CN1117105C - Catalyst for preparing syndiotactic polystyrene - Google Patents
Catalyst for preparing syndiotactic polystyrene Download PDFInfo
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- CN1117105C CN1117105C CN 99119960 CN99119960A CN1117105C CN 1117105 C CN1117105 C CN 1117105C CN 99119960 CN99119960 CN 99119960 CN 99119960 A CN99119960 A CN 99119960A CN 1117105 C CN1117105 C CN 1117105C
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- China
- Prior art keywords
- syndiotactic polystyrene
- catalyzer
- titanium compound
- alkylaluminoxane
- mole
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- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title abstract description 8
- -1 pentamethyl cyclopentadiene radical Chemical class 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 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
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- 101100277337 Arabidopsis thaliana DDM1 gene Proteins 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 150000005840 aryl radicals Chemical group 0.000 abstract 1
- 101150113676 chr1 gene Proteins 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006392 deoxygenation reaction Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910016374 CuSO45H2O Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a catalyst for preparing syndiotactic polystyrene (sPS), which comprises an organic metal compound Cp*Ti(OCH2CH=CHR1)3 and alkyl aluminoxane or alkylaluminium, wherein Cp* is a pentamethyl cyclopentadiene radical; R1 is an aryl radical group containing 6 to 20 carbon atoms. When the catalytic system is used for the syndiotactic polymerization of styrene, the catalytic system has high catalytic activity and high catalyzing efficiency; moreover, molecular weight can be controlled within a wide range ((Mw is from 1.5*10<5> to 1.0*10<6>). the catalyst can be used for industrial production.
Description
The present invention relates to be used to prepare the catalyzer of syndiotactic polystyrene.
Styrene polymer can be divided into random polystyrene (aPS), isotactic polyphenylacetylene (iPS) and syndiotactic polystyrene (sPS).The catalyst system that synthesis of syndiotactic polystyrene adopts organometallic compound and poly-methylaluminoxane (MAO) to form usually, organometallic compound is mainly cyclopentadiene titanium compound.It is CpTiCl that document EP 210615, US5252693, JP0291104 and EP389981 etc. have reported structure
3/ MAO, Cp
*TiCl
3/ MAO catalyst system is used for the situation of syndiotactic polymerization of phenylethylene, and still, its catalytic activity and catalytic efficiency are not high, MAO consumption big (Al/Ti＞800), and industrial application is undesirable.
The objective of the invention is for overcoming catalytic activity and the not high defective of catalytic efficiency in the above-mentioned document, a kind of catalyzer of new preparation styrene stereospecific polymers is provided, this catalyzer has advantages of high catalytic activity and catalytic efficiency, and molecular weight can be controlled at scope (Mw=1.5 * 10 of a broad
5～1.0 * 10
6), and the characteristics that can save the MAO consumption.
The objective of the invention is to realize by following technical scheme: a kind of catalyzer for preparing styrene stereospecific polymers comprises organic metal titanium compound I, alkylaluminoxane II and aluminum alkyls III:
Cp
*Ti(OCH
2CH＝CHR
1)
3 I
Al(R
3)
3 III
Cp in the formula
*Be the pentamethyl-cyclopentadienyl;
R
1For containing the aromatic hydrocarbon group of 6～20 carbon atoms;
R
2For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
R
3For containing the alkyl of 1～4 carbon atom;
Wherein aluminium is 50～2000 to the titanium mole ratio among the organo-metallic titanium compound I among the alkylaluminoxane II, and aluminium is 50～400 to the titanium mole ratio among the organo-metallic titanium compound I among the aluminum alkyls III.
R in the technique scheme
1Preferred version be phenyl; R
2Preferred version be methyl; The preferred value of oligomerisation degree n is 10～30; R
3Preferred version be isobutyl-; Aluminium is 50～800 to the mole ratio preferable range of titanium among the organo-metallic titanium compound I among the alkylaluminoxane II.
