the impact resistance is small, and meanwhile, the glossiness of the ABS resin is influenced. The low cis-polybutadiene rubber with specific number average molecular weight and bimodal distribution and the linear butylbenzene copolymer with specific number average molecular weight are adopted, and the combination of the low cis-polybutadiene rubber and the linear butylbenzene copolymer with specific number average molecular weight is used as a toughening agent for preparing ABS resin, so that ABS resin with good impact resistance and higher glossiness and fluidity can be obtained, and the invention is completed.
In order to achieve the above object, the present invention provides a toughening agent composition, characterized in that the composition comprises a low cis-polybutadiene rubber and a linear styrene-butadiene copolymer, wherein the molecular weight of the low cis-polybutadiene rubber is in a bimodal distribution, the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000 to 40,000, and the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5 to 6;
the molecular weight of the linear styrene-butadiene copolymer is unimodal, the number average molecular weight is in the range of 100,000-140,000, and the weight ratio of the styrene chain segment to the butadiene chain segment in the linear styrene-butadiene copolymer is 0.53-0.82:1.
In a second aspect, the present invention provides a method of preparing the above toughening agent composition, the method comprising:
(1) In the presence of a first organic solvent, a first structure regulator and a first initiator, carrying out anionic solution polymerization of butadiene until butadiene is completely polymerized, adding a 6-functional group compound for coupling reaction, and then adding a first terminator and a first antioxidant to obtain a low cis-polybutadiene solution;
(2) In the presence of a second organic solvent, a second initiator and optionally a second structure regulator, carrying out second anionic solution polymerization of styrene and butadiene until the styrene and butadiene are completely polymerized, and adding a second terminator and a second antioxidant to obtain a linear styrene-butadiene copolymer solution;
(3) Mixing the low cis-polybutadiene solution with the linear butylbenzene copolymer solution to obtain a composition solution;
(4) Removing the solvent in the composition solution to obtain colloidal particles, and drying the colloidal particles to obtain the composition.
In a third aspect the present invention provides a toughening agent composition prepared by the above preparation method.
The fourth aspect of the invention provides an application of the toughening agent composition in preparing ABS resin.
The fifth aspect of the present invention provides a method for producing an ABS resin, characterized in that styrene and acrylonitrile are copolymerized in the presence of a toughening agent composition to obtain the ABS resin;
wherein the toughening agent composition is the toughening agent composition.
The sixth aspect of the present invention provides an ABS resin produced by the above-described production method.
Through the technical scheme, the toughening agent composition, the preparation method and the application thereof, the ABS resin and the preparation method thereof have the following beneficial effects:
the toughening agent composition provided by the invention comprises low cis-polybutadiene rubber with specific number average molecular weight and bimodal distribution, and linear styrene-butadiene copolymer with specific number average molecular weight, and the toughening agent composition is used for preparing ABS resin, so that ABS resin with good impact resistance and higher glossiness and fluidity can be obtained.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the low cis-polybutadiene rubber refers to a polymer having a relatively low content of structural units obtained by cis-1, 4-polymerization, and generally refers to a polybutadiene rubber having a cis-1, 4-structural unit content of 30 to 40% by weight. In the present invention, the linear styrene-butadiene copolymer refers to a styrene-butadiene rubber having a linear molecular chain and containing both a styrene block and a styrene-butadiene random copolymer.
The first aspect of the present invention provides a toughening agent composition, characterized in that the composition comprises a low cis-polybutadiene rubber and a linear styrene-butadiene copolymer, wherein the molecular weight of the low cis-polybutadiene rubber is in a bimodal distribution, the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000 to 40,000, and the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 5 to 6;
The molecular weight of the linear styrene-butadiene copolymer is unimodal, the number average molecular weight is in the range of 100,000-140,000, and the weight ratio of the styrene chain segment to the butadiene chain segment in the linear styrene-butadiene copolymer is 0.53-0.82:1.
In the invention, the toughening agent composition comprises low cis-polybutadiene rubber with specific number average molecular weight and in bimodal distribution, and linear butylbenzene copolymer with specific number average molecular weight, the toughening system comprising the two components can obtain toughening rubber with wider particle size distribution, and can improve the interfacial compatibility between the rubber and the resin.
According to the invention, the weight ratio of the styrene segment to the butadiene segment in the toughening agent composition is 0.13-0.39:1.
In the invention, when the weight ratio of the styrene chain segment to the butadiene chain segment is controlled to meet the above range, the toughening agent composition can have proper Mooney viscosity and 5 weight percent styrene solution viscosity at 25 ℃, and when the toughening agent composition is used for preparing ABS resin, the prepared ABS resin can have excellent impact resistance and glossiness.
In the present invention, the butadiene segment in the toughening agent composition includes a butadiene segment derived from a low cis polybutadiene rubber and a butadiene segment derived from a linear styrene-butadiene copolymer.
Further, the weight ratio of styrene segments to butadiene segments in the toughening agent composition is 0.15 to 0.35:1, preferably 0.18 to 0.32:1.
According to the invention, the toughening agent composition has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 50-100.
In the present invention, the Mooney viscosity ML of the toughening agent composition at 100 ℃ is controlled 1+4 When the above range is satisfied, the excellent processability of the toughening agent composition can be ensured, and further extrusion dehydration and expansion drying of the toughening agent composition are facilitated. Swelling during drying is detrimental when the mooney viscosity of the toughening agent composition is too low, and processing and shaping are detrimental when the mooney viscosity of the toughening agent composition is too high.
Further, the toughening agent composition has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 55-95, more preferably in the range of 60-90.
According to the present invention, the toughening agent composition has a 5 wt% styrene solution viscosity in the range of 8 to 20 centipoise at 25 ℃.
In the present invention, when the 5 wt% styrene solution viscosity of the toughening agent composition at 25 ℃ satisfies the above range, it is possible to ensure that the toughening agent composition has smaller rubber particle size, thereby enabling the ABS resin prepared from the toughening agent composition to have excellent gloss and flowability.
Further, the toughening agent composition has a 5wt% styrene solution viscosity in the range of 9 to 19 centipoise at 25 ℃, preferably in the range of 10 to 18.
According to the invention, the toughener composition has a volatile content of 1wt% or less.
Further, the volatile content of the toughening agent composition is 0.75wt% or less, preferably 0.5wt% or less.
According to the invention, the toughening agent composition has a gel content of 0 to 150ppm.
In the invention, when the gel content of the toughening agent composition is controlled to meet the range, the prepared ABS resin has higher glossiness and better mechanical property.
Further, the gel content of the toughening agent composition is 0 to 100ppm, preferably 0 to 75ppm.
According to the present invention, the weight ratio of the low cis-polybutadiene rubber to the linear styrene-butadiene copolymer is 0.42 to 2.33:1.
In the invention, when the weight ratio of the low cis-polybutadiene rubber to the linear styrene-butadiene copolymer in the toughening agent composition meets the range, the toughening agent composition can have more reasonable rubber particle size distribution, and when the toughening agent composition is used for preparing ABS resin, ABS resin with better comprehensive performance can be obtained.
Further, the weight ratio of the low cis-polybutadiene rubber to the linear styrene-butadiene copolymer is 0.6-1.5:1.
Low cis polybutadiene rubber
In the invention, the molecular weight of the low cis-polybutadiene rubber is in a bimodal distribution, the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000, and the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5-6.
In the present invention, when the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is controlled to satisfy the above range, it is possible to ensure that the low cis-polybutadiene rubber has the viscosity of the styrene solution of 5 wt% at 25℃as described in the present invention; controlling the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution to satisfy the above range ensures that the low cis-polybutadiene rubber has the Mooney viscosity of the present invention.
According to the invention, the molecular weight distribution index Mw1/Mn1 of the low molecular weight component in the bimodal distribution of the low cis-polybutadiene rubber is from 1 to 1.1.
According to the invention, the molecular weight distribution index Mw2/Mn2 of the high molecular weight component in the bimodal distribution of the low cis-polybutadiene rubber is from 1 to 1.1.
