CN1587292B - Reactive Extrusion Polymerization Method of Nanoscale Dispersed Phase Styrenic Multi-block Copolymer - Google Patents
Reactive Extrusion Polymerization Method of Nanoscale Dispersed Phase Styrenic Multi-block Copolymer Download PDFInfo
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- CN1587292B CN1587292B CN 200410052647 CN200410052647A CN1587292B CN 1587292 B CN1587292 B CN 1587292B CN 200410052647 CN200410052647 CN 200410052647 CN 200410052647 A CN200410052647 A CN 200410052647A CN 1587292 B CN1587292 B CN 1587292B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 30
- 238000001125 extrusion Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 150000001993 dienes Chemical class 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 239000003505 polymerization initiator Substances 0.000 claims abstract 3
- 239000003963 antioxidant agent Substances 0.000 claims abstract 2
- 239000003607 modifier Substances 0.000 claims abstract 2
- 239000003999 initiator Substances 0.000 claims description 62
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 29
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 230000001588 bifunctional effect Effects 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- -1 dichloropropyl aluminum Chemical compound 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- 239000002841 Lewis acid Substances 0.000 claims description 9
- 150000007517 lewis acids Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical group CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- YEYZALQTJCVXIJ-HXUWFJFHSA-N (2R)-2-amino-2-(methoxymethyl)-4-(4-octylphenyl)butan-1-ol Chemical compound CCCCCCCCC1=CC=C(CC[C@@](N)(CO)COC)C=C1 YEYZALQTJCVXIJ-HXUWFJFHSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- PXXRRQOFRCDQHK-UHFFFAOYSA-N CC1=CC=CC2=CC=CC=C12.[Li] Chemical compound CC1=CC=CC2=CC=CC=C12.[Li] PXXRRQOFRCDQHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical group CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001979 organolithium group Chemical group 0.000 claims 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- UWKKBEQZACDEBT-UHFFFAOYSA-N CCCC[Mg] Chemical compound CCCC[Mg] UWKKBEQZACDEBT-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims 1
- BXILREUWHCQFES-UHFFFAOYSA-K aluminum;trichloride;hydrochloride Chemical compound [Al+3].Cl.[Cl-].[Cl-].[Cl-] BXILREUWHCQFES-UHFFFAOYSA-K 0.000 claims 1
- SPWITGQNMOBZGJ-UHFFFAOYSA-M chloro(dipentyl)alumane Chemical compound [Cl-].CCCCC[Al+]CCCCC SPWITGQNMOBZGJ-UHFFFAOYSA-M 0.000 claims 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 claims 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims 1
- ZMXPNWBFRPIZFV-UHFFFAOYSA-M dipropylalumanylium;chloride Chemical compound [Cl-].CCC[Al+]CCC ZMXPNWBFRPIZFV-UHFFFAOYSA-M 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000006384 oligomerization reaction Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 229920006132 styrene block copolymer Polymers 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 9
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052728 basic metal Inorganic materials 0.000 description 5
- 150000003818 basic metals Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UPSXAPQYNGXVBF-UHFFFAOYSA-N 2-bromobutane Chemical compound CCC(C)Br UPSXAPQYNGXVBF-UHFFFAOYSA-N 0.000 description 1
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- SFGSCWQCLSTTPQ-UHFFFAOYSA-N 5-phenylhexan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)CCC(C)C1=CC=CC=C1 SFGSCWQCLSTTPQ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
一种具有特殊结构和性能的纳米级尺度分散相多嵌段线形苯乙烯类单体/共轭二烯烃嵌段共聚物反应挤出聚合方法，包括如下步骤：将苯乙烯类单体与共轭二烯烃按一定比例混合送入螺杆挤出机的第一段，将聚合反应引发剂送入第二段，将抗氧剂和其他改性剂从螺杆挤出机的侧向加入，然后在口模段挤出。本发明所制备的苯乙烯类嵌段共聚物具有突出的断裂延伸率与力学性能。本发明将传统聚合工艺中的聚合反应和挤出加工过程在螺杆挤出机中合而为一，使整个生产周期缩短到数分钟，而且整个过程中没有溶剂参与，无需进行复杂的溶剂分离，提纯，因此生产效率高，能耗小，成本低，污染轻，具有很好的社会效益和经济效益，工业化前景看好。A nano-scale dispersed phase multi-block linear styrenic monomer/conjugated diene block copolymer reaction extrusion polymerization method with special structure and performance, comprising the following steps: combining styrenic monomers with conjugated diolefins The olefins are mixed in a certain proportion and sent to the first section of the screw extruder, the polymerization initiator is sent to the second section, the antioxidant and other modifiers are added from the side of the screw extruder, and then in the die Segment extrusion. The styrenic block copolymer prepared by the invention has outstanding elongation at break and mechanical properties. The present invention combines the polymerization reaction and extrusion process in the traditional polymerization process into one in the screw extruder, shortening the entire production cycle to several minutes, and there is no solvent involved in the whole process, and no complicated solvent separation is required. Purification, so the production efficiency is high, the energy consumption is small, the cost is low, the pollution is light, it has good social and economic benefits, and the industrialization prospect is promising.