Poly-alkylaluminoxane is that the control hydrolysis by aluminum alkyls prepares, 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 CaCl26H2O, MgCl26H2O, CuSO45H2O, CaSO42H2O, Al2 (SO4) 318H2O, MgSO47H2O, FeSO47H2O, Ti (SO4) 24H2O, Ti2 (SO4) 38H2O and ZnO47H2O etc.The mole ratio of aluminum alkyls and water is 1: 1～1: 3, 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.Concrete steps are: is slowly to be added dropwise under-20～0 ℃ in Al2 (SO4) 318H2O and the toluene mixture liquid in 1: 1～1: 2 aluminum alkyls by the Al/H2O mole ratio, and the dropping time is 0.5～4 hour.Reaction 5～40 hours is continued in elevated temperature to 20～100 ℃ gradually under this temperature then.Reaction mixture is solids removed by filtration under nitrogen protection, and solvent evaporated under reduced pressure gets white solid product, promptly obtains the alkylaluminoxane that structure is II (MAO).
The preparation method of cyclopentadiene titanium compound I is as follows: by corresponding pentamethyl-cyclopentadienyl titanous chloride and alcohol compound (HOCH
2CH=CHR
1, R wherein
1For containing the aromatic hydrocarbon group of 6～20 carbon atoms) 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.Nytron can be thing aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbon better, for example benzene, toluene etc.Concrete steps are: the mixing solutions of triethylamine and alcohol compound is slowly dropped in the benzole soln of pentamethyl-cyclopentadienyl titanous chloride; the mole ratio of pentamethyl-cyclopentadienyl titanous chloride and alcohol compound is 1.0: 3.0; the mole ratio of pentamethyl-cyclopentadienyl titanous chloride and triethylamine is 1.0: 3.0～4.5; temperature of reaction is 0～50 ℃; 4～30 hours reaction times; solids removed by filtration under the protection of inert gas; underpressure distillation removes and desolvates; the crude product hexane extraction that obtains; after removing volatile matter, get orange-red mucus.
Work as R
1During for phenyl, the general formula of cyclopentadiene titanium compound I is Cp
*Ti (OCH
2CH=CHC
6H
5)
3
Work as R
1During for phenyl, cyclopentadiene titanium compound I's
13CNMR spectrum data are:
12～14ppm Cp
*Methyl carbon
63ppm
Carbon on the base
45PPm -O-CH
2-
Carbon on 124～136ppm phenyl ring on C and the C=C is worked as R
1During for phenyl, the ultimate analysis data of cyclopentadiene titanium compound I are as follows:
Calculated value measured value C 76.32 76.48 H, 7.21 7.52 catalyst component I and II or catalyst component I and II and III can be under protection of inert gas (for example nitrogen, argon gas etc.) under 0～50 ℃, preferably 30 ℃ are reacted earlier.
Polyreaction is preferably carried out between 60～90 ℃ under 30～100 ℃.In order to obtain the polymkeric substance of ideal performance, polymerization needs the regular hour, and by several hours, preferably 0.5～6 hour, the ideal polymerization time depended on polymerization temperature, flux and other polymerizing conditions from several minutes.The polyreaction mode can adopt solution polymerization, slurry polymerization and mass polymerization.For solution polymerization and slurry polymerization, the flux of employing is aliphatic hydrocarbon or aromatic hydrocarbon, as hexane, heptane, hexanaphthene, benzene, toluene etc.The concentration of vinylbenzene in flux is in 5～100% scopes.
The present invention adopts a kind of new cyclopentadiene titanium compound as the Primary Catalysts for preparing syndiotactic polystyrene, makes the catalytic activity of catalyzer reach 6.2 * 10
6Gram PS/ mole Ti. hour, catalytic efficiency reaches 7.0 * 10
6Gram PS/ mole Ti, polymericular weight can be in Mw=1.5 * 10
5～1.0 * 10
6Regulate in the scope, and aluminium/titanium mol ratio＜400, effect preferably obtained.
