CN1076734C - Catalyst for preparing syndiotactic polystyrene - Google Patents

Catalyst for preparing syndiotactic polystyrene Download PDF

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CN1076734C
CN1076734C CN98110855A CN98110855A CN1076734C CN 1076734 C CN1076734 C CN 1076734C CN 98110855 A CN98110855 A CN 98110855A CN 98110855 A CN98110855 A CN 98110855A CN 1076734 C CN1076734 C CN 1076734C
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syndiotactic polystyrene
catalyzer
hydrogen
catalyst
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CN1235986A (en
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祝方明
周文乐
林尚安
涂建军
伍青
陈德铨
许光学
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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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    • 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 for preparing syndiotactic polystyrene (sPS), which comprises an organic metallic titanium compound Cp*Ti(OCH2CH=CR1R2)3 and alkyl aluminoxane, wherein Cp* is a pentamethyl cyclopentadiene radical; R1 and R2 are hydrogen or alkyl radicals containing 1 to 16 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; the molecular weight can be controlled within a high range (MW of 1.5*10<5> to 1.0*10<6>); the catalyst can be used for industrial production.

Description

The catalyzer of preparation syndiotactic polystyrene
The present invention relates 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 organo-metallic titanium compound and poly-methylaluminoxane (MAO) to form usually, wherein organometallic compound mainly is a 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, but its catalytic activity and catalytic efficiency are not high, and industrial application is undesirable.
The objective of the invention is the catalytic activity and the not high defective of catalytic efficiency that exist in the above-mentioned document for overcoming, a kind of catalyzer of new preparation syndiotactic polystyrene is provided, this catalyzer has advantages of high catalytic activity and catalytic efficiency, and molecular weight can be controlled at a higher scope (M w=1.5 * 10 5～1.0 * 1O 6).
The objective of the invention is to realize by following technical scheme: a kind of catalyzer for preparing syndiotactic polystyrene comprises organic metal titanium compound I and alkylaluminoxane II:
Cp *Ti(OCH 2CH＝CR 1R 2) 3 I
Cp in the formula *Be the pentamethyl-cyclopentadienyl;
R 1For hydrogen or contain the alkyl of 1～16 carbon atom;
R 2For hydrogen or contain the alkyl of 1～16 carbon atom;
R 3For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40.
R in the technique scheme 1And R 2Preferred version be hydrogen; R 3Preferred version be methyl.The preferred value of oligomerisation degree n is 1O～30, and aluminium is 50～2000 to the mole ratio of organo-metallic titanium compound I among the alkylaluminoxane II.
Poly-alkylaluminoxane is prepared by control hydrolysis by aluminum alkyls.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, CaSO 42H 2O, Al 2(SO 4) 318H 2O, MgSO 47H 2O, FeSO 47H 2O, Ti (SO 4) 24H 2O, Ti 2(SO 4) 38H 2O and ZnSO 47H 2O etc.Trimethyl aluminium (TMA) is 1: 1～1: 3 with the mole ratio of water, 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 mole ratio is slowly to be added dropwise to Al in 1: 1～1: 2 under-20～0 ℃ 2(SO 4) 318H 2In the toluene mixture liquid of O, 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.
The preparation method of organo-metallic titanium compound I is as follows: is that solvent reaction make with the hydrocarbon polymer by corresponding pentamethyl-cyclopentadienyl titanous chloride and corresponding alkenyl alcohol in the presence of chlorine hydride absorbent.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: the mixing solutions of triethylamine and corresponding alkenyl alcohol is slowly dropped in the benzole soln of pentamethyl-cyclopentadienyl titanous chloride, the mole ratio of pentamethyl-cyclopentadienyl titanous chloride and corresponding alkenyl alcohol 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 protection of inert gas, underpressure distillation are removed and to be desolvated, the crude product hexane extraction that obtains, remove volatile matter after, must orange-red mucus.
Work as R 1And R 3When being hydrogen, the ultimate analysis of organo-metallic titanium compound I, hydrogen nuclear magnetic resonance spectrum 1H NMR, nuclear magnetic resonance of carbon spectrum 13C NMR the results are shown in following data:
Ultimate analysis (element analysis)
Calcd?for?C 19H 30O 3Ti：C：64.44；H：8.47. Found：C：64.13；H：8.24
Hydrogen nuclear magnetic resonance spectrum [ 1H NMR (CDCl 3TMS intern)]
δ1.34(s，15H，Cp *)，2.07～2.09(s，6H，(OCH 2) 3)；7.42(s，9H，(CH＝CH 2) 3).
Carbon 13Nuclear magnetic resonance spectrum [ 13C NMR (CDCl 3)]
δ11.3(—CH 3)，74.5(—OCH 2—)，77.6～78.4(Cp *C)，121.3～128.1((CH＝CH 2) 3).