According to the invention, the molecular weight distribution of the low cis-polybutadiene rubber is 1.1 to 1.5, preferably 1.15 to 1.45.
According to the invention, the weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 0.01-0.25:1.
In the present invention, when the weight ratio of the low molecular weight component to the high molecular weight component of the low cis-polybutadiene rubber is controlled to satisfy the above range, it is possible to ensure that the low cis-polybutadiene rubber has a proper degree of branching and to ensure that the low cis-polybutadiene rubber has excellent processability.
Further, the weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 0.04-0.18:1.
According to the invention, the 1, 2-structure content is from 6 to 16% by weight, based on the total weight of the low cis-polybutadiene rubber.
In the present invention, the term "1, 2-structural unit" means a structural unit formed by 1, 2-polymerization of butadiene, and the content of the 1, 2-structural unit may also be referred to as vinyl content. In the present invention, when the 1, 2-structural unit content of the low cis-polybutadiene rubber is controlled to satisfy the above range, the low cis-polybutadiene rubber containing the above vinyl content is used for preparing an ABS resin, and an ABS resin having a suitable grafting efficiency and rubber phase volume fraction can be obtained, thereby improving the overall properties of the ABS resin.
Further, the 1, 2-structure content is 8 to 14% by weight based on the total weight of the low cis-polybutadiene rubber.
According to the invention, the low cis-polybutadiene rubber has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 38-58.
In the present invention, controlling the Mooney viscosity of the low cis-polybutadiene rubber to satisfy the above range enables the low cis-polybutadiene rubber to have excellent processability, and further enables ABS resins produced from a toughening agent composition comprising the low cis-polybutadiene rubber to have excellent gloss and flowability.
Further, the low cis-polybutadiene rubber has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 42-54.
According to the present invention, the low cis polybutadiene rubber has a viscosity in the range of 8 to 20 centipoise at 25℃in a 5 wt.% styrene solution.
In the present invention, when the viscosity of a 5 wt% styrene solution of low cis-polybutadiene rubber at 25 ℃ is controlled to satisfy the above range, it is possible to make the low cis-polybutadiene rubber have smaller particle diameter, and further to make ABS resin made of a toughening agent composition comprising the low cis-polybutadiene rubber have excellent gloss and fluidity.
Further, the low cis polybutadiene rubber has a viscosity of a 5 wt.% styrene solution in the range of 9 to 19 centipoise, preferably in the range of 10 to 18 centipoise at 25 ℃.
Linear butylbenzeneCopolymer
In the invention, the molecular weight of the linear styrene-butadiene copolymer is unimodal, the number average molecular weight is in the range of 100,000-140,000, and the weight ratio of the styrene chain segment to the butadiene chain segment in the linear styrene-butadiene copolymer is 0.53-0.82:1.
According to the invention, the weight ratio of the styrene block to the styrene non-block in the linear styrene-butadiene copolymer is 1.2-4:1.
In the present invention, the styrene block means that the styrene-butadiene copolymer has a molecular chain containing six or more styrene structural units in succession. In the present invention, the weight ratio of the styrene block to the styrene non-block is measured by nuclear magnetic resonance hydrogen spectrometry.
In the present invention, when the weight ratio of the styrene block to the styrene non-block in the linear styrene-butadiene copolymer is controlled to satisfy the above range, the linear styrene-butadiene copolymer can have both excellent Mooney viscosity and 5 wt% styrene solution viscosity at 25 ℃.
Further, in the linear styrene-butadiene copolymer, the weight ratio of the styrene block to the styrene non-block is 1.4-3:1.
According to the present invention, the 1, 2-structure content is 6 to 16wt% based on the total weight of the butadiene segment of the linear styrene-butadiene copolymer.
In the present invention, the term "1, 2-structural unit" means a structural unit formed by 1, 2-polymerization of butadiene, and the content of the 1, 2-structural unit may also be referred to as vinyl content. When the 1, 2-structure content in the linear styrene-butadiene copolymer is controlled to satisfy the above range, the low cis-polybutadiene rubber containing the vinyl content is used for preparing the ABS resin, so that the ABS resin with proper grafting efficiency and rubber phase volume fraction can be obtained, and the comprehensive performance of the ABS resin is improved.
Further, the 1, 2-structure content is 8 to 14wt% based on the total weight of the butadiene segment of the linear styrene-butadiene copolymer.
According to the present invention, the linear styrene-butadiene copolymer has a molecular weight distribution of 1 to 1.1.
In accordance with the present invention,mooney viscosity ML of the linear styrene-butadiene copolymer at 100 DEG C 1+4 In the range of 80-120.
In the present invention, when the Mooney viscosity of the linear styrene-butadiene copolymer is controlled to satisfy the above range, it is possible to ensure excellent processability of the linear styrene-butadiene copolymer, and thus to provide an ABS resin having excellent gloss and fluidity, which is prepared from a toughening agent composition comprising the linear styrene-butadiene copolymer.
Further, the linear styrene-butadiene copolymer has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 90-110.
According to the present invention, the linear styrene-butadiene copolymer has a viscosity of a 5 wt% styrene solution in the range of 8 to 20 centipoise at 25 ℃.
In the present invention, when the viscosity of a 5 wt% styrene solution of the linear styrene-butadiene copolymer at 25 ℃ satisfies the above range, it is possible to ensure that the linear styrene-butadiene copolymer has a smaller particle diameter, thereby enabling an ABS resin prepared from a toughening agent composition comprising the linear styrene-butadiene copolymer to have excellent gloss and flowability.
Further, the linear styrene-butadiene copolymer has a viscosity of a 5 wt% styrene solution in the range of 9 to 19 centipoise at 25 ℃, more preferably in the range of 10 to 18 centipoise.
The second aspect of the present invention provides a method for preparing a toughening agent composition, the method comprising the steps of:
(1) In the presence of a first organic solvent, a first structure regulator and a first initiator, carrying out first anionic solution polymerization of butadiene until butadiene is completely polymerized, adding a 6-functional group compound for coupling reaction, and then adding a first terminator and a first antioxidant to obtain a low cis-polybutadiene solution;
(2) In the presence of a second organic solvent, a second initiator and optionally a second structure regulator, carrying out second anionic solution polymerization of styrene and butadiene until the styrene and butadiene are completely polymerized, and adding a second terminator and a second antioxidant to obtain a linear styrene-butadiene copolymer solution;
(3) Mixing the low cis-polybutadiene solution with the linear butylbenzene copolymer solution to obtain a composition solution;
(4) Removing the solvent in the composition solution to obtain colloidal particles, and drying the colloidal particles to obtain the composition.
In the present invention, the toughener composition according to the first aspect of the present invention can be obtained by the above-described preparation method.
According to the present invention, in step (1), the molecular weight of the low cis-polybutadiene rubber in the low cis-polybutadiene solution is bimodal;
wherein the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000; the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is from 5 to 6.
According to the invention, the low cis-polybutadiene rubber in the low cis-polybutadiene solution has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 38-58.
According to the present invention, the viscosity of the 5 wt% styrene solution of the low cis-polybutadiene rubber in the low cis-polybutadiene solution is in the range of 8-20 centipoise at 25 ℃.
According to the present invention, the number average molecular weight of the linear styrene-butadiene copolymer is in the range of 100,000-140,000, and the weight ratio of the styrene segment to the butadiene segment in the linear styrene-butadiene copolymer is 0.53 to 0.82:1.
according to the invention, the linear styrene-butadiene copolymer has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 80-120.
According to the present invention, the linear styrene-butadiene copolymer has a viscosity of a 5 wt% styrene solution in the range of 8 to 20 centipoise at 25 ℃.
Low cis polybutadiene solution
According to the present invention, in the step (1), the preparation method of the low cis-polybutadiene solution comprises the steps of:
(a) In a first organic solvent, carrying out a first anionic solution polymerization reaction on 1, 3-butadiene in the presence of a first initiator and a first structure regulator until the conversion rate of the 1, 3-butadiene is more than 99%, so as to obtain a polybutadiene active chain; wherein the molar ratio of the 1, 3-butadiene to the first initiator is 550-750:1.