Below just the invention will be further elaborated by embodiment.[embodiment 1]
The preparation of cyclopentadiene titanium compound
With 1.68 gram (5.63 mmole) the pentamethyl-cyclopentadienyl titanous chlorides exsiccant of packing into; be subjected in 250 milliliters of reaction flasks of nitrogen protection; add 50 milliliters of exsiccant benzene; again under nitrogen protection with dropping funnel lentamente 0 milliliter of Dropwise 5 contain the exsiccant benzole soln of 1.72 gram (16.9 mmole) triethylamines and 2.26 gram (16.9 mmole) cinnamic alcohols; be allowed to condition under 30 ℃ the temperature reaction 24 hours; solids removed by filtration under the nitrogen protection; underpressure distillation removes and desolvates; use 40 ℃ of extractions of exsiccant hexane again; constant temperature left standstill 4 hours; under the nitrogen protection supernatant liquid is transferred in the exsiccant container; 60 ℃ of underpressure distillation remove and desolvate and volatile matter then; get the orange red oily product of 2.90 grams, yield 88.6%.The toluene solution that is made into 0.01 mol is standby.[embodiment 2]
The preparation of alkylaluminoxane (MAO)
Be equipped with and add 30 Als of gram in 500 milliliters of reactors of induction stirring through grinding
2(SO
4)
318H
2O and 80 milliliters of toluene under-10 ℃ of temperature, drip the trimethyl aluminium that 200 ml concns are 3.1 mol (TMA) toluene solution.Rate of addition is 5 ml/min, drips off in 60 minutes.Improve temperature of reaction then gradually, in 2 hours, reach 60 ℃, continue reaction 24 hours.Reaction mixture is solids removed by filtration under nitrogen protection, and partial solvent is removed in filtrate underpressure distillation under 30 ℃ temperature, and evaporated under reduced pressure under 50 ℃ temperature gets 15.4 gram white solid MAO, productive rate 39.0% again.
1The content that H NMR measures TMA among the MAO is 25.0%, and cryoscopic method is surveyed the molecular weight 1100 of MAO.[embodiment 3]
To have airtight 100 milliliters two mouthfuls flask vacuum-drying deoxygenations of charge cavity and gas introduction tube, add MAO1.92 * 10 of embodiment 2 preparations under the nitrogen protection successively
-30.24 milliliter of the cyclopentadiene titanium compound of mole, 20 milliliters of vinylbenzene and embodiment 1 preparation, 30 ℃ of lower magnetic forces stir after 10 minutes temperature are risen to 90 ℃ of polymerizations 1 hour, with 10%HCl ethanolic soln termination reaction, obtain polymkeric substance 12.96 grams, catalytic activity is 5.40 * 10
6Gram PS/ mole Ti. hour, polymericular weight Mw=5.4 * 10
5, a normality 98%, melt temperature are 271.8 ℃.[embodiment 4]
To have airtight 100 milliliters two mouthfuls flask vacuum-drying deoxygenations of charge cavity and gas introduction tube, add MAO9.60 * 10 of embodiment 2 preparations under the nitrogen protection successively
-4Mole, 20 milliliters of vinylbenzene, triisobutyl aluminium (TIBA) 7.20 * 10
-40.24 milliliter of the cyclopentadiene titanium compound of mole and embodiment 1 preparation, 30 ℃ of lower magnetic forces stir after 10 minutes temperature are risen to 90 ℃ of polymerizations 1 hour, with 10%HCl ethanolic soln termination reaction, obtain polymkeric substance 14.22 grams, and catalytic activity is 5.93 * 10
6Gram PS/ mole Ti. hour, polymericular weight Mw=5.1 * 10
5, a normality 97%, melt temperature are 270.1 ℃.[embodiment 5]
The preparation of cyclopentadiene titanium compound
