CN1076733C - Catalyst for preparing syndiotactic polystyrene - Google Patents
Catalyst for preparing syndiotactic polystyrene Download PDFInfo
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- CN1076733C CN1076733C CN98110851A CN98110851A CN1076733C CN 1076733 C CN1076733 C CN 1076733C CN 98110851 A CN98110851 A CN 98110851A CN 98110851 A CN98110851 A CN 98110851A CN 1076733 C CN1076733 C CN 1076733C
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- catalyzer
- syndiotactic polystyrene
- catalyst
- polymkeric substance
- cyclopentadienyl
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- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title abstract description 23
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 4
- 238000002360 preparation method Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 abstract 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- -1 it is heat-resisting Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a catalyst prepared from syndiotactic polystyrene, which comprises a cyclopentadienyl titanium compound R1Ti(o-*-OR2)3, alkylaluminium oxane and/or alkylaluminium, wherein R1 represents cyclopentadienyl and substituted cyclopentadienyl, R2 represents with one to six carbon atoms, and OR2 groups can be in ortho positions, meta positions or para positions of benzene rings. 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 the catalyzer of syndiotactic polystyrene preparation.
Styrene polymer can be divided into random polystyrene, isotactic polyphenylacetylene and syndiotactic polystyrene.Random polystyrene has been widely used in household electrical appliances, office appliance, packing and other Industrial materials, but it is heat-resisting, chemical resistant properties is poor.Adopt the syndiotactic polystyrene of metallocene/MAO Preparation of Catalyst, not only have the performance of random polystyrene, it is heat-resisting, chemical resistant properties strengthens.Strengthen through glass fibre, its over-all properties can be compared with engineering plastics.Document EP 210615 and US5252693 adopt CpTiCl
3/ MAO makees catalyzer; The flat 1-240503 of JP adopts Cp
*TiCl
3/ MAO makees catalyzer; US5196490 and US5045517 adopt CpTi (OPh)
3/ MAO is used for syndiotactic polymerization of phenylethylene, and the shortcoming that ubiquity catalytic activity and catalytic efficiency are not high, the styrene conversion rate is on the low side is unwell to industrial production and uses.
To the objective of the invention is to have catalyst system catalytic activity and the low shortcoming of catalytic efficiency in the above-mentioned document in order overcoming, a kind of catalyzer of new preparation styrene stereospecific polymers to be provided, this catalyzer has advantages of high catalytic activity and catalytic efficiency.
The objective of the invention is to realize by following technical scheme: a kind of catalyzer of syndiotactic polystyrene preparation comprises metallocene compound I, alkylaluminoxane II:
R in the formula
1Be cyclopentadienyl, substituted cyclopentadienyl;
R
2For containing the alkyl of 1～6 carbon atom;
R
3For containing the alkyl of 1～4 carbon atom;
OR
2Base can be in ortho position, a position or the contraposition of phenyl ring;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40.
Also can comprise component aluminum alkyls III in the technique scheme in the catalyzer, general formula is Al (R
4)
3, R wherein
4For containing the alkyl of 1～4 carbon atom.R
1Preferred version be cyclopentadienyl or pentamethyl-cyclopentadienyl; R
2Preferred version be methyl, OR
2Optimum seeking site scheme on phenyl ring is the contraposition of phenyl ring, R
3Preferred version be methyl, the value preferred version of oligomerisation degree n is 10～30; R
4Preferred version be isobutyl-; Aluminium is 50～2000 to the molar ratio range of metallocene compound I among the alkylaluminoxane II; Aluminium is 0.1～1000 to the molar ratio range of metallocene compound I among the aluminum alkyls III, and preferable range is 50～200.