(b) Coupling the polybutadiene living chain in the presence of a 6-functional coupling agent;
(c) And in the presence of a first terminator, after the product of the coupling reaction is terminated, adding a first antioxidant to obtain the low cis-polybutadiene solution.
In the present invention, the low cis-polybutadiene solution prepared by the above method can obtain the low cis-polybutadiene rubber according to the present invention.
According to the invention, in step (a), the first anionic solution polymerization causes the polymerization of 1, 3-butadiene to give a polybutadiene active chain having a number average molecular weight of 30,000 to 40,000, in particular such that the polybutadiene active chain has a molecular weight distribution index of 1 to 1.1.
According to the invention, in step (a), the first organic solvent is an inert non-polar solvent, preferably an alkane solvent and/or a cycloalkane solvent. Specifically, the alkane solvent is preferably at least one of C4 to C8 alkane solvents, more preferably one or more of n-pentane, n-hexane, n-heptane and isooctane. The naphthenic solvents are preferably one or more of C4-C8 naphthenic solvents, more preferably one or more of cyclopentane and/or cyclohexane.
In the present invention, the amount of the first organic solvent may vary within a wide range, and preferably, the content of 1, 3-butadiene is 10 to 20% by weight based on the total weight of the first organic solvent and 1, 3-butadiene.
In one specific embodiment of the present invention, the first organic solvent is a mixed solvent of cyclohexane and hexane, wherein the weight ratio of cyclohexane to hexane is 4-19:1.
in the present invention, the kind of the first initiator is not particularly limited, and the first initiator can be used for the preparation of polybutadiene rubber as is conventional in the artPreferably, the first initiator is of formula R 1 Organolithium compounds represented by Li, wherein R 1 An alkyl group selected from C1-C10; more preferably, the first initiator is one or more of n-butyllithium, sec-butyllithium, isobutyl lithium and tert-butyllithium, more preferably n-butyllithium and/or sec-butyllithium, still more preferably n-butyllithium. Wherein the first initiator is added to the polymerization system in the form of a solution, and the solvent used for dissolving the first initiator may be, for example, one or more of hexane, cyclohexane, heptane, etc., and the amount of the above solvent is not particularly limited, and preferably the solvent is used in such an amount that the concentration of the first initiator solution is preferably 0.1 to 1.0mol/L.
According to the present invention, the amount of the first initiator may be appropriately selected according to the amount of the monomer and the number average molecular weight of the low cis-polybutadiene rubber to be obtained, and may be varied within a wide range, and preferably, when the molar ratio of the 1, 3-butadiene to the first initiator is 550 to 750:1, the polybutadiene active chain obtained in the step (a) can be made to have the number average molecular weight of the present invention, and thus the low cis-polybutadiene rubber obtained can be made to have the number average molecular weight required by the present invention.
According to the present invention, the type of the first structure-adjusting agent is not particularly limited, and a structure-adjusting agent which is conventional in the art may be used, and preferably the first structure-adjusting agent is selected from an ether compound structure-adjusting agent and/or an amine compound structure-adjusting agent.
Preferably, the ether compound structure regulator is one or more of aliphatic monoether, aliphatic polyether, aromatic ether and cyclic ether.
More preferably, the aliphatic monoether is one or more of an aliphatic symmetric monoether and an aliphatic asymmetric monoether, the aliphatic symmetric monoether is one or more of methyl ether, ethyl ether, propyl ether, and butyl ether, and the aliphatic asymmetric monoether is methyl ethyl ether.
More preferably, the aliphatic polyether is one or more of an aliphatic symmetric polyether and an aliphatic asymmetric polyether, the aliphatic symmetric polyether is one or more of ethylene glycol di-C1-C4 alkyl ether, diethylene glycol di-C1-C4 alkyl ether and diethylene glycol di-C1-C4 alkyl ether, preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, and the aliphatic asymmetric polyether is ethylene glycol methyl ethyl ether and/or diethylene glycol methyl ethyl ether.
Preferably, the aromatic ether is anisole and/or diphenyl ether.
Preferably, the cyclic ether is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol C1-C4 alkyl ether and 1, 4-dioxane, preferably one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether and 1, 4-dioxane.
Preferably, the amine compound structure regulator is one or more of N, N, N ', N' -tetramethyl ethylenediamine, N, N-dimethyl tetrahydrofurfuryl amine, triethylamine and tripropylamine.
In a preferred embodiment of the present invention, the structure-modifying agent is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, more preferably one or more of tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether and tetrahydrofurfuryl alcohol propyl ether, particularly preferably tetrahydrofurfuryl alcohol ethyl ether.
In the present invention, in order to increase the reaction rate of the toughening agent composition for preparing an ABS resin while the vinyl content in the prepared low cis-polybutadiene rubber satisfies the range required by the present invention, it is preferable that the molar ratio of the first structure adjustment to the first initiator is 0.02 to 2:1.
According to the invention, in step (a), the first anionic solution polymerization reaction results in a conversion of 1, 3-butadiene of more than 99%, for example 99-100%; preferably, the conditions for the anionic solution polymerization reaction include: the temperature is 40-100deg.C, preferably 50-90deg.C; the time is 20-100min, preferably 30-60min; the gauge pressure is 0.1-1MPa, preferably 0.2-0.5MPa.
According to the present invention, in the step (b), the polybutadiene active chain is subjected to a coupling reaction in the presence of a 6-functional coupling agent, so that the molecular weight of the low cis-polybutadiene rubber obtained is bimodal, and the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000 to 40,000, and the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5 to 6.
Further, such that the weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the low cis-polybutadiene rubber produced is 0.01 to 0.25:1; the molecular weight distribution of the low cis-polybutadiene rubber is 1.1 to 1.5.
According to the present invention, the 6-functional coupling agent is selected from at least one of hexachlorodisilane, hexachloroethane, 1, 3-hexachloropropane, triethyl glycerol and trimethyl glycerol. In order to further improve the stability and reproducibility of the coupling reaction, it is preferable that the 6-functional coupling agent is selected from hexachlorodisilane and/or hexachloroethane.
According to the invention, in step (b), the molar ratio of the coupling agent to the first initiator is between 0.14 and 0.19:1.
in the present invention, when the molar ratio of the coupling agent to the first initiator satisfies the above range, the low cis-polybutadiene rubber produced can be made to have a more excellent branching degree, thereby obtaining a desired Mooney viscosity.
Further, the molar ratio of the coupling agent to the first initiator is 0.15-0.18:1.
according to the present invention, in step (b), the conditions of the coupling reaction include: the temperature is 40-100deg.C, the time is 15-40min, and the gauge pressure is 0.1-1MPa.
Further, in step (b), the conditions of the coupling reaction include: the temperature is 60-100deg.C, the time is 20-40min, and the gauge pressure is 0.1-0.5MPa.
In the present invention, preferably, the steps (a) and (b) are performed in a protective atmosphere provided by an inert gas selected from one or more of nitrogen, neon and argon.
According to the present invention, in the step (c), the coupling reaction can be terminated and the polymerization reaction can be initiated by using the first terminator, so that a polymerization solution of the low cis-polybutadiene rubber can be obtained.
According to the invention, in step (C), the first terminator is selected from one or more of C1-C4 alcohol, organic acid and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid and carbon dioxide, more preferably carbon dioxide. Carbon dioxide is adopted for termination reaction, and can form carbonate with metal ions in a polymerization system to be separated from a polymer, so that the color reaction of the metal ions is avoided, and the product has lower chromaticity. The carbon dioxide may be introduced into the reaction system in the form of a gas (for example, a carbon dioxide gas having a gauge pressure of 0.2 to 1MPa (for example, may be 0.3 to 0.6 MPa)), or may be introduced into the reaction system in the form of an aqueous dry ice solution (for example, a concentration of 0.1 to 5% by weight).
According to the present invention, it is preferable that the first terminator is used in an amount of 0.1 to 0.2 parts by weight with respect to 100 parts by weight of the 1, 3-butadiene monomer.