Description
Technical field
The present invention relates to a kind of preparation method of nanoscale disperse phase styrenic segmented copolymer, relating in particular to a kind of is reactor with the screw extrusion press, the reaction-extruding out process for polymerizing of continuous production nanoscale disperse phase styrenic block copolymer.
Background technology
Styrenic block copolymer is a kind of important high molecular polymer, is widely used in household electrical appliances, building, trolley part, asphalt modification, tackiness agent, a plurality of fields such as packing.
Use many styrenic block copolymers at present styrene-butadiene-styrene block copolymer (SBS) is arranged, styrene isoprene styrene block copolymer (SIS) (SIS), styrene butadiene random copolymer (SB), styrene/conjugated diene segmented copolymer (the block number is 5～9), the K resin, methymethacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS) etc. still, the method that at present domestic and international industrial polymerizing styrene based block copolymer adopts is the reactor solution polymerization, for example two step of the employing coupling method of U.S. Pat 3078254 disclosures synthesizes the production process route of SBS, the production process route of the synthetic SBS of reinforced method of three steps that U.S. Pat 3198774 adopts, the employings such as processing method of the synthetic star styrene/butadiene block copolymer of the polyfunctionality initiator that U.S. Pat 3957913 adopts all be the method for solution polymerization, usually the consumption of solvent is 5～20 times of polymer quality in solution polymerization process, this means has increased a large amount of separated from solvent, purify, follow-up works such as recovery, facility investment and energy consumption have not only been increased, also increased environmental protection pressure, this traditional big energy consumption, heavily contaminated, expensive, the solution polymerization route that technology is tediously long, make the production cost of styrenic block copolymer high always, limited the application widely of styrenic block copolymer.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of styrene block copolymer reacting and extruding polymerization method, to overcome the above-mentioned defective that prior art exists, satisfy the needs of relevant department.
The said styrenic block copolymer of the present invention is the linear styrene monomer/conjugated diene block copolymer of the many blocks of nano level yardstick disperse phase with special construction and performance, by a large amount of small (nano level) conjugated diene block and a small amount of random section styrene monomer of forming/conjugated diene segmented copolymer, constitutional features is as follows for a kind of for its constructional feature:
The said styrene monomer of the present invention/conjugated diene segmented copolymer is by the long block of vinylbenzene, the short block of divinyl is main, the ABAB.... type segmented copolymer (A refers to the long block of vinylbenzene, and B refers to the short block of divinyl) that is being mingled with random section composition of a spot of butylbenzene.
The prepared styrene copolymer number-average molecular weight (Mn) of the present invention is 1 * 10
4～70 * 10
4, optimum range 5 * 10
4～35 * 10
4, the weight percent content of styrene monomer in multipolymer is 50%～95%, optimum content is 93%～60%.
The preparation method of above-mentioned polymkeric substance comprises the steps:
Styrene monomer and conjugated diene are sent into first section of screw extrusion press by a certain percentage, and temperature is 0～50 ℃; Initiators for polymerization is sent into second section carry out polymerization reaction zone, temperature is 0～100 ℃, is preferably between 20～80 ℃; Third and fourth section mainly is melt conveying zone, and temperature is 80～180 ℃, at the melt conveying zone of polymerisate, oxidation inhibitor and the side direction of other properties-correcting agent from screw extrusion press is added; The 5th section is a mouthful mould section, and temperature is 180～230 ℃, and per os mould section is extruded, and cooling after the pelletizing, promptly obtains the linear styrene monomer of the many blocks of nano level yardstick disperse phase/conjugated diene copolymer pellet.
The styrene monomer of being addressed comprises a kind of or its mixture in vinylbenzene, alpha-methyl styrene or the Vinylstyrene;
The conjugated diene boiling point of being addressed should be lower more than 40 ℃ than styrene monomer boiling point, preferred divinyl or isoprene etc.;
All monomers that the present invention uses are preferably not moisture, amine, and oxy-compound, oxygen, carbonic acid gas, therefore impurity such as monomer stopper are preferably made with extra care olefinic monomer before polymerization, and its water content preferably will reach in the 10ppm, is preferably in the 7ppm.
The initiators for polymerization of being addressed can be simple function group initiator or bifunctional initiator.
The simple function group initiator of being addressed comprises simple function group organic alkali metal or alkaline-earth metal, rare earth metal initiator system, lewis acid initiator system.
The simple function group organic alkali metal of being addressed or the general formula of alkaline-earth metal are: a kind of among RMe, ROMe, RMeX or the RnMe;
R represents a kind of in alkyl, alicyclic radical, thiazolinyl, allyl group, benzyl or the aryl;
Me represents basic metal or alkaline-earth metal, as Li, and Na, K, Rb, Cs and Ca, Mg, Sr, Ba, Zn etc.;
X is a halogen; N=2;
In the present invention, this class initiator preferably uses straight chained alkyl lithium class, carbonatoms 4～10 be good, such as butyllithium;
In polymerization system, the mol ratio of polymerization single polymerization monomer and simple function group organic alkali metal or alkaline-earth metal initiator is 1 * 10
4～70 * 10
4
The rare earth metal initiator system of being addressed is the disclosed NdX-Mg of prior art (n-Bu)
2-HMPA three component initiator systems, wherein:
NdX is main initiator, and X is di(2-ethylhexyl)phosphate (the 2-ethyl is an own) ester;
HMPA represents hexamethylphosphoramide;
Mg (n-Bu)
2Be aided initiating normal-butyl magnesium, and add a spot of triethyl aluminum that increasing the dissolving situation of normal-butyl magnesium, addition is 2～10 for well with Mg/Al;
The mol ratio of HMPA/Mg is 0.3～4.0, preferred 0.5～2.0;
The mol ratio of aided initiating and main initiator is 5～35, preferred 10～30;
In the polymerization system, the mol ratio of Nd and olefinic monomer should be 3.0 * 10
-5～3.0 * 10
-4, preferably 5.0 * 10
-5～1.0 * 10
-4
Described lewis acid initiator system is the disclosed lewis acid initiator system of prior art, said Lewis acid comprises a kind of in aluminum chloride, alchlor, ethyl aluminum dichloride, two chloropropyl aluminium, dichloro amyl group aluminium, sesquialter ethyl aluminum chloride, sesquialter propyl group aluminum chloride, sesquialter butyl aluminum chloride, sesquialter amyl group aluminum chloride, aluminium diethyl monochloride, a chlorine dipropyl aluminium, a chlorine dibutyl aluminium, a chlorine diamyl aluminium, titanium tetrachloride, tin tetrachloride, boron trifluoride or the boron tribromide etc., and it is good using the aluminum chloride effect; The employed thinner of Lewis acid initiator system is an alkyl halide, as: monochloro methane, methylene dichloride, tertiary butyl chloride, tert.-butyl bromide, a kind of or its mixture in 2-chloro-butane and 2-bromo-butane or the monochloroethane.In polymerization system of the present invention, polymerization of olefin monomers and lewis acidic mol ratio are 1 * 10
4～70 * 10
4
Described bifunctional initiator comprises a kind of in bifunctional organic lithium initiator, basic metal or alkaline-earth metal-polycyclic aromatic hydrocarbons composite initiator system.
The bifunctional organic lithium initiator of being addressed is the disclosed any bifunctional organic lithium initiator of prior art, it can be the mixture of a kind of bifunctional alkyl lithium initiator or several bifunctional alkyl lithium initiators, as: two lithiums of two halogenated alkanes and the two lithiums of oligopolymer thereof, such as: LiRLi, Li (DO) nR (DO) nLi, wherein: R is that carbonatoms is 4～10 alkyl, DO is that carbonatoms is 4～8 a kind of conjugated diene or the mixture of several conjugated dienes, with, 1, the 3-divinyl is good, n is the oligomerisation degree, and n is generally 2～8, preferably 3～6; For example: 1,4-two lithium butane, 1,2-two lithiums-1,2 diphenylethane, 1,4-two lithiums-1,1,4,4-tetraphenyl butane, 1,4-dimethyl-1,4-diphenyl butane two lithiums, polyhutadiene two lithium oligopolymers, polyisoprene two lithium oligopolymers; Two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof, such as: 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, the two lithiums of 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, 1, the two lithiums of 1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, 1,1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1,1 '-(1, the 4-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, the two lithiums of 1,1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, in polymerization system of the present invention, the mol ratio of polymerization single polymerization monomer and bifunctional organic lithium initiator is 1 * 10
4～70 * 10
4
Basic metal of being addressed or alkaline-earth metal-polycyclic aromatic hydrocarbons composite initiator system is to use aromatic hydrocarbon, such as naphthalene or biphenyl etc., makes with basic metal or alkaline-earth metal reaction, and preferred naphthalene sodium, naphthalene lithium or alpha-methyl-naphthalene lithium etc. are good with naphthalene lithium effect.In polymerization system of the present invention, the mol ratio of polymerization single polymerization monomer and basic metal or alkaline-earth metal-polycyclic aromatic hydrocarbons composite initiator should be 1 * 10
4～35 * 10
4
The screw extrusion press of being addressed comprises single screw extrusion machine, intermeshing counter-rotating twin-screw forcing machine or non-intermeshing counter-rotating twin-screw forcing machine, the engagement co-rotating twin screw extruder, the length-to-diameter ratio of screw extrusion press (L/D) is 20/1～60/1, preferably get 30/1～45/1 this scope, select engagement co-rotating twin screw extruder best results; Screw speed is controlled at 20～300rpm, when rotating speed is lower than 20rpm, causes the overstand of material, mixes inhomogeneously, and production efficiency is low; When rotating speed is higher than 300rpm, can cause high molecular polymer shear degradation and residence time deficiency, therefore, the control screw speed is controlled between 60～1000s the mean residence time of material in screw extrusion press.
The prepared linear styrene monomer/conjugated diene copolymer of the many blocks of nano level yardstick disperse phase of the present invention is compared with general linear styrene monomer/conjugated diene block copolymer, has outstanding tension set, exceed several times of the latter and even tens times, and other mechanical properties are not inferior yet.
The present invention adopts reactive extrusion technology, with the screw extrusion press is that reactor carries out monomer polymerization and modification, compare with traditional reactor, reactive extrusion technology integrates polyreaction in the conventional polymerization process and extrusion process in screw extrusion press, make the whole production cycle shorten to several minutes, and there is not solvent to participate in the whole process substantially, need not to carry out complex solvent separation, purify, so production efficiency height, energy consumption is little, cost is low, pollute gently, and screw extrusion press has good mixing ability, the high fluid of viscosity there is good transport capacity, the deliming ability, advantages such as the continuity of producing is good all have the incomparable many superiority of conventional polymerization process method technically and economically.Compare with the polymerization technique of present industrial styrene block copolymer, the present invention has the equipment less investment, technology is fairly simple, continuously, technical process and with short production cycle, technological process less energy consumption, pollute advantages such as little, comply with the requirement of the world to the environmental protection aspect, have good social benefit and economic benefit, industrial prospect is good.
Description of drawings
Fig. 1 is transmission electron microscope photo (* 50000).
Embodiment
Further specify the present invention below in conjunction with embodiment, but the scope of also unrestricted claim protection of the present invention adopts following testing method in an embodiment:
Molecular weight and distribution thereof: GPC test
Tensile strength: GB/T1040-92
Flexural strength: GB/9341-88
Notched Izod impact strength: GB/1842-80
Block copolymer structure and monomeric unit assay: by infrared spectra, proton nmr spectra and carbon-13 nmr spectra are measured.
Segmented copolymer microscopic pattern test: transmission electron microscope
The mensuration of monomer conversion: at first be dissolved in the polymer samples of certainweight in the tetrahydrofuran (THF), adopt methyl alcohol that it is precipitated then, under 40 ℃, be evacuated to constant weight through overanxious being placed in the vacuum drying oven, calculate monomer conversion by the weight before and after the comparative sample.
Embodiment 1
To reach the styrene monomer of polymerization requirement of the present invention after the refinement treatment, divinylic monomer is freezing to-10 ℃, under the conveying of volume pump, successively is transported to mix monomer storage tank at 80: 20 according to the phenylethylene/butadiene weight ratio, and makes both thorough mixing even.Mix monomer and n-butyl lithium initiator reacted in twin screw extruder extrude, obtain number-average molecular weight and be 270,000 nano-grade size disperse phase (dispersed phase size measured of transmission electron microscope for less than 10 nanometers, and be evenly distributed) many block styrene/conjugated diene shape block copolymer product A.Transmission electron microscope picture is seen Fig. 1.Processing condition are provided with as follows:
Each segment temperature of screw rod: 20/45/140/180/200 ℃, the monomer mass flow: 6 kilograms/hour, initiator mass rate: 1.5 Grams Per Hours, screw speed: 100rpm.
The The performance test results of product A
Embodiment 2
Adopt the identical processing condition of embodiment 1, with 1,4-two lithium butane are initiator, and the initiator mass rate is 1.6 Grams Per Hours, and the The performance test results of product B is as follows:
Embodiment 3
Adopt the identical processing condition of embodiment 1, with NdX-Mg (n-Bu)
2-HMPA three component initiator systems are initiator, wherein the ratio of each component is: Mg/Nd=20; Mg/Al=9; HMPA/Mg=1.5, initiator and monomer mass throughput ratio are 4 * 10
-5, the The performance test results of products C is as follows:
Embodiment 4
Adopting the identical processing condition of embodiment 1, is initiator with the naphthalene lithium, and the initiator mass rate is 6.0 Grams Per Hours, and the The performance test results of product D is as follows:
Embodiment 5
Adopting the identical processing condition of embodiment 1, is initiator with the titanium tetrachloride, is initiator diluent with the methylene dichloride, and initiator concentration is 1M, and the titanium tetrachloride mass rate is 7.4 Grams Per Hours, and the The performance test results of product E is as follows:
Claims (1)
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| US10689469B2 (en) | 2016-04-11 | 2020-06-23 | East China University Of Science And Technology | Method of reactive extrusion copolymerization of vinyl monomers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357566A (en) * | 2001-12-29 | 2002-07-10 | 中国科学院长春应用化学研究所 | Prepn of polystyrene/nylon 6 blocking plate with resistance to chloroethane and fluoroethane and high impact strength |
| US20030170306A1 (en) * | 2000-06-16 | 2003-09-11 | Raether Roman Benedikt | Use of polymeric reaction product |
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| US20030170306A1 (en) * | 2000-06-16 | 2003-09-11 | Raether Roman Benedikt | Use of polymeric reaction product |
| CN1357566A (en) * | 2001-12-29 | 2002-07-10 | 中国科学院长春应用化学研究所 | Prepn of polystyrene/nylon 6 blocking plate with resistance to chloroethane and fluoroethane and high impact strength |
Non-Patent Citations (2)
| Title |
|---|
| 张鹰 烟伟 高世双 郑安呐 韩哲文.反应挤出法合成S/B多嵌段共聚物的研究.高分子学报 5.2002,(5),全文. |
| 张鹰 烟伟 高世双 郑安呐 韩哲文.反应挤出法合成S/B多嵌段共聚物的研究.高分子学报 5.2002,(5),全文. * |
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|---|---|---|---|---|
| US10689469B2 (en) | 2016-04-11 | 2020-06-23 | East China University Of Science And Technology | Method of reactive extrusion copolymerization of vinyl monomers |
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