With 1.16 gram (3.89 mmole) the pentamethyl-cyclopentadienyl titanous chlorides exsiccant of packing into; be subjected in 150 milliliters of reaction flasks of nitrogen protection; add 30 milliliters of exsiccant benzene; under nitrogen protection, drip 30 milliliters of exsiccant benzole solns that contain 1.78 gram (17.5 mmole) triethylamines and 1.38 gram (11.7 mmole) cinnamic alcohols lentamente again with dropping funnel; be allowed to condition under 30 ℃ the temperature reaction 24 hours; solids removed by filtration under the nitrogen protection; underpressure distillation removes and desolvates; use 40 ℃ of extractions of exsiccant hexane again; constant temperature left standstill 4 hours; under the nitrogen protection supernatant liquid is transferred in the exsiccant container; 60 ℃ of underpressure distillation remove and desolvate and volatile matter then; get the orange red oily product of 1.86 grams, yield 89.6%.The toluene solution that is made into 0.01 mol is standby.[embodiment 6]
To have airtight 100 milliliters two mouthfuls flask vacuum-drying deoxygenations of charge cavity and gas introduction tube, add MAO1.92 * 10 of embodiment 2 preparations under the nitrogen protection successively
-30.24 milliliter of the cyclopentadiene titanium compound of mole, 20 milliliters of vinylbenzene and embodiment 5 preparations, 30 ℃ of lower magnetic forces stir after 10 minutes temperature are risen to 90 ℃ of polymerizations 1 hour, with 10%HCl ethanolic soln termination reaction, obtain polymkeric substance 13.03 grams, catalytic activity is 5.43 * 10
6Gram PS/ mole Ti. hour, polymericular weight Mw=5.5 * 10
5, a normality 98%, melt temperature are 271.1 ℃.[embodiment 7]
To have airtight 100 milliliters two mouthfuls flask vacuum-drying deoxygenations of charge cavity and gas introduction tube, add MAO9.60 * 10 of embodiment 2 preparations under the nitrogen protection successively
-4Mole, 20 milliliters of vinylbenzene, triisobutyl aluminium (TIBA) 7.20 * 10
-40.24 milliliter of the cyclopentadiene titanium compound of mole and embodiment 5 preparations, 30 ℃ of lower magnetic forces stir after 10 minutes temperature are risen to 90 ℃ of polymerizations 1 hour, with 10%HCl ethanolic soln termination reaction, obtain polymkeric substance 14.83 grams, and catalytic activity is 6.18 * 10
6Gram PS/ mole Ti. hour, polymericular weight Mw=5.0 * 10
5, a normality 98%, melt temperature are 270.0 ℃.[embodiment 8]
To have airtight 100 milliliters two mouthfuls flask vacuum-drying deoxygenations of charge cavity and gas introduction tube, add the MAO 8.0 * 10 of embodiment 2 preparations under the nitrogen protection successively
-4Mole, 20 milliliters of vinylbenzene, triisobutyl aluminium (TIBA) 6.0 * 10
-40.20 milliliter of the cyclopentadiene titanium compound of mole and embodiment 5 preparations, 30 ℃ of lower magnetic forces stir after 10 minutes temperature are risen to 90 ℃ of polymerizations 2 hours, with 10%HCl ethanolic soln termination reaction, obtain polymkeric substance 14.50 grams, and catalytic activity is 6.96 * 10
6Gram PS/ mole Ti. hour, polymericular weight Mw=5.0 * 10
5, a normality 98%, melt temperature are 270.0 ℃.[embodiment 9]
The preparation of MAO
Be equipped with and add 41.3 Als of gram in 500 milliliters of reactors of induction stirring through grinding
2(SO
4)
318H
2O and 80 milliliters of toluene under-10 ℃ of temperature, drip the trimethyl aluminium that 200 ml concns are 3.1 mol (TMA) toluene solution.Rate of addition is 5 ml/min, drips off in 60 minutes.Improve temperature of reaction then gradually, in 2 hours, reach 60 ℃, continue reaction 24 hours.Reaction mixture is solids removed by filtration under nitrogen protection, and partial solvent is removed in filtrate underpressure distillation under 30 ℃ temperature, and evaporated under reduced pressure under 50 ℃ temperature gets 12.3 gram white solid MAO, productive rate 37.0% again.[embodiment 10]
