CN103965410B - With rare earth integrated rubber for the toughener method that substance law prepares ABS resin in situ - Google Patents
With rare earth integrated rubber for the toughener method that substance law prepares ABS resin in situ Download PDFInfo
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- CN103965410B CN103965410B CN201410173018.1A CN201410173018A CN103965410B CN 103965410 B CN103965410 B CN 103965410B CN 201410173018 A CN201410173018 A CN 201410173018A CN 103965410 B CN103965410 B CN 103965410B
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- abs resin
- rare earth
- styrene
- integrated rubber
- isoprene
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 114
- 229920001971 elastomer Polymers 0.000 title claims abstract description 101
- 239000005060 rubber Substances 0.000 title claims abstract description 101
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 67
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000000126 substance Substances 0.000 title claims abstract description 15
- 239000012745 toughening agent Substances 0.000 title claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 title abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003292 glue Substances 0.000 claims abstract description 37
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 27
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 19
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229920006031 tri-component-copolymer Polymers 0.000 claims abstract description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 58
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 46
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 150000001993 dienes Chemical class 0.000 claims description 20
- -1 rare earth neodymium carboxylate Chemical class 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 229920001897 terpolymer Polymers 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- ACOLQZDYRBEHEV-UHFFFAOYSA-K decanoate;neodymium(3+) Chemical compound [Nd+3].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O ACOLQZDYRBEHEV-UHFFFAOYSA-K 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical class CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- KLPPPZWWHMSHBQ-UHFFFAOYSA-N C(C)(C)O[Nd] Chemical compound C(C)(C)O[Nd] KLPPPZWWHMSHBQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- 229910000091 aluminium hydride Inorganic materials 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 2
- AZFVLHQDIIJLJG-UHFFFAOYSA-N chloromethylsilane Chemical compound [SiH3]CCl AZFVLHQDIIJLJG-UHFFFAOYSA-N 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
- 238000006392 deoxygenation reaction Methods 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- OCFSGVNHPVWWKD-UHFFFAOYSA-N butylaluminum Chemical compound [Al].[CH2]CCC OCFSGVNHPVWWKD-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 229920005683 SIBR Polymers 0.000 abstract description 43
- 239000002904 solvent Substances 0.000 abstract description 13
- 150000001206 Neodymium Chemical class 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 82
- 238000010792 warming Methods 0.000 description 40
- 230000032683 aging Effects 0.000 description 23
- 238000009826 distribution Methods 0.000 description 23
- 239000000470 constituent Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000012916 structural analysis Methods 0.000 description 11
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 235000010446 mineral oil Nutrition 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 6
- KBDQJVBIULYIPC-UHFFFAOYSA-N bis(2-ethylhexyl)phosphane Chemical compound CCCCC(CC)CPCC(CC)CCCC KBDQJVBIULYIPC-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical class OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Natural products CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention discloses a kind of with rare earth integrated rubber for the toughener method that substance law prepares ABS resin in situ, first with the coordination compound of rare earth neodymium as catalyst, with styrene as solvent, it is prepared for rare earth neodymium series styrene/isoprene/butadiene tri-component copolymer integrated rubber, and with the styrene glue of prepared rare earth integrated rubber Nd SIBR as raw material, acrylonitrile monemer is added by proportioning, the method using conventional free radical polymerization prepares ABS resin, it is achieved thereby that use substance law in situ to prepare ABS resin from rare earth integrated rubber glue.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of with rare earth integrated rubber for toughener original position
Substance law prepares the method for ABS resin.
Background technology
ABS resin be acrylonitrile (A)/styrene (S) copolymer and acrylonitrile (A)/butadiene (B)/
The mixture of styrene (S) graft copolymer, acrylonitrile/styrol copolymer AS is resin-phase, acrylonitrile
/ Butadiene/Styrene graft copolymer is rubber phase.ABS resin is as a kind of important engineering plastics, extensively
It is applied to the fields such as electronics, instrument, automobile, building materials.ABS resin production technology mainly has at present: emulsion
Polymerization, mass polymerization, continuous bulk polymerization process is because its product purity is high, performance is well increasingly subject to
The attention of people.
The preparation method of classical substance law ABS resin is first toughening rubber to be cut into fritter, is then placed in
Stirring and dissolving in styrene/acrylonitrile, then use the polymerization of free radical initiation grafting to obtain ABS resin.Preparation
Process is divided into two parts of production of the production of toughening rubber, ABS resin, it is generally required to complete two units.
The production unit of toughening rubber needs to deviate from solvent through post processing, extruding is dried, packaging pressing section, and
ABS resin production unit again need cut rubber, in styrene/acrylonitrile dissolving rubber workshop section.The present invention
Use substance law in situ that the working set of toughening rubber, ABS resin two units of production is become a unit, directly
It is connected in styrene and prepares toughening rubber, and then use styrene rubber solution to prepare ABS resin, shorten
The technological process of production of ABS resin, eliminates post processing abjection solvent, the extruding stem needed for toughening rubber produces
Dry, packaging three workshop sections of molding and ABS resin production unit needed for cutting rubber, dissolving rubber two
Workshop section, drastically increases production efficiency.Gel in toughening rubber is to cause ABS resin to produce the flake flaw
The main cause of defect, the toughening rubber that therefore ABS resin the is used requirement extremely strict (to gel content
As require that gel content is less than 150ppm).Extruding drying section is that toughening rubber generation gel is of paramount importance
Link, owing to using styrene rubber solution directly to prepare ABS resin, eliminates the dried place of glue extruding
Science and engineering section, the gel having efficiently controlled toughening rubber produces, and drastically increases ABS resin product quality.