Poly-alkylaluminoxane (MAO) is prepared by the aluminum alkyls control hydrolysis, and hydrolytic reagent 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, CuSO
42H
2O, MgSO
47H
2O, FeSO
47H
2O, Ti (SO
4)
24H
2O, Ti
2(SO
4)
38H
2O and ZnSO
47H
2O etc.Aluminum alkyls is 1: 1～3.0 for the mole ratio with water, and temperature of reaction is-20～100 ℃, and the reaction times is 5～40 hours, and reaction solvent can be alkane and aromatic hydrocarbons.Aluminum alkyls commonly used has trimethyl aluminium, triethyl aluminum, three different basic 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, makes temperature of reaction rise to 20～100 ℃, under this temperature, reacts 2～40 hours, and reaction with solid filtering, must contain the toluene solution that structure is the alkylaluminoxane of II after finishing.
The preparation method of metallocene compound I is as follows: in the presence of chlorine hydride absorbent, is that solvent make with tetrahydrofuran (THF) or hydrocarbon polymer by corresponding cyclopentadienyl titanous chloride and p methoxy phenol.Chlorine hydride absorbent can be various aminated compoundss, wherein is advisable with alkylamine, for example triethylamine.Hydrocarbon polymer can be aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbon better, for example benzene, toluene etc.Concrete steps are: the tetrahydrofuran (THF) mixing solutions of triethylamine and p methoxy phenol is slowly dropped in the tetrahydrofuran solution of pentamethyl-cyclopentadienyl titanous chloride, the mole ratio of pentamethyl-cyclopentadienyl titanous chloride and p methoxy phenol is 1: 3.0～3.5, the mole ratio of pentamethyl-cyclopentadienyl titanous chloride and triethylamine is 1: 3.0～3.5, temperature of reaction is 0～60 ℃, reaction times is 1～30 hour, solids removed by filtration, underpressure distillation removes and desolvates, the crude product hexane extraction that obtains gets the xanchromatic solid at-20 ℃ of recrystallizations.
Work as R
1Be pentamethyl-cyclopentadienyl, R
2Be methyl, OR
2When the contraposition of phenyl ring, the ultimate analysis of compound, proton nmr spectra
1HNMR, carbon-13 nmr spectra
13NMR, mass spectrum MS the results are shown in following data:
Fig. 1 is the DSC spectrogram of compound (A).
Fig. 2 is a compound (A)
13The CNMR spectrogram.
Fig. 3 is a compound (A)
1The HNMR spectrogram.
Fig. 4 is the mass spectrum of compound (A).
Its data are respectively as follows:
Elementary analysis (element analysis) Calcd for C31H
36O
6Ti， C：67.39 H：6.52
Found： C：66.99 H：6.51
Proton nmr spectra [1HNMR(CDCl
3)]
δ1.95[S，15H(CH
3)
5C
5] δ3.79[S，9H(OCH
3)
3]δ6.76[m，12Hph
3]
Carbon-13 nmr spectra [13CNMR(CDCl
3)]
δ11.49[(CH
3)
5C
5] δ55.76(OCH
3)
δ114.14(ph C-3.5) δ119.28(ph C-2.6)
δ125.17(Cp C) δ153.03(ph C-4)
δ159.40(ph C-1)
Mass spectrum [MS (m/2, % intensity)] 552 (61.74 M+)，429(100，M-OC
6H
40CH
3 +)
306[11.20 M-2(OC
6H
40CH
3)
+]， 135[5.67 C
5(CH
3)
5 +]
Polymerisation is preferably carried out between 50～95 ℃ at 25～110 ℃. In order to obtain the polymerization of ideal performance Thing, polymerization need to be used the regular hour, from a few minutes kind by several hours, preferably 1～10 hour, desirable polymerization time Depend on polymerization temperature and other polymerizing condition.
The present invention adopts a kind of new metallocene compound as the major catalyst for preparing syndiotactic polytyrene, makes urging of catalyst Change the most effective 110.9 kg of polymer/gram titanium that reaches, obtained good effect.