To have airtight 100 milliliters two mouthfuls flask vacuum-drying deoxygenations of charge cavity and gas introduction tube, add MAO1.92 * 10 of embodiment 8 preparations under the nitrogen protection successively
-30.24 milliliter of the cyclopentadiene titanium compound of mole, 20 milliliters of vinylbenzene and embodiment 5 preparations, 30 ℃ of lower magnetic forces stir after 10 minutes temperature are risen to 90 ℃ of polymerizations 1 hour, with 10%HCl ethanolic soln termination reaction, obtain polymkeric substance 6.89 grams, and catalytic activity is 2.87 * 10
6Gram PS/ mole Ti. hour, polymericular weight Mw=5.9 * 10
5, a normality 98%, melt temperature are 271.5 ℃.[embodiment 11]
To have airtight 100 milliliters two mouthfuls flask vacuum-drying deoxygenations of charge cavity and gas introduction tube, add the MAO 9.60 * 10 of embodiment 8 preparations under the nitrogen protection successively
-4Mole, 20 milliliters of vinylbenzene, triisobutyl aluminium (TIBA) 7.20 * 10
-40.24 milliliter of the cyclopentadiene titanium compound of mole and embodiment 5 preparations, 30 ℃ of lower magnetic forces stir after 10 minutes temperature are risen to 90 ℃ of polymerizations 1 hour, with 10%HCl ethanolic soln termination reaction, obtain polymkeric substance 13.63 grams, and catalytic activity is 5.68 * 10
6Gram PS/ mole Ti. hour, polymericular weight Mv=5.2 * 10
5, a normality 98%, melt temperature are 271.0 ℃.
Claims (6)
1, a kind of catalyzer that is used to prepare syndiotactic polystyrene comprises organic metal titanium compound (I), alkylaluminoxane (II) and aluminum alkyls (III);
Cp
*Ti(OCH
2CH＝CHR
1)
3 I
Al(R
3)
3 III
In the formula: Cp
*Be the pentamethyl-cyclopentadienyl;
R
1For containing the aromatic hydrocarbon group of 6～20 carbon atoms;
R
2For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
R
3For containing the alkyl of 1～4 carbon atom;
Wherein aluminium is 50～2000 to the titanium mole ratio in the organo-metallic titanium compound (I) in the alkylaluminoxane (II), and aluminium is 50～400 to the titanium mole ratio in the organo-metallic titanium compound (I) in the aluminum alkyls (III).
2, the catalyzer that is used to prepare syndiotactic polystyrene according to claim 1 is characterized in that R
1Be phenyl.
3, the catalyzer that is used to prepare syndiotactic polystyrene according to claim 1 is characterized in that R
2Be methyl.
4, the catalyzer that is used to prepare syndiotactic polystyrene according to claim 1 is characterized in that the value of the oligomerisation degree n of alkylaluminoxane is 10～30.
5, the catalyzer that is used to prepare syndiotactic polystyrene according to claim 1 is characterized in that R
3Be isobutyl-.
6, the catalyzer that is used to prepare syndiotactic polystyrene according to claim 1 is characterized in that the middle aluminium of alkylaluminoxane (II) is 50～800 to the mole ratio of titanium in the organo-metallic titanium compound (I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119960 CN1117105C (en) | 1999-11-03 | 1999-11-03 | Catalyst for preparing syndiotactic polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119960 CN1117105C (en) | 1999-11-03 | 1999-11-03 | Catalyst for preparing syndiotactic polystyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1295086A CN1295086A (en) | 2001-05-16 |
| CN1117105C true CN1117105C (en) | 2003-08-06 |
Family
ID=5281249
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99119960 Expired - Fee Related CN1117105C (en) | 1999-11-03 | 1999-11-03 | Catalyst for preparing syndiotactic polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1117105C (en) |
-
1999
- 1999-11-03 CN CN 99119960 patent/CN1117105C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1295086A (en) | 2001-05-16 |
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