Toughening rubber is typically with prepared by the method for polymerisation in solution, such as: use with lithium alkylide for initiator
The method of anionic solution polymerization prepares linear, the low cis polybutadiene rubber of star；Urge with cobalt system Z-N
Agent is the cis-rich polybutadiene rubber using the method being coordinated polymerisation in solution to prepare of representative；Due to benzene second
Alkene also has higher polymerization activity in above-mentioned polymerization, and styrene can be polymerized anti-by full entry
Should, the most above-mentioned preparation method cannot select styrene to be solvent, generally use saturated alkane (hexamethylene,
Hexane, raffinate oil) it is solvent.
The invention is characterized in that the system using substance law in situ to prepare ABS resin, toughening rubber and ABS resin
For completing at same unit, selected method must simultaneously meet following requirements: owing to using styrene
For solvent, therefore cause catalyst system and catalyzing that styrene polymerization must be had highly controllable selectivity；Due to system
Initiation catalyst system and catalyzing needed for standby toughening rubber will remain in glue, and therefore toughening rubber is prepared and used
The necessary active height of initiation catalyst system and catalyzing, the characteristic that consumption is few, and metal ion valence stability, it is impossible to
Use and there is the transition-metal catalyst of characteristic of appraising at the current rate (variation of valence of transition metal causes polymer ageing-resistant
Degradation)；Owing to the gel content of toughening rubber is required high by ABS resin, therefore toughening rubber institute
The catalyst system and catalyzing that causes used must have low gel or the characteristic without gel；Owing to gelatin viscosity is to ABS tree
The morphosis of fat and the impact of rubber size size are relatively big, and therefore toughening rubber is prepared used initiation and urged
Change system must have the characteristic of relatively low gelatin viscosity.
Active anionic polymerization method with lithium alkylide as initiator, owing to the selectivity of styrene polymerization cannot
Controlling, can react with full entry, therefore cannot use styrene is solvent, it is impossible to meet wanting of the present invention
Ask；Coordination polymerization process with cobalt, nickel as catalyst, owing to the active center of catalyst is valence state mutability
Transition metal, remain in the aged deterioration easily causing ABS resin in glue, can not meet the present invention's
Requirement.Rare earth metal complex catalyst system and catalyzing, because its active height, selectivity are good, rare earth metal valence state
Characteristic constant, that rare-earth rubber gel content is low, the present invention selects rare earth metal complex to be catalyst.
Compared with traditional polybutadiene rubber, butadiene-styrene rubber, integrated rubber SIBR is as phenylethylene resin series
Toughening rubber more efficiently improve the shock resistance of phenylethylene resin series, show the most excellent
Combination property.The Chinese patent ZL200310101975.5 of Li Yang et al. discloses a class ultrahigh impact strength
Polystyrene resin and preparation method thereof, the integrated rubber SIBR using active anionic polymerization method to prepare
It is dissolved in styrene, is prepared for Izod impact strength by free yl graft polymerization method and is up to 380J/m
Polystyrene resin with ultrahigh impact strength.The Chinese patent CN101899131A of Li Yang et al. (application number:
201010110104.X) disclose class ABS (Acrylonitrile Butadiene Styrene) resin with ultrahigh impact strength and preparation method thereof, using
Integrated rubber SIBR prepared by active anionic polymerization method is dissolved in styrene/acrylonitrile, by freedom
Base graft polymerization procedure is prepared for ABS (Acrylonitrile Butadiene Styrene) resin with ultrahigh impact strength.Above-mentioned two inventions all use with alkyl
Lithium be initiator be toughener by integrated rubber SIBR prepared by active anionic polymerization, by traditional side
SIBR is cut into fritter and is re-dissolved in styrene or styrene/acrylonitrile by method, free yl graft polymerization system
Standby HIPS and ABS, rather than the employing disclosed in this invention substance law toughness reinforcing rubber with styrene as solvent in situ
ABS resin directly prepared by glue glue.More merit attention is some the lithium system prepared by active anionic polymerization
Integrated rubber Li-SIBR structurally has with the neodymium series integrated rubber Nd-SIBR prepared by rare-earth catalysis system
There is significant difference, compared with lithium system integrated rubber, the suitable 1，4-polybutadiene knot of rare earth neodymium system integrated rubber
Structure content, suitable Isosorbide-5-Nitrae-polyisoprene structural content are higher, and high suitable Isosorbide-5-Nitrae structure contributes to rare earth neodymium assembly
Rubber is become to have more preferably rebound performance.
The Chinese patent ZL201010271998.0 of Li Yang et al. disclose rare earth catalyst system and catalyzing styrene/
Isoprene/butadiene ternary atactic copolymer and preparation method thereof, uses rare earth neodymium coordination compound, Organoaluminoxy
The catalyst system and catalyzing that alkane, cyclopentadiene and alkadienes are formed, is prepared for benzene in saturated alkane, aromatic solvent
Ethylene/isoprene/butadiene ternary atactic copolymer.Chinese patent CN102786621A (the Shen of Li Yang et al.
Please number: 201210251817.7) disclose a class based on rare-earth catalysis system high-cis styrene/isoprene
/ butadiene terpolymer and preparation method thereof, uses rare earth neodymium coordination compound, alkyl aluminum, chloride and diene
The catalyst system and catalyzing that hydrocarbon is formed, is prepared for high-cis styrene/isoprene in saturated alkane, aromatic solvent
/ butadiene terpolymer.It is solvent that above-mentioned two inventions all use saturated alkane, aromatic hydrocarbons, and non-invention
Disclosed with styrene as solvent.The key character of the present invention is that employing rare-earth catalysis system preparation increases
During tough rubber styrene/isoprene/butadiene terpolymer, styrene is solvent, is again single
Body.