In the present invention, in order to improve the antioxidant properties of the low cis-polybutadiene rubber produced, the method preferably further comprises: mixing the product from the termination of step (c) with a first antioxidant.
In the present invention, the kind of the first antioxidant is not particularly limited, and for example, one or more selected from the group consisting of 4, 6-bis (octylthiomethyl) orthocresol (trade name: antioxidant 1520), N-octadecyl beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: antioxidant 1076), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (trade name: antioxidant 4020), N-isopropyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010 NA) and N-phenyl-2-naphthylamine (trade name: antioxidant D) may be used, preferably a mixture of antioxidant 1520 and antioxidant 1076, and particularly a combination of antioxidant 1520 and antioxidant 1076 in a weight ratio of 0.5 to 5:1, preferably 1:1 may be used.
In the present invention, the amount of the first antioxidant may vary within a wide range, and preferably, in the step (c), the amount of the first antioxidant is 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the 1, 3-butadiene monomer.
Linear styrene-butadiene copolymer solution
According to the present invention, in the step (2), the preparation method of the linear styrene-butadiene copolymer solution comprises the steps of:
(i) In a second organic solvent, carrying out a second anionic solution polymerization reaction on 1, 3-butadiene and styrene in the presence of a second initiator and optionally a second structure regulator until the conversion rate of the 1, 3-butadiene and the styrene is more than 99%, so as to obtain a butadiene-styrene copolymer active chain; preferably, the butadiene-styrene copolymer has a number average molecular weight of 100,000-140,000 for the active chains;
(ii) And in the presence of a second terminator, after terminating the product of the second polymerization anion reaction, adding a second antioxidant to obtain a linear styrene-butadiene copolymer solution.
According to the present invention, the method for preparing the linear styrene-butadiene copolymer will be capable of obtaining the linear styrene-butadiene copolymer of the present invention, and for this reason, the method will be limited to a method capable of obtaining the above-mentioned linear styrene-butadiene copolymer of the present invention.
According to the present invention, the second anionic solution polymerization reaction of step (i) will yield 1, 3-butadiene and styrene copolymer living chains, and the reaction process will be controlled to yield linear styrene-butadiene copolymer living chains having a number average molecular weight of 100,000-140,000, in particular such that the molecular weight distribution index of the linear styrene-butadiene copolymer living chains is 1.0 to 1.1.
According to the invention, in step (i), the weight ratio of styrene to 1, 3-butadiene is between 0.53 and 0.82:1.
in the present invention, in the step (i)The kind of the second initiator is not particularly limited, and various organolithium initiators conventionally used in the art for the preparation of polybutadiene rubber can be used, and preferably the first initiator is represented by the formula R 1 Organolithium compounds represented by Li, wherein R 1 An alkyl group selected from C1-C10; more preferably, the first initiator is one or more of n-butyllithium, sec-butyllithium, isobutyl lithium and tert-butyllithium, more preferably n-butyllithium and/or sec-butyllithium, still more preferably n-butyllithium. Wherein the second initiator is added to the polymerization system in the form of a solution, and the solvent used for dissolving the second initiator may be, for example, one or more of hexane, cyclohexane, heptane, etc., and the amount of the above solvent is not particularly limited, and preferably the amount of the solvent is such that the concentration of the second initiator solution is preferably 0.1 to 1.0mol/L.
According to the present invention, the amount of the second initiator may be appropriately selected according to the amount of the monomer and the number average molecular weight of the linear styrene-butadiene copolymer to be obtained, and may be widely varied, and preferably, when the total molar amount of the 1, 3-butadiene and the styrene and the molar amount of the first initiator are 1300 to 1900:1, the butadiene-styrene active chain obtained in the step (i) may be made to have the number average molecular weight of the present invention, and thus the linear styrene-butadiene copolymer obtained may be made to have the number average molecular weight of the present invention.
In the present invention, the first initiator and the second initiator may be the same or different.
According to the present invention, the type of the first structure-adjusting agent is not particularly limited, and a structure-adjusting agent which is conventional in the art may be used, and preferably the first structure-adjusting agent is selected from an ether compound structure-adjusting agent and/or an amine compound structure-adjusting agent.
Preferably, the ether compound structure regulator is one or more of aliphatic monoether, aliphatic polyether, aromatic ether and cyclic ether.
More preferably, the aliphatic monoether is one or more of an aliphatic symmetric monoether and an aliphatic asymmetric monoether, the aliphatic symmetric monoether is one or more of methyl ether, ethyl ether, propyl ether, and butyl ether, and the aliphatic asymmetric monoether is methyl ethyl ether.
More preferably, the aliphatic polyether is one or more of an aliphatic symmetric polyether and an aliphatic asymmetric polyether, the aliphatic symmetric polyether is one or more of ethylene glycol di-C1-C4 alkyl ether, diethylene glycol di-C1-C4 alkyl ether and diethylene glycol di-C1-C4 alkyl ether, preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, and the aliphatic asymmetric polyether is ethylene glycol methyl ethyl ether and/or diethylene glycol methyl ethyl ether.
Preferably, the aromatic ether is anisole and/or diphenyl ether.
Preferably, the cyclic ether is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol C1-C4 alkyl ether and 1, 4-dioxane, preferably one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether and 1, 4-dioxane.
Preferably, the amine compound structure regulator is one or more of N, N, N ', N' -tetramethyl ethylenediamine, N, N-dimethyl tetrahydrofurfuryl amine, triethylamine and tripropylamine.
In a preferred embodiment of the present invention, the structure-modifying agent is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, more preferably one or more of tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether and tetrahydrofurfuryl alcohol propyl ether, particularly preferably tetrahydrofurfuryl alcohol ethyl ether.
In the present invention, in order to increase the reaction rate of the toughening agent composition for preparing ABS resin while the 1, 2-structure content and the styrene block content in the prepared linear styrene-butadiene copolymer satisfy the range required by the present invention, it is preferable that the molar ratio of the first structure modifier to the first initiator is 0.02 to 2:1.
In the present invention, the first structure-adjusting agent and the second structure-adjusting agent may be the same or different.
According to the invention, in step (i), the second organic solvent is an inert non-polar solvent, preferably an alkane solvent and/or a cycloalkane solvent. Specifically, the alkane solvent is preferably at least one of C4 to C8 alkane solvents, more preferably one or more of n-pentane, n-hexane, n-heptane and isooctane. The naphthenic solvents are preferably one or more of C4-C8 naphthenic solvents, more preferably cyclopentane and/or cyclohexane.
In the present invention, the amount of the second organic solvent may vary within a wide range, and preferably, the content of 1, 3-butadiene and styrene is 10 to 20% by weight based on the total weight of the second organic solvent, 1, 3-butadiene and styrene.
In the present invention, the first organic solvent and the second organic solvent may be the same or different.
In one specific embodiment of the present invention, the second organic solvent is a mixed solvent of cyclohexane and hexane, wherein the weight ratio of cyclohexane to hexane is 4-19:1.
According to the invention, in step (i), the second anionic solution polymerization reaction results in a conversion of 1, 3-butadiene and styrene of more than 99%, for example 99-100%; preferably, the conditions for the anionic solution polymerization reaction include: the temperature is 40-100deg.C, preferably 50-100deg.C; the time is 30-80min, preferably 40-60min; the gauge pressure is 0.1-1MPa, preferably 0.2-0.5MPa.
In the present invention, preferably, the steps (i) and (ii) are performed in a protective atmosphere provided by an inert gas selected from one or more of nitrogen, neon and argon.
According to the present invention, in the step (ii), the polymerization reaction may be terminated by using a second terminator, and a polymerization solution of the linear styrene-butadiene copolymer may be obtained.
According to the invention, in step (ii), the second terminator is selected from one or more of C1-C4 alcohol, organic acid and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid and carbon dioxide, more preferably carbon dioxide. Carbon dioxide is adopted for termination reaction, and can form carbonate with metal ions in a polymerization system to be separated from a polymer, so that the color reaction of the metal ions is avoided, and the product has lower chromaticity. The carbon dioxide may be introduced into the reaction system in the form of a gas (for example, a carbon dioxide gas having a gauge pressure of 0.2 to 1MPa (for example, may be 0.3 to 0.6 MPa)), or may be introduced into the reaction system in the form of an aqueous dry ice solution (for example, a concentration of 0.1 to 5% by weight).
