CN1065881C - Catalyst for preparing block copolymer of syndiotactic polystyrene and polyethylene - Google Patents
Catalyst for preparing block copolymer of syndiotactic polystyrene and polyethylene Download PDFInfo
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- CN1065881C CN1065881C CN98110751A CN98110751A CN1065881C CN 1065881 C CN1065881 C CN 1065881C CN 98110751 A CN98110751 A CN 98110751A CN 98110751 A CN98110751 A CN 98110751A CN 1065881 C CN1065881 C CN 1065881C
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- China
- Prior art keywords
- syndiotactic polystyrene
- polyethylene
- catalyst
- titanium compound
- alkylaluminoxane
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Abstract
The present invention relates to a catalyst used for preparing a block polymer (PE-b-sPS) 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 an aromatic 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 be used to prepare the catalyzer of syndiotactic polystyrene and polyethylene block multipolymer.
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.EP210615 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 the block copolymerization of vinylbenzene and ethene simultaneously.
The purpose of this invention is to provide a kind of new preparation syndiotactic polystyrene and the catalyzer of polyethylene block multipolymer, 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
Cp is a cyclopentadienyl in the formula;
R
1Be furan 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
26H2
O, 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 has 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 furfuryl alcohol (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 furfuryl alcohol mixing solutions are slowly dropped in the benzole soln of cyclopentadienyl titanous chloride, the mole ratio of cyclopentadienyl titanous chloride and furfuryl alcohol 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, jonquilleous mucus.
Work as R
1During for furyl, the ultimate analysis of chemical compounds I, hydrogen nuclear magnetic resonance spectrum
1HNMR, nuclear magnetic resonance of carbon spectrum
13CNMR, mass spectrum MS and infrared spectra the results are shown in following data:
Ultimate analysis (element analyses)
Calcd?for?C
20H
20O
6Ti：C：59．42；H：4．99。Found：C：59．84；H：4．64
Hydrogen nuclear magnetic resonance spectrum [
1HNMR (CDCl
3TMS intern)]:
δ5．10(s，6H，(OCH
2)
3)，6．20-6．28(m，9H，(CCHCHCHO)
3)，
6．32-6．36(m，5H，Cp?H)。
Carbon
13Nuclear magnetic resonance spectrum [
13CNMR (CDCCl
3)]:
δ69．8(OCH
2)，154．6(C)，110．0(CH-CH)，106．9(CH=CH-O)，141．4(CH-O)，
113．9-114．2(Cp?C)。
Mass spectrum [MS (m/z, %intensity)]:
39(100，CH
2CCH
+)，53(70，CH
2CCH
2CH
+)，69(40，OCH
2CCHO
+)，
81(75，CH
2CHCHCHO
+?or?OTiO
+)，95(40，OTiOCH
2 +)，98(74，OCH
2CCHCHCHO
+)
112(10，CpTi
+)，129(3，CpTiO
+)，169(5，M-(OCH
2CCHCHCHO)-(OCCHCHCH)
+)，
339(5，M-Cp
+)。
Infrared spectra (Infrared FTIR)
The wave number vibration
3114 luxuriant ring C-H stretching vibrations, furan nucleus=C-H stretching vibration
The hydrocarbon key asymmetrical stretching vibration [VasC-H (O-CH of 2903-2846
2-C)]
1602-1503 furan nucleus skeletal vibration
Near the general frequency absorption band of luxuriant ring 1735
1447 luxuriant ring skeletal vibrations
Two key stretching vibration (V of 1644 furan nucleuss
C-c)
1068-1096 carbon-oxygen bond stretching vibration [V
C-O (Ti)]
The plain bending of C-H vibration on the 1011 luxuriant rings
The out-of-plane deformation vibration of 913885 furan nucleuss=C-H
The eigen vibration of three adjacent hydrogen on the 814-737 furan nucleus
589 titanium carbon bond stretching vibration (V
Ti-c)
421 titanyl key stretching vibration (V
Ti-o)
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 11.2 kg of polymer/gram titanium that reached of catalytic efficiency of catalyzer, has obtained effect preferably.
Below just the invention will be further elaborated by embodiment
[embodiment 1]
The preparation of cyclopentadiene titanium compound
With 2.41g (11.0mmol) the cyclopentadienyl titanous chloride exsiccant of packing into; be subjected in the 250ml reaction flask of nitrogen protection; add 50ml exsiccant benzene; again under nitrogen protection with dropping funnel lentamente Dropwise 5 0ml contain 3.34g (33.0mmol; 4.60ml) triethylamine and 3.24g (33.0mmol; 2.86ml) the exsiccant benzole soln of furfuralcohol; be allowed to condition under 18 ℃ 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 golden yellow oily product 4.08g, yield 92%.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, filtrate is taken out 1h with vacuum pump under 20 ℃, remove part toluene, under 30 ℃, take out 1h again, under 40 ℃, volatile matters such as toluene are removed at last, obtained 13.0g white solid MAO, productive rate about 32.5%, after measured, the average oligomerisation degree of methylaluminoxane (MAO) is 18.