United States Patent (USP) US3264374, US4311819, US6310151, US3299178, US5096970,
US20030134999, US20040030071 disclose a series of elastomeric method in styrene solvent,
Be respectively adopted active anionic polymerization method, transition metal-catalyzed coordination polymerization process, catalyzing of rare-earth metal are joined
Position polymerization is prepared for polybutadiene rubber, butadiene/styrene copolymers rubber, but is all not directed to dilute
Earth metal is styrene catalyzed/isoprene/butadiene terpolymer integrated rubber, more it is not involved with dilute
Soil integrated rubber is the toughener method that substance law prepares ABS resin in situ.
Summary of the invention
The invention provides a kind of side preparing ABS resin with rare earth integrated rubber for toughener substance law in situ
Method, first with the coordination compound of rare earth neodymium as catalyst, with styrene as solvent, is prepared for rare earth neodymium series benzene second
Alkene/isoprene/butadiene terpolymer integrated rubber, and with prepared rare earth integrated rubber Nd-SIBR
Styrene glue be raw material, by proportioning add acrylonitrile monemer, use conventional free radical polymerization method system
Standby ABS resin, thus realize using substance law in situ to prepare ABS resin from rare earth integrated rubber glue.
Technical scheme is as follows:
A kind of with rare earth integrated rubber for the toughener method that substance law prepares ABS resin in situ, its feature exists
Following two step is included in the method:
Step one: prepare rare earth integrated rubber glue
(1) rare-earth catalysis system is prepared
Rare-earth catalysis system is made up of following A, tetra-parts of B, C, D, and the mol ratio of each component is: B:A=
(5-25): 1, C:A=(0.1-9): 1, D:A=(5-30): 1；Wherein:
A is selected from the rare earth neodymium carboxylate of rare earth neodymium organic compound, rare earth neodymium phosphonate, alkoxyl neodymium
Kind or several mixture, preferably be selected from (2-ethylhexyl) phosphonic acids neodymium list-2-Octyl Nitrite, two (2-ethyls
Hexyl) phosphonic acids neodymium, neodymium caprate, neodymium naphthenate, neodymium iso-octanate, three (isopropoxy) neodymium；
The B mixture of one or more in the trialkylaluminium of alkyl aluminum, alkyl aluminium hydride, preferably is selected from hydrogen
Change diisobutyl aluminum, triisobutyl aluminium, triethyl aluminum；
One or more in alkyl chloride, chlorosilane, chloro alkyl aluminum, sesquialter alkyl aluminum chloride of C
Mixture, preferably be selected from a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter ethylmercury chloride aluminum, chloroform,
Dichloromethane, monochloro methane, Silicon chloride., chloromethyl silane；
The D mixture of one or more in diolefin butadiene, isoprene, pentadiene；
Under noble gas argon or nitrogen are protected, in dry hydrogen-catalyst reactor, pressProportioningAdd successively
Enter A, B, D, C, at 10 DEG C-80 DEG C react 0.5h-24h, obtain for prepare rare earth styrene/
The rare-earth catalysis system of isoprene/butadiene terpolymer integrated rubber；
(2) under noble gas argon or nitrogen are protected, add successively in the polymer reactor of dry deoxygenation by proportioning
Entering styrene, conjugated diene isoprene and butadiene, gelatin concentration is 8-40g/ mL, is subsequently adding
Stating the rare-earth catalysis system prepared by step (1), rare earth catalyst consumption is Nd/ conjugated diene monomer
Mol ratio is 1 × 10-4-4×10-3, at 0 DEG C-100 DEG C react 0.5h-24h, obtain rare earth styrene/
The styrene glue of isoprene/butadiene terpolymer integrated rubber；Rare earth styrene/isoprene/fourth
The weight average molecular weight of diene terpolymer is 10 × 104-100×104, preferably 15 × 104-60×104；
In terms of styrene/isoprene/butadiene tri-component copolymer total amount 100%, styrene-content mass percent is
5%-60%, preferably 15%-50%；Butadiene content mass percent is 10%-70%, preferably 20%-45%；
Isoprene content mass percent is 10%-70%, preferably 20%-45%；
Step 2: prepare high-impact ABS resin
According to the requirement of integrated rubber, acrylonitrile content in ABS resin, acrylonitrile is joined above-mentioned steps
In the glue of the rare earth styrene/isoprene/butadiene tri-component copolymer integrated rubber prepared by (2),
The most optional styrene of adding regulates gelatin concentration；Can be selected for chain-transferring agent to regulate ABS resin
Molecular weight, chain-transferring agent be selected from ethylbenzene, ethylbenzene consumption mass percent is 5%-35%；At mass polymerization
In course of reaction, ethylbenzene has the effect of diluent simultaneously；The weight average molecular weight of ABS resin phase is 10 × 104-
80×104, preferably 15 × 104-60 × 104；Integrated rubber content mass percent in ABS resin
For 5%-35%, preferably 10%-25%；Acrylonitrile content mass percent in ABS resin is 5%-50%,
It is preferably 10%-35%；Use free radical polymerisation process initiated polymerization carry out, initiating method be thermal initiation or
Initiator causes, and initiator is selected from peroxide, azo heat decomposition type initiator, and peroxide thermally decomposes