According to the present invention, it is preferable that the second terminator is used in an amount of 0.1 to 0.2 parts by weight with respect to 100 parts by weight of the total amount of the 1, 3-butadiene monomer and the styrene monomer.
In the present invention, the first terminator and the second terminator may be the same or different.
In the present invention, in order to improve the oxidation resistance of the produced linear styrene-butadiene rubber, preferably, the method further comprises: mixing the product resulting from the termination of step (ii) with a second antioxidant.
In the present invention, the kind of the second antioxidant is not particularly limited, and for example, one or more selected from the group consisting of 4, 6-bis (octylthiomethyl) orthocresol (trade name: antioxidant 1520), N-octadecyl beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: antioxidant 1076), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (trade name: antioxidant 4020), N-isopropyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010 NA) and N-phenyl-2-naphthylamine (trade name: antioxidant D) may be used, and preferably a mixture of antioxidant 1520 and antioxidant 1076, particularly a combination of antioxidant 1520 and antioxidant 1076 in a weight ratio of 0.5 to 5:1, preferably 1:1 may be used.
In the present invention, the amount of the second antioxidant may vary within a wide range, and preferably, in the step (ii), the second antioxidant is used in an amount of 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the total amount of 1, 3-butadiene and styrene.
In the present invention, the first antioxidant and the second antioxidant may be the same or different.
According to the present invention, in the step (3), the low cis-polybutadiene solution and the linear styrene-butadiene copolymer solution are used in such an amount that the weight ratio of the low cis-polybutadiene rubber to the linear styrene-butadiene copolymer in the composition is 0.42 to 2.33:1, preferably 0.6-1.5:1.
according to the invention, in step (4), the water content of the colloidal particles is 40-60wt%.
In the present invention, the method for removing the solvent from the composition solution is not particularly limited, and for example, steam coagulation may be used.
According to the invention, the toughener composition has a volatile content of 1wt% or less.
In a third aspect the present invention provides a toughening agent composition prepared by the above preparation method.
In a fourth aspect, the present invention provides the use of the above plasticizer composition for preparing ABS resin.
The fifth aspect of the present invention provides a method for producing an ABS resin, characterized in that styrene and acrylonitrile are copolymerized in the presence of a toughening agent composition to obtain the ABS resin;
Wherein the toughening agent composition is the toughening agent composition.
The sixth aspect of the present invention provides an ABS resin produced by the above-described production method.
The present invention will be described in detail by examples.
In the examples and comparative examples below, the monomer conversion is determined gravimetrically, i.e. the weight of polymer after removal of solvent, as a percentage of the theoretical polymer yield.
Low cis polybutadiene rubber and 1, 2-polymerized structural units, 1,4 in linear styrene-butadiene copolymerThe polymerization structural unit, the styrene content, the styrene block content and the styrene non-block content are tested by using a Bruker AVANCE400 type superconducting nuclear magnetic resonance spectrometer (1H-NMR), the resonance frequency of a 1H core is 300.13MHz, the spectrum width is 2747.253Hz, the pulse width is 5.0 mu s, the data point is 16K, the diameter of a sample tube is 5mm, and the solvent is deuterated chloroform CDCl 3 The sample concentration was 15% (W/V), the test temperature was ambient, the number of scans was 16, and the sample was scaled with a tetramethylsilane chemical shift of 0 ppm.
Molecular weight and molecular weight distribution were determined using an HLC-8320 type gel permeation chromatograph from eastern co., japan, wherein the test conditions include: the chromatographic column is TSKgel SuperMultiporeHZ-N, the standard column is TSKgel SuperMultiporeHZ, the solvent is chromatographic pure THF, the calibration standard sample is polystyrene, the mass concentration of the sample is 1mg/ml, the sample injection amount is 10.00 mu l, the flow rate is 0.35ml/min, and the test temperature is 40.0 ℃.
The styrene solution viscosity of 5 wt.% rubber at 25℃was determined using a Peking Yanshan petrochemical company, inc. Standard Q/SH3155.SXL.C26-2019, and was measured using a Fender viscometer at a constant temperature of 25 ℃.
The Mooney viscosity was measured according to GB/T1232.1 standard using a GT-7080-S2 Mooney viscometer manufactured by Gotech company of Taiwan, wherein the preheating time was 1min, the rotation time was 4min, and the test temperature was 100deg.C.
The melt index of the ABS resin is measured according to the GB/T3682.1-2018 standard, and the notched impact strength (23 ℃) of the cantilever beam is measured according to the GB/T1843-2018 standard; 60℃gloss is measured according to GB/T8807-2018 standard.
The pressure of carbon dioxide is hereinafter referred to as gauge pressure.
Cyclohexane and hexane are supplied by national pharmaceutical agents, polymeric grades, molecular sieves soaked to a water content below 10ppm; butadiene, supplied by the petrification, polymerization grade; THF is provided by the national medicine reagent company, is chromatographically pure, and is soaked for more than 15 days by adopting a molecular sieve after hexane is diluted by 10 times, and the dosage in the system is calculated according to pure substances; tetrahydrofurfuryl alcohol diethyl ether is provided by national drug reagent company, analytically pure, hexane is diluted 20 times and soaked by molecular sieve for more than 15 days, and the dosage in the system is calculated according to pure substances; n-butyllithium is manufactured by the reagent Co.Ltd Provided, 1.6mol.L -1 Diluted to 0.4mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the Hexachloroethane was supplied by enokak reagent company, analytically pure, diluted to 0.1mol.l -1 The method comprises the steps of carrying out a first treatment on the surface of the The anti-aging agents 1520 and 1076 are provided by national pharmaceutical agents company and are diluted to a mass concentration of 10%, and the dosage in the system is calculated according to pure substances.
Polybutadiene rubber 720AX, available from Asahi Karaku chemical, with the structural parameters detailed in Table 2;
linear styrene-butadiene copolymer 1322, available from mexico Dai Nasuo, with the structural parameters detailed in table 4.
Example 1
This example illustrates the toughening agent composition of the present invention and a method of making the same.
(1) Adding nonpolar hydrocarbon solvent, 1, 3-butadiene monomer and structure regulator (the types and the amounts are shown in table 1 and are all metered by pure compounds) into a reactor under the protection of nitrogen, heating to a specified temperature, adding organolithium initiator (the types and the amounts are shown in table 1 and are all metered by pure compounds), and then carrying out anionic solution polymerization reaction (the reaction temperature is 90 ℃ C., the time is 30min and the pressure is 0.3 MPa) at the specified reaction pressure until the 1, 3-butadiene monomer is completely converted; then adding a coupling agent (the types and the amounts of which are shown in the table 1 and the amounts of which are all measured by pure compounds) into the product of the anionic solution polymerization reaction to perform the coupling reaction at the specified temperature and pressure (the coupling reaction temperature is 80 ℃, the time is 30min and the pressure is 0.3 MPa); terminating the coupling reaction by using a terminating agent (the types and the amounts of the terminating agent are shown in Table 1), adding an antioxidant (1.2 g of a combined antioxidant of 1520 and 1076 in a weight ratio of 1:1) for mixing to obtain a polymerization solution LCBR1 of the low cis-polybutadiene rubber, carrying out steam coagulation desolventizing treatment and drying on part of the obtained LCBR1 polymerization solution, and carrying out structure and performance measurement, wherein the results are shown in Table 2.