The invention will be further elaborated below by embodiment.[embodiment 1]
The preparation of metallocene compound
In thorough drying, repeatedly add 120ml tetrahydrofuran (THF) (THF) respectively in the flask at the bottom of the metathetical 250ml garden through high pure nitrogen, 4.36g (0.118mol) potassium metal and 15ml (0.118mol) pentamethyl-cyclopentadiene refluxed 6 hours, was cooled to stirring at normal temperature 18 hours.After being chilled to 0 ℃, add 15ml (0.118mol) trimethylchlorosilane, reacted 4 hours, filter, with the 80mlTHF washing, THF is removed in vacuum distilling.Slowly add 200ml heptane and 9mlTiCl again
4Mixed solution, refluxed 1 hour, vacuum distilling remove desolvate thick product, under 200 ℃/16mmHg, distil 15.00g pentamethyl-cyclopentadienyl titanous chloride (Cp
*TiCl
3), Cp wherein
*Be the pentamethyl-cyclopentadienyl.
Get the Cp of above-mentioned preparation
*TiCl
33.373g, with the 70mlTHF dissolving, under 0 ℃, slowly drip 4.8ml (3.473g) triethylamine, slowly drip the 70mlTHF solution of 4.268g p methoxy phenol again, normal temperature stirred 18 hours down, filtered, and THF is removed in vacuum distilling, gets red buttery liquid.Red oily liquids was stirred 20 hours down at 50 ℃ with the 140ml hexane, filter, with liquid recrystallization to-18 ℃ of temperature, remove hexane and get yellow crystals 3.86g, the fusing point of yellow crystals is 134.6 ℃.It is mixed with 1 * 10
-5Mol Ti/ml toluene solution is called catalyst A.[embodiment 2]
The preparation of methylaluminoxane
The toluene solution 130ml that will contain 30.5g (0.423mol) trimethyl aluminium slowly is added drop-wise under-10～0 ℃ of temperature and contains 25g (0.677mol) Al
2(SO
4)
318H
2O) in the 100ml toluene solution, then reaction mixture was stirred 20 hours down at 60 ℃, filter, solid is given a baby a bath on the third day after its birth inferior with 100ml toluene, get water white toluene solution, is concentrated into 150ml, is referred to as catalyst B.Every milliliter of toluene solution contains methylaluminoxane (MAO) 1.5 * 10 by analysis
-3Mol contains trimethyl aluminium (TMA) 2.05 * 10
-4Mol.[embodiment 3]
The dry there-necked flask of 100ml after repeatedly the rare gas element pump drainage is replaced, is added 20ml vinylbenzene, 0.78ml catalyst B and 7.5 * 10
-5The mol triisobutyl aluminium after stirring 30 minutes under 70 ℃, adds the 0.4ml catalyst A, add 10%HCl-EtOH (ethanol) 30ml after two hours and stop polymerization, with polymkeric substance EtOH thorough washing, get polymkeric substance 12.5g 60 ℃ of following vacuum-dryings, catalytic efficiency is 6.54 * 10
4Gps/gTi, catalytic activity is 3.27 * 10
4Gps/gTi.h.The insoluble part proportion of boiling butanone is 95.4% in the polymkeric substance, and the fusing point of polymkeric substance is 269 ℃, and the Mn of polymkeric substance is 18 * 10
5[embodiment 4]
With the dry there-necked flask of 100ml after rare gas element pump drainage displacement repeatedly, add 20ml vinylbenzene, 1.6ml catalyst B, after stirring 30 minutes under 70 ℃, add the 0.4ml catalyst A, add 10%HCl-EtOH 30ml after two hours and stop polymerization, polymkeric substance EtOH thorough washing, get polymkeric substance 10.7g 60 ℃ of following vacuum-dryings, catalytic efficiency is 5.59 * 10
4Gps/gTi, catalytic activity is 2.8 * 10
4Gps/gTi.h.The insoluble part proportion of boiling butanone is 96.3% in the polymkeric substance, and the fusing point of polymkeric substance is 269.7 ℃, and the Mn of polymkeric substance is 7.0 * 10
5[embodiment 5]
With the dry there-necked flask of 100ml after rare gas element pump drainage displacement repeatedly, add 20ml vinylbenzene, 0.5ml catalyst B and 0.15ml triisobutyl aluminium, after stirring 30 minutes under 90 ℃, add the 0.4ml catalyst A, add 10%HCl-EtOH 30ml after two hours and stop polymerization, polymkeric substance EtOH thorough washing, get polymkeric substance 11.8g 60 ℃ of following vacuum-dryings, catalytic efficiency is 6.17 * 10