[embodiment 3]
The preparation of cyclopentadiene titanium compound
With 2.12g (9.66mmol) 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 2.93g (28.9mmol with dropping funnel; 4.03ml) triethylamine and 2.83g (28.9mmol; 4.00ml) the exsiccant benzole soln of furfuralcohol; 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 golden yellow oily product 3.55g, yield 91%.The toluene solution that is made into 0.02M is standby.
[embodiment 4]
To the 250ml there-necked flask vacuum-drying 2h of stirring be housed, inflated with nitrogen is kept malleation, add 20ml toluene, the MAO0.21g of embodiment 2 preparations, the cyclopentadiene titanium compound 0.29ml of embodiment 1 preparation activates 3 minutes down at 65 ℃, takes the nitrogen in the reaction flask away, feed the ethene of 0.213Mpa immediately, and kept this stress reaction 5 minutes, and change the ethene in the bottle into nitrogen again, add the triisobutyl aluminium of the 1M of 1ml immediately, 10ml vinylbenzene, continuation is reacted 2.5h down at 65 ℃, and reaction product is filtered and vacuum-drying after 5% acidic methanol termination, get copolymerization product 4.2g, catalytic efficiency is 11.2 kg of polymer/gram titanium.Copolymerization product obtains multipolymer through 40 ℃ of tetrahydrofuran (THF) extractings.Insolubles is syndiotactic polystyrene and Natene.Dsc analysis shows that the Tg of multipolymer is 91 ℃, and two melting peaks are respectively 265 ℃ and 130 ℃, proves that institute's synthetic multipolymer has the PE-b-sPS segmented copolymer of syndiotactic styrenic chain.
[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 MAO0.24g of embodiment 2 preparations, the cyclopentadiene titanium compound 0.35ml of embodiment 3 preparations activates 3 minutes down at 65 ℃, takes the nitrogen in the reaction flask away, feed the ethene of 0.118Mpa immediately, and kept this stress reaction 10 minutes, and change the ethene in the bottle into nitrogen again, add the triisobutyl aluminium of the 1M of 1ml immediately, 10ml vinylbenzene, continuation was reacted 50 minutes down at 65 ℃, and reaction product is filtered and vacuum-drying after 5% acidic methanol termination, get copolymerization product 1.8g, catalytic efficiency 5.4 kg of polymer/gram titanium.Copolymerization product obtains multipolymer through 40 ℃ of tetrahydrofuran (THF) extractings.Insolubles is syndiotactic polystyrene and Natene.Dsc analysis shows that the Tg of multipolymer is 91 ℃, and two melting peaks are respectively 260.4 ℃ and 131 ℃, proves that institute's synthetic multipolymer has the PE-b-sPS segmented copolymer of syndiotactic styrenic chain.
Claims (3)
1, a kind of catalyzer that is used to prepare syndiotactic polystyrene and polyethylene block multipolymer comprises organic metal titanium compound I and alkylaluminoxane II;
CpTi(OCH
2R
1)
3 Ⅰ
Cp is a cyclopentadienyl in the formula;
R
1Be furan 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 described catalyzer that is used to prepare syndiotactic polystyrene and polyethylene block multipolymer of claim 1, it is characterized in that R
2Be methyl.
3, according to the described catalyzer that is used to prepare syndiotactic polystyrene and polyethylene block multipolymer of claim 1, the value that it is characterized in that oligomerisation degree n is 10～30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110751A CN1065881C (en) | 1998-03-30 | 1998-03-30 | Catalyst for preparing block copolymer of syndiotactic polystyrene and polyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110751A CN1065881C (en) | 1998-03-30 | 1998-03-30 | Catalyst for preparing block copolymer of syndiotactic polystyrene and polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1230558A CN1230558A (en) | 1999-10-06 |
| CN1065881C true CN1065881C (en) | 2001-05-16 |
Family
ID=5220774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110751A Expired - Fee Related CN1065881C (en) | 1998-03-30 | 1998-03-30 | Catalyst for preparing block copolymer of syndiotactic polystyrene and polyethylene |
Country Status (1)
| Country | Link |
|---|---|
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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 CN98110751A patent/CN1065881C/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 |
|---|---|
| CN1230558A (en) | 1999-10-06 |
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Addressee: China Petrochemical Corporation Document name: Notification of Termination of Patent Right |
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Granted publication date: 20010516 Termination date: 20100330 |