(2) Under the protection of nitrogen, adding nonpolar hydrocarbon solvent, 1, 3-butadiene monomer, styrene monomer and structure regulator (the types and the amounts are shown in Table 3, the amounts listed in the Table are all metered by pure compounds) into a reactor, heating to a specified temperature, adding organolithium initiator (the types and the amounts listed in the Table are all metered by pure compounds), and then carrying out anionic solution polymerization reaction (the polymerization temperature is 90 ℃ C., the polymerization time is 60min, and the polymerization pressure is 0.3 MPa) at the specified temperature and the specified reaction pressure until the 1, 3-butadiene and the styrene monomer are completely converted; terminating the polymerization reaction by using a terminating agent (the types and the amounts of the terminating agent are shown in Table 3), adding an antioxidant (1.2 g of a combined antioxidant of 1520 and 1076 in a weight ratio of 1:1) and mixing to obtain a polymerization solution LBS1 of the linear styrene-butadiene copolymer, performing steam coagulation desolventizing treatment and drying on part of the obtained LBS1 polymerization solution, and measuring the structure and the performance, wherein the result is shown in Table 4.
(3) The LCBR1 solution and LBS1 solution were mixed in a 1:1 weight ratio to give a toughener composition solution ZHW, and the resulting ZHW polymerized solution was steam coagulated to desolventize and dried, and structural and performance measurements were made, with the results shown in table 5.
Examples 2 to 9
This example illustrates a toughening agent composition and a method of making the same.
According to the method of example 1, except that the reaction was performed using the parameters shown in tables 1 and 3, thereby obtaining LCBR2, LCBR3, LBS2, LBS3, LBS4, LBS5, respectively, the resulting polymers were subjected to structure and property measurement, the results are shown in tables 2 and 4, then LCBR and LBS were mixed in the weight ratio shown in Table 5, thereby obtaining toughening agent compositions ZHW-9, and the resulting ZHW polymerization solution was subjected to steam coagulation desolventizing treatment and dried, and the results are shown in Table 5.
Table 1 (Low cis polybutadiene rubber)
| Examples of the invention | LCBR1 | LCBR2 | LCBR3 |
| Solvent cyclohexane/g | 2300 | 2300 | 2300 |
| 1, 3-butadiene/g | 374 | 374 | 374 |
| N-butyllithium/nmol | 10.5 | 12.0 | 9.5 |
| Butadiene/n-butyllithium | 660 | 577 | 729 |
| Structure regulator/g | Tetrahydrofurfuryl alcohol diethyl ether 0.2 | Tetrahydrofurfuryl alcohol diethyl ether 0.2 | Tetrahydrofurfuryl alcohol diethyl ether 0.2 |
| Structure regulator/n-butyllithium | 0.15 | 0.13 | 0.16 |
| Coupling agent hexachloroethane/nmol | 1.83 | 2.18 | 1.59 |
| Coupling agent/n-butyllithium | 0.17 | 0.18 | 0.17 |
| Terminator carbon dioxide, g | 0.5 | 0.5 | 0.5 |
Table 2 (Low cis polybutadiene rubber)
| Examples of the invention | LCBR1 | LCBR2 | LCBR3 | 720AX |
| Mn 1/ten thousand as low molecular component | 3.6 | 3.1 | 4.0 | 4.8 |
| Low molecular weight component Mw1/Mn1 | 1.03 | 1.03 | 1.03 | 1.03 |
| Low molecular weight component/wt% | 4 | 2 | 8 | 8 |
| High molecular component Mn 2/ten thousand | 19.1 | 16.5 | 21.1 | 15.8 |
| High molecular weight component Mw2/Mn2 | 1.04 | 1.04 | 1.05 | 1.04 |
| High molecular weight component/wt% | 96 | 98 | 92 | 92 |
| Mn2/Mn1 | 5.31 | 5.32 | 5.28 | 3.29 |
| Weight of low molecular weight component/weight of high molecular weight component | 0.042 | 0.020 | 0.087 | 0.087 |
| Mw/Mn | 1.17 | 1.12 | 1.19 | 1.24 |
| 1, 2-Structure content/wt% | 12.2 | 12.1 | 12.6 | 12.4 |
| 5% styrene solution viscosity/cp | 15.4 | 11.7 | 15.8 | 24.6 |
| Mooney viscosity | 52 | 46 | 49 | 37 |
| Gel content/ppm | 28 | 41 | 47 | 54 |
Table 3 (Linear styrene-butadiene copolymer)
| Examples of the invention | LBS1 | LBS2 | LBS3 | LBS4 | LBS5 |
| Cyclohexane/g | 2300 | 2300 | 2300 | 2300 | 2300 |
| 1, 3-butadiene/g | 225 | 225 | 225 | 240 | 210 |
| Styrene/g | 150 | 150 | 150 | 135 | 165 |
| N-butyllithium/nmol | 3.2 | 3.7 | 2.8 | 3.2 | 3.2 |
| Structure regulator/g | Tetrahydrofuran 0.2 | Tetrahydrofuran 0.2 | Tetrahydrofurfuryl alcohol diethyl ether 0.1 | - | Tetrahydrofurfuryl alcohol diethyl ether 0.1 |
| Carbon dioxide/g | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Table 4 (Linear styrene-butadiene copolymer)
| Examples of the invention | LBS1 | LBS2 | LBS3 | LBS4 | LBS5 | 1322 |
| Number average molecular weight/ten thousand | 11.9 | 10.2 | 13.6 | 12.0 | 12.1 | 14.8 |
| Molecular weight distribution | 1.07 | 1.06 | 1.05 | 1.08 | 1.08 | 1.17 |
| Styrene content/wt% | 40.2 | 40.1 | 40.2 | 36.2 | 44.3 | 31.3 |
| Styrene segment/butadiene segment | 0.67 | 0.67 | 0.67 | 0.57 | 0.80 | 0.46 |
| Block styrene content/wt% | 28.4 | 28.8 | 23.9 | 25.7 | 28.1 | 23.8 |
| Styrene non-block content/wt% | 11.8 | 11.3 | 16.3 | 10.5 | 16.2 | 7.5 |
| Styrene block/styrene non-block | 2.41 | 2.55 | 1.47 | 2.45 | 1.73 | 3.17 |
| 1, 2-Structure content/wt% | 9.8 | 9.6 | 12.8 | 7.8 | 12.6 | 8.2 |
| Mooney viscosity | 98 | 86 | 107 | 83 | 117 | 131 |
| 5% styrene solution viscosity/cp | 13.7 | 10.4 | 17.2 | 14.8 | 11.3 | 24.2 |
TABLE 5
Application example 1
This application example is for explaining the ABS resin and the preparation method thereof.
25g of the toughening agent composition ZHW is mixed with 130g of styrene, 50g of acrylonitrile, 20g of ethylbenzene and 0.02g of dibenzoyl peroxide, polymerized at 110 ℃ for 2 hours, 120 ℃ for 2 hours, 140 ℃ for 2 hours and 160 ℃ for 2 hours, and the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvent to obtain the ABS1 resin, and the structure and performance are measured, and the result is shown in Table 6.
Application examples 2 to 9
ABS resin was prepared by the method shown in application example 1, except that ZHW2-ZHW9 was used as a toughening agent instead of ZHW1, ABS2-ABS9 resin was prepared, and structural and performance measurements were performed, and the results are shown in Table 6.
Comparative application example 1
ABS resin was prepared by the method shown in application example 1, LCBR1 prepared in example 1 was used as a toughening agent instead of ZHW1 to prepare DABS1 resin, and the structure and performance were measured, and the results are shown in Table 6.
Comparative application example 2
ABS resin was prepared by the method shown in application example 1, LBS1 prepared in example 1 was used as a toughening agent instead of ZHW1, DABS2 resin was prepared, and structural and performance measurements were performed, and the results are shown in Table 6.
Comparative application example 3
ABS resin was prepared by the method shown in application example 1, and a toughening agent composition DZHW3 was prepared by using 720AX (test data see Table 2) produced by Asahi chemical industry instead of LCBR1 and LBS1 of example 1 in a ratio of 1:1, to prepare DABS3 resin, and the results of the structure and performance measurements were shown in Table 6.
Comparative application example 4
ABS resin was prepared by the method shown in application example 1, and a toughening agent composition DZHW4 was prepared by using Dai Nasuo produced 1322 (test data are shown in Table 4) instead of LBS1 and LCBR1 of example 1 in a ratio of 1:1, thereby preparing DABS4 resin, and the results of the structure and performance measurements are shown in Table 6.