4Gps/gTi, catalytic activity is 3.08 * 10
4Gps/gTi.h.The insoluble part proportion of boiling butanone is 94.8% in the polymkeric substance, and the fusing point of polymkeric substance is 268.3 ℃, and the Mn of polymkeric substance is 4.8 * 10
5[embodiment 6]
The dry there-necked flask of 100ml after repeatedly the rare gas element pump drainage is replaced, is added 20ml vinylbenzene, 0.28ml catalyst A and 4.6 * 10
-4The mol triisobutyl aluminium after stirring 10 minutes under 70 ℃, adds the 0.55ml catalyst B, add 10%HCl-EtOH 30ml after two hours and stop polymerization, with polymkeric substance EtOH thorough washing, get polymkeric substance 12.4g 60 ℃ of following vacuum-dryings, catalytic efficiency is 9.26 * 10
4Gps/gTi, catalytic activity is 4.63 * 10
4Gps/gTi.h.The insoluble part proportion of boiling butanone is 95.6% in the polymkeric substance, and the fusing point of polymkeric substance is 268.9 ℃, and the Mn of polymkeric substance is 4.6 * 10
5[embodiment 7]
The dry there-necked flask of 100ml after repeatedly the rare gas element pump drainage is replaced, is added 20ml vinylbenzene, 0.11ml catalyst A and 2.6 * 10
-4The mol triisobutyl aluminium after stirring 10 minutes under 90 ℃, adds the 0.2ml catalyst B, add 10%HCl-EtOH 30ml after two hours and stop polymerization, with polymkeric substance EtOH thorough washing, get polymkeric substance 3.9g 60 ℃ of following vacuum-dryings, catalytic efficiency is 8.16 * 10
4Gps/gTi, catalytic activity is 4.08 * 10
4Gps/gTi.h.The insoluble part proportion of boiling butanone is 96.2% in the polymkeric substance, and the fusing point of polymkeric substance is 268.7 ℃, and the Mn of polymkeric substance is 4.7 * 10
5[embodiment 8]
The dry there-necked flask of 100ml after repeatedly the rare gas element pump drainage is replaced, is added 20ml vinylbenzene, 0.2ml catalyst A and 3.4 * 10
-4The mol triisobutyl aluminium after stirring 10 minutes under 70 ℃, adds the 0.26ml catalyst B, add 10%HCl-EtOH 30ml after two hours and stop polymerization, with polymkeric substance EtOH thorough washing, get polymkeric substance 6.1g 60 ℃ of following vacuum-dryings, catalytic efficiency is 6.38 * 10
4Gps/gTi, catalytic activity is 3.19 * 10
4Gps/gTi.h.The insoluble part proportion of boiling butanone is 96.3% in the polymkeric substance, and the fusing point of polymkeric substance is 267.9 ℃, and the Mn of polymkeric substance is 3.9 * 10
5[embodiment 9]
The dry there-necked flask of 100ml after repeatedly the rare gas element pump drainage is replaced, is added 20ml vinylbenzene, 0.2ml catalyst A and 1.7 * 10
-4The mol triisobutyl aluminium after stirring 10 minutes under 70 ℃, adds the 0.4ml catalyst B, add 10%HCl-EtOH 30ml after two hours and stop polymerization, with polymkeric substance EtOH thorough washing, get polymkeric substance 10.6g 60 ℃ of following vacuum-dryings, catalytic efficiency is 11.09 * 10
4Gps/gTi, catalytic activity is 5.54 * 10
4Gps/gTi.h.The insoluble part proportion of boiling butanone is 95.7% in the polymkeric substance, and the fusing point of polymkeric substance is 269.4 ℃, and the Mn of polymkeric substance is 4.2 * 10
5
Claims (10)
1, a kind of catalyzer of syndiotactic polystyrene preparation comprises metallocene compound I, alkylaluminoxane II:
R in the formula
1Be cyclopentadienyl or substituted cyclopentadienyl;
R
2For containing the alkyl of 1～6 carbon atom;
R
3For containing the alkyl of 1～4 carbon atom;
OR
2Base can be in ortho position, a position or the contraposition of phenyl ring;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40.