Type initiator selected from peroxidating two acyl, peroxy dicarbonate, peroxycarboxylic acid esters, alkyl peroxide,
Peroxidating two alkane, preferably is selected from dibenzoyl peroxide, peroxidating two o-methyl-benzene formyl, acetyl peroxide
Isobutyryl, the different lactone of peroxy dicarbonate two, peroxy dicarbonate di-t-butyl cyclohexyl, peroxidating spy penta
Tert-butyl acrylate, peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide, 1,1-bis-
(tert-butyl peroxide) hexamethylene, cumyl peroxide, 3,6,9-trimethyl-3,6,9-triethyl group
The mixture of one or more initiators in-1,4,7-three peroxide alkane；Azo heat decomposition type initiator is selected from
In azodiisobutyronitrile, azo-bis-iso-dimethyl, azo isobutyl cyano group Methanamide, 2,2'-Azobis(2,4-dimethylvaleronitrile)
The mixture of one or more initiators；Reaction uses traditional method that polymer is carried out post processing after terminating,
Obtain ABS resin.The initiator of radical polymerization can select the mixed of one or more in above-mentioned initiator
Compound, initiator can be simple function group, difunctional, trifunctional or multifunctional initiator.Public
The substance law opened, continuous bulk prepare the technology of ABS resin and method all can be applicable to step 2 of the present invention
The process of preparation ABS resin.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment, but and the model of unrestricted the claims in the present invention protection
Enclose.It is as follows that Inventive polymers properity analyzes method: integrated rubber SIBR microstructure uses nuclear-magnetism
Resonance wave spectrum (NMR) test, molecular weight and molecular weight distribution thereof use chromatograph of gel permeation (GPC) test,
Izod notched impact strength (Izod) is according to ISO180:2000 standard testing.
Embodiment 1
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 1.8ml neodymium caprate NdV3(0.167
Mol/L hexane solution), 4.5ml triisobutyl aluminium TIBA (hexane solution of 1.0mol/L), 0.3
Ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 0.6ml Silicon chloride. SiCl4(0.667
The hexane solution of mol/L) reaction 40min, mix homogeneously, stand-by after ageing.
50g styrene (St), 5g1,3-butadiene (Bd), 5g is added in 200ml polymer reactor
Isoprene (Ip)；([Nd]/conjugated diene monomer mol ratio is 4 to add the catalyst after 1.6ml ageing
×10-4), open stirring, under the conditions of 70 DEG C, react 4h, prepare that SIBR glue is stand-by (takes out simultaneously
A small amount of SIBR glue uses traditional treatment method to carry out after drying forming, structural analysis)；Add styrene
8.6g, acrylonitrile 15.9g, ethylbenzene 15.9g, 1,1-bis-(tert-butyl peroxide) hexamethylene (mass fraction
The mineral oil solution of 50%) 0.1593g, it is warming up to 105 DEG C and starts polymerization, at 105 DEG C, react 2h, then
It is warming up to 125 DEG C of reaction 4h, then is warming up to 145 DEG C of reaction 4h, then be warming up to 180 DEG C of reaction 2h, prepare
ABS resin, product is dried 24 hours in vacuum drying oven at 80 DEG C, the structure of test sample and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 10.5%, Bd group
Point mass fraction is 46.5%, Ip constituent mass mark is 43.0%；Weight average molecular weight 23.5 × 104, molecule
Amount distribution 5.2.Integrated rubber content mass fraction in ABS resin is 9.5%；ABS resin phase weight average
Molecular weight is 24.4 × 104, molecular weight distribution 2.2；ABS resin Izod notched impact strength is 15.6
kJ/m2；Acrylonitrile content mass percent in ABS resin is 18.9%.
Embodiment 2
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 1.5ml neodymium caprate NdV3(0.167
Mol/L hexane solution), 3.8ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L),
0.5ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 1.2ml aluminium diethyl monochloride (0.8mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
In 200ml polymer reactor add 50g styrene (St), 7.5g1,3-butadiene (Bd),
2.5g isoprene (Ip)；Add catalyst ([the Nd]/conjugated diene monomer mole after 2.4ml ageing
Ratio is 6 × 10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare SIBR glue stand-by (simultaneously
Take out a small amount of SIBR glue use traditional treatment method to carry out after drying forming, structural analysis)；Add benzene second
Alkene 56.8g, acrylonitrile 9.4g, dibenzoyl peroxide 0.2720g, be warming up to 87 DEG C and start polymerization,
React 2h at 87 DEG C, then be warming up to 125 DEG C of reaction 4h, then be warming up to 145 DEG C of reaction 4h, then be warming up to
180 DEG C of reaction 2h, prepare ABS resin, and product is dried 24 hours in vacuum drying oven at 80 DEG C, surveys
The structure of test agent and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 7.5%, Bd component
Mass fraction is 72.4%, Ip constituent mass mark is 20.1%；Weight average molecular weight 18.2 × 104, molecular weight
Distribution 3.6.Integrated rubber content mass fraction in ABS resin is 8.3%；ABS resin phase weight average divides
Son amount is 18.5 × 104, molecular weight distribution 2.2；ABS resin Izod notched impact strength is 10.5
kJ/m2；Acrylonitrile content mass percent in ABS resin is 10.1%.