Comparative application example 5
ABS resin was prepared by the method shown in application example 1, 720AX (test data see Table 2) produced by Asahi chemical Co., ltd., instead of LCBR1 of example 1, 1322 (test data see Table 4) produced by Dai Nasuo was used instead of LBS1 and 720AX of example 1 to prepare a toughening agent composition DZHW5 in a ratio of 1:1, thereby preparing DABS5 resin, and the results of the structure and property measurement are shown in Table 6.
TABLE 6
| Sample numbering | Melt index g/10min | Impact strength of cantilever beam/KJ/m 2 | Gloss (60 degree) |
| ABS1 | 32.8 | 20.6 | 98 |
| ABS2 | 33.4 | 20.2 | 99 |
| ABS3 | 30.6 | 21.1 | 96 |
| ABS4 | 31.5 | 20.8 | 97 |
| ABS5 | 32.9 | 19.8 | 96 |
| ABS6 | 33.8 | 19.3 | 98 |
| ABS7 | 30.8 | 20.7 | 98 |
| ABS8 | 32.1 | 19.1 | 98 |
| ABS9 | 32.3 | 20.4 | 95 |
| DABS1 | 31.5 | 16.4 | 92 |
| DABS2 | 34.5 | 14.7 | 94 |
| DABS3 | 29.8 | 18.9 | 88 |
| DABS4 | 30.4 | 19.6 | 86 |
| DABS5 | 26.8 | 18.4 | 82 |
As can be seen from Table 6, by using the toughening agent composition containing the present invention as a toughening agent, the melt flow rate can be obtainedThe rate is more than 30g/10min, and the impact strength of the cantilever beam is 19KJ/m 2 ABS resin with 60 deg. glossiness over 95 deg.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (17)
1. 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, the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000 to 40,000, and the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5 to 6;
The molecular weight of the linear styrene-butadiene copolymer is unimodal, the number average molecular weight is in the range of 100,000-140,000, and the weight ratio of the styrene chain segment to the butadiene chain segment in the linear styrene-butadiene copolymer is 0.53-0.82:1.
2. The toughening agent composition according to claim 1, wherein the weight ratio of styrene segments to butadiene segments in the toughening agent composition is 0.13-0.39:1, preferably 0.15-0.35:1, more preferably 0.18-0.32:1.
3. The toughening agent composition according to claim 1 or 2, wherein the toughening agent composition has a mooney viscosity ML at 100 ℃ 1+4 In the range of 50-100, preferably 55-95, more preferably 60-90;
preferably, the toughening agent composition has a 5 wt% styrene solution viscosity at 25 ℃ in the range of 8 to 20 centipoise, preferably in the range of 9 to 19 centipoise, more preferably in the range of 10 to 18;
preferably, the content of volatile components in the toughening agent composition is less than or equal to 1wt%;
preferably, the gel content of the toughening agent composition is from 0 to 150ppm, preferably from 0 to 100ppm.
4. A toughener composition according to any one of claims 1-3, wherein the weight ratio of the low cis polybutadiene rubber to the linear styrene-butadiene copolymer is 0.42-2.33:1, preferably 0.6-1.5:1.
5. The toughener composition of any one of claims 1-4, wherein the low molecular weight component in the bimodal distribution of the low cis polybutadiene rubber has a molecular weight distribution index, mw1/Mn1, of 1-1.1;
preferably, the molecular weight distribution index Mw2/Mn2 of the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is from 1 to 1.1;
preferably, the molecular weight distribution of the low cis polybutadiene rubber is 1.1 to 1.5, preferably 1.15 to 1.45.
6. The toughening agent composition according to any one of claims 1 to 5, wherein the weight ratio of low molecular weight component to high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 0.01 to 0.25:1, preferably 0.04 to 0.18:1;
preferably, the 1, 2-structure content is from 6 to 16wt%, preferably from 8 to 14wt%, based on the total weight of the low cis polybutadiene rubber;
preferably, the low cis polybutadiene rubber has a Mooney viscosity ML at 100 DEG C 1+4 In the range 38-58, preferably in the range 42-54;
preferably, the low cis polybutadiene rubber has a viscosity of a 5 wt.% styrene solution in the range of 8 to 20 centipoise at 25 ℃, preferably in the range of 9 to 19 centipoise, more preferably in the range of 10 to 18 centipoise.
7. The toughening agent composition according to any one of claims 1 to 6, wherein the weight ratio of styrene blocks to styrene non-blocks in the linear styrene-butadiene copolymer is 1.2 to 4:1, preferably 1.4 to 3:1;
preferably, the 1, 2-structure content is 6 to 16wt%, preferably 8 to 14wt%, based on the total weight of butadiene segments of the linear styrene-butadiene copolymer;
preferably, the linear styrene-butadiene copolymer has a molecular weight distribution of 1 to 1.1;
preferably, the linear styrene-butadiene copolymer has a Mooney viscosity ML at 100deg.C 1+4 In the range 80-120, preferably in the range 90-110;
preferably, the linear styrene-butadiene copolymer has a viscosity of a 5 wt.% styrene solution in the range of 8 to 20 centipoise at 25 ℃, preferably in the range of 9 to 19 centipoise, more preferably in the range of 10 to 18 centipoise.
8. A method of preparing a toughening agent composition, the method comprising the steps of:
(1) In the presence of a first organic solvent, a first structure regulator and a first initiator, carrying out first anionic solution polymerization of butadiene until butadiene is completely polymerized, adding a 6-functional group compound for coupling reaction, and then adding a first terminator and optionally a first antioxidant to obtain a low cis-polybutadiene solution;
(2) In the presence of a second organic solvent, a second initiator and optionally a second structure regulator, carrying out second anionic solution polymerization of styrene and butadiene until the styrene and butadiene are completely polymerized, and adding a second terminator and optionally a second antioxidant to obtain a linear styrene-butadiene copolymer solution;
(3) Mixing the low cis-polybutadiene solution with the linear butylbenzene copolymer solution to obtain a composition solution;
(4) Removing the solvent in the composition solution to obtain colloidal particles, and drying the colloidal particles to obtain the composition.
9. The production process according to claim 8, wherein in the step (1), the molecular weight of the low cis-polybutadiene rubber in the low cis-polybutadiene solution is bimodal;
wherein the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000; the ratio Mn2/Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is from 5 to 6;
preferably, the low cis-polybutadiene rubber in the low cis-polybutadiene solution has a Mooney viscosity ML at 100 DEG C 1+4 In the range of 38-58, a 5 wt.% styrene solution having a viscosity in the range of 8-20 centipoise at 25 ℃;
Preferably, the number average molecular weight of the linear styrene-butadiene copolymer is in the range of 100,000-140,000, and the weight ratio of the styrene segment to the butadiene segment in the linear styrene-butadiene copolymer is 0.53-0.82:1, a step of;
preferably, the linear styrene-butadiene copolymer has a Mooney viscosity ML at 100deg.C 1+4 In the range of 80-120;
preferably, the linear styrene-butadiene copolymer has a viscosity of a 5 wt% styrene solution in the range of 8-20 centipoise at 25 ℃.