2, according to the catalyzer of the described syndiotactic polystyrene preparation of claim 1, it is characterized in that R
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl.
3, according to the catalyzer of the described syndiotactic polystyrene preparation of claim 1, it is characterized in that R
2Be methyl.
4, according to the catalyzer of the described syndiotactic polystyrene preparation of claim 1, it is characterized in that OR
2Contraposition at phenyl ring.
5, according to the catalyzer of the described syndiotactic polystyrene preparation of claim 1, it is characterized in that R
3Be methyl.
6, according to the catalyzer of the described syndiotactic polystyrene preparation of claim 1, it is characterized in that oligomerisation degree n value is 10～30.
7,, it is characterized in that aluminium among the alkylaluminoxane II is 50～2000 to the mol ratio of metallocene compound I according to the catalyzer of the described syndiotactic polystyrene of claim 1 preparation.
8, according to the catalyzer of the described syndiotactic polystyrene preparation of claim 1, it is characterized in that also containing in the catalyzer component aluminum alkyls III, general formula is Al (R
4)
3, R wherein
4For containing the alkyl of 1～4 carbon atom.
9, the catalyzer of described according to Claim 8 syndiotactic polystyrene preparation is characterized in that R
4Be isobutyl-.
10, the catalyzer of described according to Claim 8 syndiotactic polystyrene preparation is characterized in that aluminium among the aluminum alkyls III is 0.1～1000 to the mol ratio of metallocene compound I.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110851A CN1076733C (en) | 1998-05-20 | 1998-05-20 | Catalyst for preparing syndiotactic polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110851A CN1076733C (en) | 1998-05-20 | 1998-05-20 | Catalyst for preparing syndiotactic polystyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235984A CN1235984A (en) | 1999-11-24 |
| CN1076733C true CN1076733C (en) | 2001-12-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110851A Expired - Fee Related CN1076733C (en) | 1998-05-20 | 1998-05-20 | Catalyst for preparing syndiotactic polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1076733C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093140C (en) * | 1999-06-24 | 2002-10-23 | 中国石油化工集团公司 | Catalyst for preparing syndiotactic poly styrene |
| KR100690352B1 (en) * | 2005-04-02 | 2007-03-12 | 주식회사 엘지화학 | Method of producing styrenic polymers using high speed catalytic dispersion technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988010275A1 (en) * | 1987-06-17 | 1988-12-29 | The Dow Chemical Company | Catalyst and process for preparation of syndiotactic polystyrene |
| JPH02102206A (en) * | 1988-10-11 | 1990-04-13 | Asahi Chem Ind Co Ltd | Manufacture of stereoregular polystyrene |
-
1998
- 1998-05-20 CN CN98110851A patent/CN1076733C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988010275A1 (en) * | 1987-06-17 | 1988-12-29 | The Dow Chemical Company | Catalyst and process for preparation of syndiotactic polystyrene |
| JPH02102206A (en) * | 1988-10-11 | 1990-04-13 | Asahi Chem Ind Co Ltd | Manufacture of stereoregular polystyrene |
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|---|---|
| CN1235984A (en) | 1999-11-24 |
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