CN1073124C - Catalyst for preparing copolymer of syndiotactic polystyrene and block polyethylene - Google Patents

Catalyst for preparing copolymer of syndiotactic polystyrene and block polyethylene Download PDF

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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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syndiotactic polystyrene
catalyzer
catalyst
titanium compound
alkylaluminoxane
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CN1230556A (en
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林尚安
王正辉
许光学
周文乐
涂建军
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
National Sun Yat Sen University
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
National Sun Yat Sen University
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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 catalyzer of preparation syndiotactic polystyrene and polyethylene block multipolymer
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;
CpTi(OCH 2R 1) 3 Ⅰ
Figure C9811075000031
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-
Figure C9811075000041
) 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;
CpTi(OCH 2R 1) 3 Ⅰ
Figure C9811075000021
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.
CN98110750A 1998-03-30 1998-03-30 Catalyst for preparing copolymer of syndiotactic polystyrene and block polyethylene Expired - Fee Related CN1073124C (en)

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Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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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