Embodiment 3
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 2.0ml neodymium caprate NdV3(0.167
Mol/L hexane solution), 6.5ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L),
0.3ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 1.0ml chloroform (1.0mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
50g styrene (St), 5g1,3-butadiene (Bd), 5g is added in 200ml polymer reactor
Isoprene (Ip)；([Nd]/conjugated diene monomer mol ratio is 6 to add the catalyst after 2.9ml ageing
×10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare that SIBR glue is stand-by (takes out simultaneously
A small amount of SIBR glue uses traditional treatment method to carry out after drying forming, structural analysis)；Add styrene 8.6
G, acrylonitrile 15.9g, ethylbenzene 15.9g, 1,1-bis-(tert-butyl peroxide) hexamethylene (mass fraction 50%
Mineral oil solution) 0.1593g, be warming up to 105 DEG C and start polymerization, at 105 DEG C, react 2h, then heat up
To 125 DEG C of reaction 4h, then it is warming up to 145 DEG C of reaction 4h, then is warming up to 180 DEG C of reaction 2h, prepare ABS
Resin, product is dried 24 hours in vacuum drying oven at 80 DEG C, the structure of test sample and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 17.1%, Bd group
Point mass fraction is 42.5%, Ip constituent mass mark is 40.4%；Weight average molecular weight 23.2 × 104, molecule
Amount distribution 3.8.Integrated rubber content mass fraction in ABS resin is 19.5%；ABS resin is mutually overlapping
Average molecular weight is 25.2 × 104, molecular weight distribution 2.4；ABS resin Izod notched impact strength is 17.1
kJ/m2；Acrylonitrile content mass percent in ABS resin is 20.1%.
Embodiment 4
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 0.4175g bis-(2-ethylhexyl) phosphine
Acid neodymium Nd (P204)3, 5.6ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L), 0.4
Ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 1.1ml chloroform (1.0mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
50g styrene (St), 5g1,3-butadiene (Bd), 5g is added in 200ml polymer reactor
Isoprene (Ip)；([Nd]/conjugated diene monomer mol ratio is 6 to add the catalyst after 1.9ml ageing
×10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare that SIBR glue is stand-by (takes out simultaneously
A small amount of SIBR glue uses traditional treatment method to carry out after drying forming, structural analysis)；Add acrylonitrile 5.5
G, 1,1-bis-(tert-butyl peroxide) hexamethylene (mineral oil solution of mass fraction 50%) 0.1210g, rise
Temperature causes polymerization to 105 DEG C, reacts 2h, then is warming up to 125 DEG C of reaction 4h, then be warming up at 105 DEG C
145 DEG C reaction 4h, then be warming up to 180 DEG C reaction 2h, prepare ABS resin, product in vacuum drying oven in
It is dried 24 hours at 80 DEG C, the structure of test sample and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 20.0%, Bd group
Point mass fraction is 44.0%, Ip constituent mass mark is 36.0%；Weight average molecular weight 17.2 × 104, molecule
Amount distribution 5.0.Integrated rubber content mass fraction in ABS resin is 20.1%；ABS resin is mutually overlapping
Average molecular weight is 32.5 × 104, molecular weight distribution 2.5；ABS resin Izod notched impact strength is 22.1
kJ/m2；Acrylonitrile content mass percent in ABS resin is 22.6%.
Embodiment 5
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 0.2222g bis-(2-ethylhexyl) phosphine
Acid neodymium Nd (P204)3, 3.0ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L), 0.2
Ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 1.2ml chloroform (1.0mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
45g styrene (St), 9g1,3-butadiene (Bd), 9g is added in 200ml polymer reactor
Isoprene (Ip)；([Nd]/conjugated diene monomer mol ratio is 3 to add the catalyst after 2.9ml ageing
×10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare that SIBR glue is stand-by (takes out simultaneously
A small amount of SIBR glue uses traditional treatment method to carry out after drying forming, structural analysis)；Add styrene 9.5
G, acrylonitrile 17.4g, 1,1-bis-(tert-butyl peroxide) hexamethylene (mineral oil solution of mass fraction 50%)
0.0681g, is warming up to 105 DEG C and starts polymerization, reacts 2h, then be warming up to 125 DEG C of reactions at 105 DEG C
4h, then it is warming up to 145 DEG C of reaction 4h, then it is warming up to 180 DEG C of reaction 2h, prepare ABS resin, product
Vacuum drying oven is dried 24 hours at 80 DEG C, the structure of test sample and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 10.3%, Bd group
Point mass fraction is 48.0%, Ip constituent mass mark is 41.7%；Weight average molecular weight 35.2 × 104, molecule
Amount distribution 4.3.Integrated rubber content mass fraction in ABS resin is 20.3%；ABS resin is mutually overlapping
Average molecular weight is 36.3 × 104, molecular weight distribution 2.0；ABS resin Izod notched impact strength is 25.7
kJ/m2；Acrylonitrile content mass percent in ABS resin is 19.1%.
Embodiment 6
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 0.2470g bis-(2-ethylhexyl) phosphine
Acid neodymium Nd (P204)3, 1.2ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L), 0.2
Ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 8.0ml chloroform (1.0mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
50g styrene (St), 2g1,3-butadiene (Bd), 2g is added in 200ml polymer reactor
Isoprene (Ip)；([Nd]/conjugated diene monomer mol ratio is to add the catalyst after 3.4ml ageing
12×10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare that SIBR glue is stand-by (takes simultaneously
Go out a small amount of SIBR glue use traditional treatment method to carry out after drying forming, structural analysis)；Add styrene
35.7g, acrylonitrile 14.7g, azodiisobutyronitrile 0.1893g, be warming up to 80 DEG C and start polymerization, at 80 DEG C
Lower reaction 2h, then it is warming up to 125 DEG C of reaction 4h, then it is warming up to 145 DEG C of reaction 4h, then it is warming up to 180 DEG C
Reaction 2h, prepares ABS resin, and product is dried 24 hours in vacuum drying oven at 80 DEG C, test sample
Structure and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 48.2%, Bd group
Point mass fraction is 24.1%, Ip constituent mass mark is 27.7%；Weight average molecular weight 9.5 × 104, molecular weight
Distribution 3.5.Integrated rubber content mass fraction in ABS resin is 10.3%；ABS resin phase weight average
Molecular weight is 56.2 × 104, molecular weight distribution 3.2；ABS resin Izod notched impact strength is 9.7
kJ/m2；Acrylonitrile content mass percent in ABS resin is 25.7%.