10. The production method according to claim 8 or 9, wherein in step (1), the production method of the low cis-polybutadiene solution comprises the steps of:
(a) In a first organic solvent, carrying out a first anionic solution polymerization reaction on 1, 3-butadiene in the presence of a first initiator and a first structure regulator until the conversion rate of the 1, 3-butadiene is more than 99%, so as to obtain a polybutadiene active chain; wherein the molar ratio of the 1, 3-butadiene to the first initiator is 550-750:1, a step of; preferably, the polybutadiene active chain has a number average molecular weight of 30,000 to 40,000;
(b) Coupling the polybutadiene living chain in the presence of a 6-functional coupling agent;
(c) In the presence of a first terminator, after the product of the coupling reaction is terminated, adding a first antioxidant to obtain the low cis-polybutadiene solution;
Preferably, in step (a), the conditions of the first anionic solution polymerization reaction include: the temperature is 40-100deg.C, preferably 50-90deg.C; the time is 20-100min, preferably 30-60min; the gauge pressure is 0.1-1MPa, preferably 0.2-0.5MPa;
preferably, in step (a), the molar ratio of the first structure modifier to the first initiator is from 0.02 to 2:1.
preferably, in step (b), the 6-functional coupling agent is selected from at least one of hexachlorodisilane, hexachloroethane, 1, 3-hexachloropropane, triethyl glycerol and trimethyl glycerol, more preferably hexachlorodisilane and/or hexachloroethane;
preferably, in step (b), the molar ratio of the coupling agent to the first initiator is from 0.14 to 0.19:1, preferably 0.15-0.18:1, a step of;
preferably, in step (b), the conditions of the coupling reaction comprise: the temperature is 40-100deg.C, the time is 15-40min, and the gauge pressure is 0.1-1MPa;
preferably, in step (c), the first terminator is used in an amount of 0.1 to 0.2 parts by weight with respect to 100 parts by weight of the 1, 3-butadiene monomer;
preferably, in step (c), the first antioxidant is used in an amount of 0.1 to 0.3 parts by weight relative to 100 parts by weight of the 1, 3-butadiene monomer.
11. The production method according to any one of claims 8 to 10, wherein in the step (2), the production method of the linear styrene-butadiene copolymer solution comprises the steps of:
(i) In a second organic solvent, carrying out a second anionic solution polymerization reaction on 1, 3-butadiene and styrene in the presence of a second initiator and optionally a second structure regulator until the conversion rate of the 1, 3-butadiene and the styrene is more than 99%, so as to obtain a butadiene-styrene copolymer active chain; preferably, the butadiene-styrene copolymer has a number average molecular weight of 100,000-140,000 for the active chains;
(ii) In the presence of a second terminator, after terminating the product of the second polymerization anion reaction, adding a second antioxidant to obtain a linear styrene-butadiene copolymer solution;
preferably, in step (i), the weight ratio of styrene to 1, 3-butadiene is from 0.53 to 0.82:1;
preferably, in step (i), the ratio of the total molar amount of 1, 3-butadiene and styrene to the molar amount of the second initiator is from 1300 to 1900:1, a step of;
preferably, in step (i), the molar ratio of the second structure modifier to the second initiator is from 0.02 to 1:1.
preferably, in step (ii), the conditions of the second anionic solution polymerization reaction include: the temperature is 40-100deg.C, preferably 50-100deg.C; the time is 30-80min, preferably 40-60min; the gauge pressure is 0.1-1MPa, preferably 0.2-0.5MPa;
Preferably, in step (ii), the second terminator is used in an amount of 0.02 to 0.8 parts by weight relative to 100 parts by weight of the total amount of 1, 3-butadiene and styrene;
preferably, in step (ii), the second antioxidant is used in an amount of 0.1 to 0.3 parts by weight relative to 100 parts by weight of the total amount of 1, 3-butadiene and styrene.
12. The process of any one of claims 8-11, wherein the first initiator and the second initiator are each independently of the other of formula R 1 Organolithium compounds represented by Li, wherein R 1 An alkyl group selected from C1-C10;
preferably, the first initiator and the second initiator are each independently selected from at least one of n-butyllithium, sec-butyllithium, isobutyl lithium and tert-butyllithium, preferably n-butyllithium and/or sec-butyllithium;
preferably, the first organic solvent and the second organic solvent are each independently an inert non-polar organic solvent, preferably cyclohexane: a mixed solvent with the weight ratio of hexane of 4-19:1;
preferably, the first terminator and the second terminator are each independently selected from at least one of a C1-C4 alcohol, an organic acid, and carbon dioxide, preferably from at least one of isopropanol, stearic acid, citric acid, and carbon dioxide, more preferably carbon dioxide.
13. The production process according to any one of claims 8 to 12, wherein in the step (3), the low cis-polybutadiene solution and the linear styrene-butadiene copolymer solution are used in such an amount that the weight ratio of the low cis-polybutadiene rubber and the linear styrene-butadiene copolymer in the composition is 0.42 to 2.33:1, preferably 0.6-1.5:1.
preferably, in step (4), the water content of the colloidal particles is 40-60wt%;
preferably, the toughener composition has a volatile content of 1wt% or less.
14. A toughening agent composition made by the method of any of claims 8 to 13.
15. Use of the toughening agent composition according to any one of claims 1 to 7 and 14 for preparing ABS resins.
16. The preparation method of the ABS resin is characterized in that styrene and acrylonitrile are copolymerized in the presence of a toughening agent composition to obtain the ABS resin;
wherein the toughening agent composition is the toughening agent composition of any one of claims 1 to 7 and 14.
17. An ABS resin produced by the production process according to claim 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210507036.3A CN117070005A (en) | 2022-05-10 | 2022-05-10 | Toughening agent composition, preparation method and application thereof, ABS resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210507036.3A CN117070005A (en) | 2022-05-10 | 2022-05-10 | Toughening agent composition, preparation method and application thereof, ABS resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117070005A true CN117070005A (en) | 2023-11-17 |
Family
ID=88714031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210507036.3A Pending CN117070005A (en) | 2022-05-10 | 2022-05-10 | Toughening agent composition, preparation method and application thereof, ABS resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117070005A (en) |
-
2022
- 2022-05-10 CN CN202210507036.3A patent/CN117070005A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109503746B (en) | Low cis-polybutadiene rubber and preparation method thereof, HIPS resin and preparation method thereof, and ABS resin | |
| CN109251262B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| JP4989020B2 (en) | Transparent impact resistance improved polystyrene based on styrene butadiene block copolymer, polymer mixture containing the same, and production method thereof | |
| CN109251264B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| WO2013128977A1 (en) | Method for producing branched conjugated diene polymer | |
| CN106414529B (en) | Polyalkenyl coupling agent and conjugated diolefin polymer prepared therefrom | |
| CN104558455B (en) | A kind of butylbenzene copolymer and its preparation method and application | |
| CN105175659A (en) | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor | |
| CN109503747B (en) | Low cis-polybutadiene rubber and preparation method thereof, HIPS resin and preparation method thereof, and ABS resin | |
| CN103382241A (en) | Star-shaped isoprene-b-butadiene styrene terpolymer and preparation method thereof | |
| CN109251263B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| CN109181813A (en) | A kind of star viscosity index improver and preparation method thereof for lubricating oil | |
| CN110387012A (en) | Branched functionalized solution-polymerized styrene-butadiene rubber and preparation method thereof | |
| US9567409B2 (en) | Preparation method of vinyl aromatic hydrocarbon-conjugated diene block copolymer using coupling reaction with improved ion stability | |
| CN117070005A (en) | Toughening agent composition, preparation method and application thereof, ABS resin and preparation method thereof | |
| CN110305240B (en) | Preparation method of polybutadiene oligomer, grafting modifier and rare earth isoprene rubber | |
| CN107286292A (en) | A kind of preparation method of random distribution high-phenylethylene medium vinyl content solution polymerized butadiene styrene rubber | |
| USH1956H1 (en) | Enhanced hydrogenation catalyst removal from block copolymers by reduction in polymer cement viscosity by increasing the vinyl content of the block copolymers | |
| CN113698558B (en) | Styrene-butadiene copolymer and preparation method and application thereof | |
| CN114085434B (en) | Low cis-polybutadiene rubber, preparation method and application thereof, HIPS resin and preparation method thereof | |
| CN110563861B (en) | Epoxy-terminated polydiene hydrocarbon liquid rubber and preparation method thereof | |
| CN111978446B (en) | Polybutadiene rubber, preparation method and application thereof, and aromatic vinyl resin and preparation method thereof | |
| CN114478917B (en) | Styrene-butadiene rubber and preparation method and application thereof | |
| CN113461858B (en) | Low cis-polybutadiene rubber and preparation method thereof, HIPS and preparation method thereof | |
| CN111978447A (en) | Low cis-polybutadiene rubber, preparation method and application thereof, aromatic vinyl resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |