CN1073124C - Catalyst for preparing copolymer of syndiotactic polystyrene and block polyethylene - Google Patents
Catalyst for preparing copolymer of syndiotactic polystyrene and block polyethylene Download PDFInfo
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- CN1073124C CN1073124C CN98110750A CN98110750A CN1073124C CN 1073124 C CN1073124 C CN 1073124C CN 98110750 A CN98110750 A CN 98110750A CN 98110750 A CN98110750 A CN 98110750A CN 1073124 C CN1073124 C CN 1073124C
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- Prior art keywords
- syndiotactic polystyrene
- catalyzer
- catalyst
- titanium compound
- alkylaluminoxane
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- -1 polyethylene Polymers 0.000 title claims abstract description 14
- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 11
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 title abstract description 5
- 229920001577 copolymer Polymers 0.000 title description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- FCAJYRVEBULFKS-UHFFFAOYSA-N 2-(oxolan-2-yl)ethanol Chemical compound OCCC1CCCO1 FCAJYRVEBULFKS-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 235000005291 Rumex acetosa Nutrition 0.000 description 2
- 240000007001 Rumex acetosella Species 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000003513 sheep sorrel Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a catalyst used for preparing a block polymer (sPS-b-PE) of syndiotactic polystyrene and polyethylene, which comprises an organic metallic titanium compound CpTi(OCH2R1)3 and alkylaluminium oxane, wherein Cp is cyclopentadienyl, and R1 is a heterocyclic group containing 4 to 20 carbon atoms. With the characteristics of high catalytic activity and high catalytic efficiency, the catalyst can be used in industrial production.
Description
The present invention relates to prepare the catalyzer of syndiotactic polystyrene and polyethylene block multipolymer (sPS-b-PE).
Styrene polymer can be divided into random polystyrene, isotactic polyphenylacetylene and syndiotactic polystyrene.The catalyzer that synthesis of syndiotactic polystyrene adopts organo-metallic titanium compound and poly-methylaluminoxane (MAO) to form usually.The organo-metallic titanium compound is mainly cyclopentadiene titanium compound.Document EP 210615 and US5252693 etc. have reported employing CpTiCl
3/ MAO catalyzer is used for the situation of syndiotactic polymerization of phenylethylene, but its catalytic activity and catalytic efficiency are not high, and is industrial undesirable, and this catalyzer also is not suitable for being used for vinylbenzene and ethylene block copolymerization closes simultaneously.
The objective of the invention is for a kind of new preparation syndiotactic polystyrene and the catalyzer of polyethylene block multipolymer are provided, this catalyzer has high catalytic activity and catalytic efficiency.
The objective of the invention is to realize by following technical scheme: a kind of catalyzer for preparing syndiotactic polystyrene and polyethylene block multipolymer comprises organic metal titanium compound I and alkylaluminoxane II;
Cp is a cyclopentadienyl in the formula;
R
1Be the tetrahydrofuran (THF) group;
R
2For containing the alkyl of 1~4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6~40;
Aluminium is 50~2000 to the molar ratio range of organo-metallic titanium compound I in the alkylaluminoxane II.
R in the technique scheme
2Preferred version be methyl, the value preferable range of oligomerisation degree n is 10~30.
Poly-alkylaluminoxane (MAO) is that the control hydrolysis by aluminum alkyls prepares, and reactants water can be the water that contains in the inorganic salt of crystal water, and the inorganic salt that contain crystal water can be CaCl
26H
2O, MgCl
26H
2O, CuSO
45H
2O, Al
2(SO
4)
318H
2O, CaSO
42H
2O, MgSO
47H
2O, FeSO
47H
2O, Ti (SO
4)
24H
2O, Ti
2(SO
4)
38H
2O and ZnSO
47H
2O etc.The mole ratio of trimethyl aluminium and water is 1: 1~3.0, and temperature of reaction is-20~100 ℃, and the reaction times is 10~40 hours.Aluminum alkyls commonly used have trimethyl aluminium,, triethyl aluminum, triisobutyl aluminium etc.Concrete steps are: aluminum alkyls is pressed Al/H
2The O mol ratio is 1: 1~2.5 slowly to be added dropwise to Al under-20~0 ℃
2(SO
4)
318H
2In the toluene solution of O, the dropping time is 0.5~5 hour; After dropwising, make temperature of reaction rise to 20~100 ℃, under this temperature, reacted 5~40 hours, after reaction finished, with solid filtering, evaporation removed to desolvate and obtains white solid product, promptly obtains the alkylaluminoxane that structure is an II.
The preparation method of cyclopentadiene titanium compound I is as follows: by corresponding cyclopentadienyl titanous chloride and tetrahydrofurfuryl carbinol (HO-
) in the presence of chlorine hydride absorbent, be that solvent reaction makes with the hydrocarbon polymer.Chlorine hydride absorbent can be various aminated compoundss, wherein is advisable with trialkylamine, for example triethylamine.Hydrocarbon polymer can be aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbon better.For example benzene, toluene etc.Concrete steps are: ethamine and tetrahydrofurfuryl carbinol mixing solutions are slowly dropped in the benzole soln of cyclopentadienyl titanous chloride, the mole ratio of cyclopentadienyl titanous chloride and tetrahydrofurfuryl carbinol is 1: 3.0~3.5, the mole ratio of cyclopentadienyl titanous chloride and triethylamine is 1: 3.0~3.5, temperature of reaction is 0~60 ℃, and the reaction times is 1~30 hour, solids removed by filtration, underpressure distillation removes and desolvates, the crude product hexane extraction that obtains, remove volatile matter after, mucus russet.
Work as R
1During for tetrahydrofuran (THF), the ultimate analysis of chemical compounds I, hydrogen nuclear magnetic resonance spectrum
1H NMR, nuclear magnetic resonance of carbon spectrum
13C NMR, mass spectrum MS and infrared spectra the results are shown in following data:
Ultimate analysis (element analyses)
Calcd?for?C
20H
34O
6Ti:C:57.42;H:8.19.Found:C:57.30;H:7.90
Hydrogen nuclear magnetic resonance spectrum [
1H NMR (CDCl
3TMS intern)]:
δ1.78(m,12H,(C-CH
2CH
2-C)
3),3.85(d,6H,(OCH
2C)
3),
4.19-4.25(m,9H,(CCHO?OCH
2)
3),6.35-6.37(d,5H,CpH).
Carbon
13Nuclear magnetic resonance spectrum [
13C NMR (CDCCl
3)]:
δ64.8(Ti-OCH
2-),79.2(-CH
2CH
2-),80.0(-CH-),79.4(CH
2-O),114.0(CpC).
Mass spectrum [MS (m/z, %intensity)]:
41(60,CH
2CHCH
+),43(100,CH
2CHO
+),65(30,C
5H
5 +),66(32,C
5H
5 +),
64(10,TiO
+),71(100,OCHCH
2CH
2CH
2 +),85(13,CH
2CHCH
2CH
2CH
2O
+),
113(4,CpTi
+),129(28,CpTiO
+),165(18,M-Cp-(OCH
2CHCH
2CH
2CH
2O)
2 +),
213(11,M-(OCH
2CHCH
2CH
2CH
2O)
2 +),249(18,M-Cp-(OCH
2CHCH
2CH
2CH
2O)
+),
315(10,M-OCH
2CHCH
2CH
2CH
2O
+),351(22,M-Cp
+).
Infrared spectra (Infrared FTIR)
Wave number | Vibration |
?3100 ?2966-2868 ?1735-1644 ?1447 ?1131-1068 ?990 ?589 | The hydrocarbon key asymmetrical stretching vibration [VasC-H (O-CH of luxuriant ring C-H stretching vibration 2-C)] the luxuriant ring skeletal vibration of the general frequency absorption band carbon-oxygen bond stretching vibration [V of luxuriant ring c-0(Ti)], and titanium carbon bond stretching vibration (V is vibrated in the plain bending of C-H on the luxuriant ring of tetrahydrofuran (THF) ring skeletal vibration Ti-c) |
Catalyst component I and II can be under protection of inert gas (for example nitrogen, argon gas etc.) under 0~50 ℃, preferably 25 ℃ are carried out pre-mixing.
Polyreaction is preferably carried out between 30~60 ℃ at 25~100 ℃.In order to obtain the polymkeric substance of ideal performance, polymerization need be used the regular hour, and by several hours, preferably 1~10 hour, the ideal polymerization time depended on polymerization temperature, solvent and other polymerizing condition from several minutes.The polyreaction mode can adopt solution polymerization, slurry polymerization and mass polymerization.For solution polymerization and slurry polymerization, the solvent of employing is aliphatic hydrocarbon or aromatic hydrocarbon, as hexane, heptane, hexanaphthene, benzene, toluene etc.The concentration of vinylbenzene in solvent is in 5~100% scopes, and ethylene pressure is in 0.1~1.0MPa scope.
The present invention adopts a kind of new metallocene-titanium metal compound as the Primary Catalysts for preparing syndiotactic polystyrene and polyethylene block multipolymer, makes the higher 14.1 kg of polymer/gram titanium that reached of catalytic efficiency of catalyzer, has obtained effect preferably.
Below just the invention will be further elaborated [embodiment 1] by embodiment
The preparation of cyclopentadiene titanium compound
With 1.51g (6.88mmol) the cyclopentadienyl titanous chloride exsiccant of packing into; be subjected in the 250ml reaction flask of nitrogen protection; add 40ml exsiccant benzene; again under nitrogen protection with dropping funnel lentamente Dropwise 35 ml contain 2.08g (20.6mmol; 2.87ml) triethylamine and 2.10g (20.6mmol; 2.00ml) the exsiccant benzole soln of tetrahydrofurfuryl carbinol; be allowed to condition under 20 ℃ the temperature and react 24h; filter; drain solvent, use the n-hexane extraction of 40 ℃ of exsiccant again, constant temperature leaves standstill 2h; supernatant liquid is transferred in the container of dried and clean inflated with nitrogen; drain solvent, get sorrel oily product 2.52g, yield 88%.The toluene solution that is made into 0.02M is standby.[embodiment 2]
The preparation of MAO
Be equipped with and add 30 Als of gram in the 500ml reactor of induction stirring through milling
2(SO
4)
318H
2O and 70ml toluene, under-10 ℃ of temperature, dripping 200ml concentration is the trimethyl aluminium toluene solution of 3.1M.Rate of addition is 5 ml/min, drips off in 60 minutes.Improve temperature of reaction then gradually, in 2h, make temperature reach 60 ℃, continue reaction 24h.Reaction mixture is removed solid after filtration, and filtrate is taken out 1h with vacuum pump under 30 ℃, removes part toluene, under 50 ℃, drain again, volatile matters such as toluene are removed, obtain 12.8g white solid MAO, productive rate is about 32.0%, and after measured, the average oligomerisation degree of methylaluminoxane (MAO) is 16.[embodiment 3]
To the 250ml there-necked flask vacuum-drying 2h of stirring be housed, inflated with nitrogen is kept malleation, add 20ml toluene, the MAO 0.35g of embodiment 2 preparations, the cyclopentadiene titanium compound 0.38ml of embodiment 1 preparation, add 10ml vinylbenzene down at 65 ℃, reacted 30 minutes, take the nitrogen in the reaction flask away, feed the ethene of 0.213MPa immediately, and keep this and press reaction 90 minutes, reaction product is after 5% acidic methanol termination, filter and vacuum-drying, get copolymerization product 5.1g, catalytic efficiency is 14.1 kg of polymer/gram titanium.Copolymerization product obtains multipolymer through 40 ℃ of tetrahydrofuran (THF) extractings, and insolubles is the homopolymer of vinylbenzene and ethene.Dsc analysis shows that multipolymer Tg is 89.3 ℃, and two melting peaks are respectively 255.8 ℃ and 130.2 ℃, proves that institute's synthetic multipolymer has the sPS-b-PE segmented copolymer of syndiotactic styrenic block.[embodiment 4]
The preparation of cyclopentadiene titanium compound
With 2.22g (10.1mmol) the cyclopentadienyl titanous chloride exsiccant of packing into; be subjected in the 250ml reaction flask of nitrogen protection; add 45ml exsiccant benzene; under nitrogen protection, drip 45ml lentamente again and contain 3.08g (30.3mmol with dropping funnel; 4.25ml) triethylamine and 3.10g (30.3mmol; 2.94ml) the exsiccant benzole soln of tetrahydrofurfuryl carbinol; be allowed to condition under 25 ℃ the temperature and react 24h; filter; drain solvent, use the n-hexane extraction of 40 ℃ of exsiccant again, constant temperature leaves standstill 2h; supernatant liquid is transferred in the container of dried and clean inflated with nitrogen; drain solvent, get sorrel oily product 3.82g, yield 91%.The toluene solution that is made into 0.02M is standby.[embodiment 5]
To the 250ml there-necked flask vacuum-drying 2h of stirring be housed, inflated with nitrogen is kept malleation, add 20ml toluene, the MAO 0.35g of embodiment 2 preparations, the cyclopentadiene titanium compound 0.4ml of embodiment 4 preparations, add 10ml vinylbenzene down at 60 ℃, reacted 30 minutes, take the nitrogen in the reaction flask away, feed the ethene of 0.118Mpa immediately, and kept this stress reaction 90 minutes, reaction product is after 5% acidic methanol termination, filter and vacuum-drying, get copolymerization product 3.8g, catalytic efficiency is 9.8 kg of polymer/gram titanium.Copolymerization product obtains multipolymer through 40 ℃ of tetrahydrofuran (THF) extractings, and insolubles is the homopolymer of vinylbenzene and ethene.Dsc analysis shows that multipolymer Tg is 89 ℃, and two melting peaks are respectively 259.5 ℃ and 131 ℃, proves that institute's synthetic multipolymer has the sPS-b-PE segmented copolymer of syndiotactic styrenic block.
Claims (3)
1, a kind of catalyzer for preparing syndiotactic polystyrene and polyethylene block multipolymer comprises organic metal titanium compound I and alkylaluminoxane II;
Cp is a cyclopentadienyl in the formula;
R
1Be the tetrahydrofuran (THF) group;
R
2For containing the alkyl of 1~4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6~40;
Aluminium is to the mol ratio 50~2000 of organo-metallic titanium compound I in the alkylaluminoxane II.
2, according to the catalyzer of described preparation syndiotactic polystyrene of claim 1 and polyethylene block multipolymer, it is characterized in that R
2Be methyl.
3, according to the catalyzer of described preparation syndiotactic polystyrene of claim 1 and polyethylene block multipolymer, the value that it is characterized in that oligomerisation degree n is 10~30.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN98110750A CN1073124C (en) | 1998-03-30 | 1998-03-30 | Catalyst for preparing copolymer of syndiotactic polystyrene and block polyethylene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN98110750A CN1073124C (en) | 1998-03-30 | 1998-03-30 | Catalyst for preparing copolymer of syndiotactic polystyrene and block polyethylene |
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CN1073124C true CN1073124C (en) | 2001-10-17 |
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ID=5220773
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5100983A (en) * | 1990-03-07 | 1992-03-31 | Tosoh Corporation | Process for producing syndiotactic polymer of aromatic vinyl compounds |
US5652315A (en) * | 1992-06-04 | 1997-07-29 | Mitsui Toatsu Chemicals, Inc. | Method for preparing ethylene copolymer |
-
1998
- 1998-03-30 CN CN98110750A patent/CN1073124C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5100983A (en) * | 1990-03-07 | 1992-03-31 | Tosoh Corporation | Process for producing syndiotactic polymer of aromatic vinyl compounds |
US5652315A (en) * | 1992-06-04 | 1997-07-29 | Mitsui Toatsu Chemicals, Inc. | Method for preparing ethylene copolymer |
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Publication number | Publication date |
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CN1230556A (en) | 1999-10-06 |
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