Embodiment 7
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 0.2764g bis-(2-ethylhexyl) phosphine
Acid neodymium Nd (P204)3, 3.7ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L), 0.3
Ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 0.8ml chloroform (1.0mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
In 200ml polymer reactor add 50g styrene (St), 10g1,3-butadiene (Bd),
10g isoprene (Ip)；Add catalyst ([the Nd]/conjugated diene monomer mole after 2.3ml ageing
Ratio is 3.6 × 10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare SIBR glue stand-by (same
Time take out a small amount of SIBR glue use traditional treatment method to carry out after drying forming, structural analysis)；Add third
Alkene nitrile 6.5g, 1,1-bis-(tert-butyl peroxide) hexamethylene (mineral oil solution of mass fraction 50%) 0.1430
G, is warming up to 105 DEG C and starts polymerization, reacts 2h, then is warming up to 125 DEG C of reaction 4h, then rise at 105 DEG C
Temperature is to 145 DEG C of reaction 4h, then is warming up to 180 DEG C of reaction 2h, prepares ABS resin, and product dries in vacuum
Case is dried 24 hours at 80 DEG C, the structure of test sample and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 17.1%, Bd group
Point mass fraction is 45.0%, Ip constituent mass mark is 37.9%；Weight average molecular weight 15.8 × 104, molecule
Amount distribution 4.0.Integrated rubber content mass fraction in ABS resin is 30.2%；ABS resin is mutually overlapping
Average molecular weight is 30.9 × 104, molecular weight distribution 2.2；ABS resin Izod notched impact strength is 29.7
kJ/m2；Acrylonitrile content mass percent in ABS resin is 22.7%.
Embodiment 8
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 0.2764g bis-(2-ethylhexyl) phosphine
Acid neodymium Nd (P204)3, 3.7ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L), 0.3
Ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 0.8ml chloroform (1.0mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
In 200ml polymer reactor add 50g styrene (St), 10g1,3-butadiene (Bd),
10g isoprene (Ip)；Add catalyst ([the Nd]/conjugated diene monomer mole after 2.3ml ageing
Ratio is 3.6 × 10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare SIBR glue stand-by (same
Time take out a small amount of SIBR glue use traditional treatment method to carry out after drying forming, structural analysis)；Add benzene
Ethylene 10.3g, acrylonitrile 18.8g, 1,1-bis-(tert-butyl peroxide) hexamethylene (ore deposit of mass fraction 50%
Thing oil solution) 0.3767g, it is warming up to 105 DEG C and starts polymerization, at 105 DEG C, react 2h, then be warming up to
125 DEG C are continued reaction 4h, then are warming up to 145 DEG C of reaction 4h, then be warming up to 180 DEG C of reaction 2h, prepare
ABS resin, product is dried 24 hours in vacuum drying oven at 80 DEG C, the structure of test sample and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 17.1%, Bd group
Point mass fraction is 45.0%, Ip constituent mass mark is 37.9%；Weight average molecular weight 15.8 × 104, molecule
Amount distribution 4.0.Integrated rubber content mass fraction in ABS resin is 20.3%；ABS resin is mutually overlapping
Average molecular weight is 36.3 × 104, molecular weight distribution 2.0；ABS resin Izod notched impact strength is 25.7
kJ/m2；Acrylonitrile content mass percent in ABS resin is 19.1%.
Embodiment 9
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 0.2764g bis-(2-ethylhexyl) phosphine
Acid neodymium Nd (P204)3, 3.7ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L), 0.3
Ml isoprene (Ip), after 30 DEG C of reaction 10min, adds 0.8ml chloroform (1.0mol/L
Hexane solution) reaction 40min, mix homogeneously, stand-by after ageing.
In 200ml polymer reactor add 50g styrene (St), 10g1,3-butadiene (Bd),
10g isoprene (Ip)；Add catalyst ([the Nd]/conjugated diene monomer mole after 2.3ml ageing
Ratio is 3.6 × 10-4), open stirring, under the conditions of 50 DEG C, react 6h, prepare SIBR glue stand-by (same
Time take out a small amount of SIBR glue use traditional treatment method to carry out after drying forming, structural analysis)；Add third
Alkene nitrile 7.7g, ethylbenzene 8.2g, 3,6,9-trimethyl-3,6,9-triethyl group-1,4,7-three peroxide alkane (divide by quality
The mineral oil solution of several 40%) 0.3735g, it is warming up to 135 DEG C and starts polymerization, at 135 DEG C, react 2h,
It is warming up to 155 DEG C of reaction 4h again, then is warming up to 175 DEG C of reaction 4h, then be warming up to 200 DEG C of reaction 2h, system
Obtaining ABS resin, product is dried 24 hours in vacuum drying oven at 80 DEG C, test sample structure and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 17.1%, Bd group
Point mass fraction is 45.0%, Ip constituent mass mark is 37.9%；Weight average molecular weight 15.8 × 104, molecule
Amount distribution 4.0.Integrated rubber content mass fraction in ABS resin is 28.3%；ABS resin is mutually overlapping
Average molecular weight is 30.5 × 104, molecular weight distribution 2.0；ABS resin Izod notched impact strength is 28.7
kJ/m2；Acrylonitrile content mass percent in ABS resin is 24.2%.
Embodiment 10
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 0.1634g (2-ethylhexyl) phosphonic acids
Neodymium list-2-Octyl Nitrite Nd (P507)3, the 2.7ml diisobutylaluminium hydride DIBAH (normal hexane of 1.0mol/L
Solution), 0.2ml butadiene solution (now joining the hexane solution of 1.0mol/L), 30 DEG C reaction 10min
After, add 1.6ml aluminium diethyl monochloride (hexane solution of 1.0mol/L) reaction 40min, mixing
Uniformly, stand-by after ageing.
In 200ml polymer reactor add 40g styrene (St), 10g1,3-butadiene (Bd), 10
G isoprene (Ip)；([Nd]/conjugated diene monomer mol ratio is to add the catalyst after 2.5ml ageing
3×10-4), open stirring, under the conditions of 70 DEG C, react 6h, prepare that SIBR glue is stand-by (takes out simultaneously
A small amount of SIBR glue uses traditional treatment method to carry out after drying forming, structural analysis)；Add styrene 32.4
G, acrylonitrile 53.7g, peroxidized t-butyl perbenzoate (mineral oil solution of mass fraction 50%) 0.6052
G, is warming up to 120 DEG C and causes polymerization, reacts 2h, then is warming up to 145 DEG C of reaction 4h, then rise at 120 DEG C
Temperature is to 165 DEG C of reaction 4h, then is warming up to 180 DEG C of reaction 2h, prepares ABS resin, and product dries in vacuum
Case is dried 24 hours at 80 DEG C, the structure of test sample and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 13.5%, Bd group
Point mass fraction is 45.2%, Ip constituent mass mark is 41.3%；Weight average molecular weight 55.1 × 104, molecule
Amount distribution 6.2.Integrated rubber content mass fraction in ABS resin is 19.8%；ABS resin is mutually overlapping
Average molecular weight is 42.5 × 104, molecular weight distribution 3.0；ABS resin Izod notched impact strength is 15.2
kJ/m2；Acrylonitrile content mass percent in ABS resin is 33.6%.
Embodiment 11
Under room temperature, in the hydrogen-catalyst reactor of 20ml, it is sequentially added into 1.9ml isopropoxy neodymium (0.1mol/L
Toluene solution), 2.9ml diisobutylaluminium hydride DIBAH (hexane solution of 1.0mol/L), 0.2
Ml butadiene solution (now joins the hexane solution of 1.0mol/L), after 30 DEG C of reaction 10min, adds
0.4ml sesquialter ethylmercury chloride aluminum Et3Al2Cl3(hexane solution of 0.75mol/L) reaction 40min, mixing
Uniformly, stand-by after ageing.
40g styrene (St), 2g1,3-butadiene (Bd), 6g is added in 200ml polymer reactor
Isoprene (Ip)；([Nd]/conjugated diene monomer mol ratio is 9 to add the catalyst after 3.2ml ageing
×10-4), open stirring, under the conditions of 70 DEG C, react 6h, prepare that SIBR glue is stand-by (takes out simultaneously
A small amount of SIBR glue uses traditional treatment method to carry out after drying forming, structural analysis)；Add styrene 42.5
G, acrylonitrile 14.6g, ethylbenzene 18.6g, 3,6,9-trimethyl-3,6,9-triethyl group-1,4,7-three peroxide alkane
(mineral oil solution of mass fraction 40%) 0.0396g, is warming up to 135 DEG C and starts polymerization, anti-at 135 DEG C
Answer 2h, then be warming up to 155 DEG C of reaction 4h, then be warming up to 175 DEG C of reaction 4h, then be warming up to 200 DEG C instead
Answering 2h, prepare ABS resin, product is dried 24 hours in vacuum drying oven at 80 DEG C, test sample
Structure and performance.
Sample structure and performance are as follows: in integrated rubber SIBR St constituent mass mark be 25.7%, Bd group
Point mass fraction is 14.3%, Ip constituent mass mark is 60.0%；Weight average molecular weight 12.3 × 104, molecule
Amount distribution 4.5.Integrated rubber content mass fraction in ABS resin is 7.5%；ABS resin phase weight average
Molecular weight is 25.4 × 104, molecular weight distribution 1.9；ABS resin Izod notched impact strength is 14.5
kJ/m2；Acrylonitrile content mass percent in ABS resin is 20.4%.
Claims (10)
1. the method preparing ABS resin for toughener original position substance law with rare earth integrated rubber, it is characterised in that
The method includes following two step:
Step one: prepare rare earth integrated rubber glue
(1) rare-earth catalysis system is prepared
Rare-earth catalysis system is made up of following A, tetra-parts of B, C, D, and the mol ratio of each component is: B:A=
(5-25): 1, C:A=(0.1-9): 1, D:A=(5-30): 1；Wherein:
A one in the rare earth neodymium carboxylate of rare earth neodymium organic compound, rare earth neodymium phosphonate, alkoxyl neodymium
Or several mixture；
The B mixture of one or more in the trialkylaluminium of alkyl aluminum, alkyl aluminium hydride；
Mixing of one or more in alkyl chloride, chlorosilane, chloro alkyl aluminum, sesquialter alkyl aluminum chloride of C
Compound；
The D mixture of one or more in diolefin butadiene, isoprene, pentadiene；
Under noble gas argon or nitrogen are protected, in dry hydrogen-catalyst reactor, depend on by said ratio
Secondary addition A, B, D, C, react 0.5h-24h at 10 DEG C-80 DEG C, obtain for preparing rare earth benzene second
The rare-earth catalysis system of alkene/isoprene/butadiene terpolymer integrated rubber；
(2) under noble gas argon or nitrogen are protected, in the polymer reactor of dry deoxygenation, benzene second it is sequentially added into
Alkene, conjugated diene isoprene and butadiene, gelatin concentration is 8-40g/100mL, is subsequently adding above-mentioned
Rare-earth catalysis system prepared by step (1), rare earth catalyst consumption is rubbing of Nd/ conjugated diene monomer
Your ratio is 1 × 10-4-4×10-3, at 0 DEG C-100 DEG C, react 0.5h-24h, obtain rare earth styrene/different
The styrene glue of pentadiene/butadiene terpolymer integrated rubber；Rare earth styrene/isoprene/fourth two
The weight average molecular weight of alkene terpolymer integrated rubber is 10 × 104-100×104；With rare earth styrene/isoamyl
Diene/butadiene terpolymer integrated rubber total amount 100% is counted, styrene-content matter in rare earth integrated rubber
Amount percent is 5%-60%, and butadiene content mass percent is 10%-70%, isoprene content quality hundred
Mark is 10%-70%；
Step 2: preparation ABS resin
According to the requirement of integrated rubber, acrylonitrile content in ABS resin, acrylonitrile is joined above-mentioned steps
In the glue of the rare earth styrene/isoprene/butadiene tri-component copolymer integrated rubber prepared by (2),
The most optionally select to add styrene regulation gelatin concentration；Select chain-transferring agent to regulate dividing of ABS resin
Son amount, chain-transferring agent is selected from ethylbenzene, and ethylbenzene consumption mass percent is 5%-35%；The weight average of ABS resin phase
Molecular weight is 10 × 104-80 × 104, integrated rubber content mass percent in ABS resin is 5%-
35%；Acrylonitrile content mass percent in ABS resin is 5%-50%；Use free radical polymerisation process
Initiated polymerization is carried out, and initiating method is that thermal initiation or initiator cause, initiator selected from peroxide,
The double nitrile heat decomposition type initiator of azo, reaction carries out post processing to polymer after terminating, obtains ABS resin.
Method the most according to claim 1, it is characterised in that: in rare-earth catalysis system, A is selected from (2-ethyl
Hexyl) phosphonic acids neodymium list-2-Octyl Nitrite, two (2-ethylhexyl) phosphonic acids neodymium, neodymium caprate, neodymium naphthenate,
The mixture of one or more in neodymium iso-octanate or three (isopropoxy) neodymium.
Method the most according to claim 1 and 2, it is characterised in that: in rare-earth catalysis system, B is selected from hydrogenation
The mixture of one or more in diisobutyl aluminum, triisobutyl aluminium or triethyl aluminum.
Method the most according to claim 3, it is characterised in that: in rare-earth catalysis system, C is different selected from a chlorine two
Butyl aluminum, aluminium diethyl monochloride, sesquialter ethylmercury chloride aluminum, chloroform, dichloromethane, monochloro methane,
The mixture of one or more in Silicon chloride. or chloromethyl silane.
5. according to the method described in claim 1 or 2 or 4, it is characterised in that: with rare earth styrene/isoprene
/ butadiene terpolymer integrated rubber total amount 100% is counted, styrene-content quality hundred in rare earth integrated rubber
Mark is 15%-50%, and butadiene content mass percent is 20%-45%, isoprene content mass percent
For 20%-45%.
6. according to the method described in claim 1 or 2 or 4, it is characterised in that: rare earth styrene/isoprene/
The weight average molecular weight of butadiene terpolymer integrated rubber is 15 × 104-60×104；The weight of ABS resin phase
Average molecular weight is 15 × 104-60 × 104。
7. according to the method described in claim 1 or 2 or 4, it is characterised in that: rare earth styrene/isoprene/
Butadiene terpolymer integrated rubber content mass percent in ABS resin is 10%-25%；Propylene
Nitrile content mass percent in ABS resin is 10%-35%.
Method the most according to claim 3, it is characterised in that: with rare earth styrene/isoprene/butadiene
Terpolymer integrated rubber total amount 100% is counted, and in rare earth integrated rubber, styrene-content mass percent is
15%-50%, butadiene content mass percent is 20%-45%, and isoprene content mass percent is
20%-45%.
Method the most according to claim 3, it is characterised in that: rare earth styrene/isoprene/butadiene three
The weight average molecular weight of membered copolymer integrated rubber is 15 × 104-60×104；The weight average molecular weight of ABS resin phase
It is 15 × 104-60 × 104。
Method the most according to claim 3, it is characterised in that: rare earth styrene/isoprene/butadiene three
Membered copolymer integrated rubber content mass percent in ABS resin is 10%-25%；Acrylonitrile is at ABS
Content mass percent in resin is 10%-35%.
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| CN1309674A (en) * | 1998-07-18 | 2001-08-22 | 拜尔公司 | Method for polymerizing conjugated diolefins (dienes) with rare-earth catalysts in presence of vinylaromatic solvents |
| CN102786621A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method |
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| CN101899131A (en) * | 2010-02-10 | 2010-12-01 | 大连理工大学 | ABS (Acrylonitrile Butadiene Styrene) resin with ultrahigh impact strength and preparation method thereof |
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| CN102786621A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method |
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