Mass spectrum [MS (m/z, % intensity)] 27 (CH=CH 2 +), 41 (CH 2CH=CH 2 +), 57 (OCH 2CH=CH 2 +), 64 (TiO +), 79 (TiOCH +), 93 (TiOCH 2CH +), 107 (TiOCH 2CH=CH 2 +), 135 (C 10H + 15[Cp *] +), 183 (Cp *Ti +), 199 (Cp *TiO +), 240 (Cp *TiOCH 2CH=CH 2 +), 297 (Cp *Ti (OCH 2CH=CH 2) 2 +), 354 (Cp *Ti (OCH 2CH=CH 2 +)).
Catalyst component I and II 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, 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.
The present invention adopts the Primary Catalysts of a kind of new organo-metallic titanium compound as the preparation syndiotactic polystyrene, make the catalytic activity of catalyzer reach 121 kg of polymer/gram titanium/hour, catalytic efficiency reaches 121 kg of polymer/gram titanium, polymericular weight can be at M w=1.5 * 10 5～1.0 * 10 6Regulate in the scope, obtained effect preferably.
Below just the invention will be further elaborated [embodiment 1] by embodiment
The preparation of organo-metallic titanium compound
With 1.68g (5.63mmol) the pentamethyl-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 the exsiccant benzole soln of 1.72g (16.9mmol) triethylamine and 0.98g (16.9mmol) vinyl carbinol; be allowed to condition under 30 ℃ the temperature and react 24h; solids removed by filtration under the nitrogen protection; underpressure distillation removes and desolvates; extract down in 40 ℃ with the exsiccant hexane again; constant temperature leaves standstill 4h; under the nitrogen protection supernatant liquid is transferred in the exsiccant container; remove 60 ℃ of following underpressure distillation then and desolvate and volatile matter; get the orange red oily product of 1.55g, yield 77.6%.The toluene solution that is made into 0.02M is standby.[embodiment 2]
The preparation of MAO
Be equipped with and add the Al of 30g in the 500ml reactor of induction stirring through milling 2(SO 4) 318H 2O and 80ml toluene, under-10 ℃ of temperature, dripping 200ml concentration is trimethyl aluminium (TMA) toluene solution of 3.1mol/L.Rate of addition is 5ml/min, and 60min drips off.Improve temperature of reaction then gradually, in 2h, reach 60 ℃, continue reaction 24h.Reaction mixture is solids removed by filtration under nitrogen protection, and partial solvent is removed in filtrate underpressure distillation under 30 ℃ of temperature, and evaporated under reduced pressure under 50 ℃ temperature gets 15.4g 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 two mouthfuls of flask vacuum-drying of airtight 100ml deoxygenation of charge cavity and gas introduction tube; add MAO 0.11g, the toluene 10ml of embodiment 2 preparations and the organo-metallic titanium compound 0.1ml of embodiment 1 preparation under the nitrogen protection successively, 25 ℃ of lower magnetic forces inject vinylbenzene 10ml after stirring 10min.Behind 80 ℃ of polymerization 1h, with 10% ethanol solution hydrochloride termination reaction, obtain polymkeric substance 7.4g, catalytic activity is 7.72 * 10 4GPS/gTi.h, polymericular weight M w=4.8 * 10 5, a normality is 97%, melt temperature is 269.5 ℃.[embodiment 4]
The preparation of organo-metallic titanium compound
With 1.16g (3.89mmol) the pentamethyl-cyclopentadienyl titanous chloride exsiccant of packing into; be subjected in the 150ml reaction flask of nitrogen protection; add 30ml exsiccant benzene; under nitrogen protection, drip 30ml lentamente again and contain 1.78g (17.5mmol with dropping funnel;) the exsiccant benzole soln of triethylamine and 0.68g (11.7mmol) vinyl carbinol; be allowed to condition under 30 ℃ the temperature and react 24h; solids removed by filtration under the nitrogen protection; underpressure distillation removes and desolvates; use 40 ℃ of extractions of exsiccant hexane again; constant temperature leaves standstill 4h; 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 1.12g, yield 88.1%.The toluene solution that is made into 0.01M is standby.[embodiment 5]
To have two mouthfuls of flask vacuum-drying of airtight 100ml deoxygenation of charge cavity and gas introduction tube; the organo-metallic titanium compound 0.1ml that adds MAO 17.5mg, vinylbenzene 10ml, 1M triisobutyl aluminium hexane solution 0.15ml and embodiment 4 preparations of embodiment 2 preparations under the nitrogen protection successively; behind 90 ℃ of following polymerization 1h; with 10% ethanol solution hydrochloride termination reaction; obtain polymkeric substance 5.8g, catalytic activity is 1.21 * 10 5GPS/gTi.h, polymericular weight M w=5.2 * 10 5, a normality is 98%, melt temperature is 270.2 ℃.[embodiment 6]
To have two mouthfuls of flask vacuum-drying of airtight 100ml deoxygenation of charge cavity and gas introduction tube; the organo-metallic titanium compound 0.1ml that adds MAO 11.6mg, vinylbenzene 10ml, 1M triisobutyl aluminium hexane solution 0.2ml and embodiment 4 preparations of embodiment 2 preparations under the nitrogen protection successively; behind 90 ℃ of following polymerization 1h; with 10% ethanol solution hydrochloride termination reaction; obtain polymkeric substance 4.8g, catalytic activity is 1.0 * 10 5GPS/gTi.h, polymericular weight M w=3.1 * 10 5, a normality is 97%, melt temperature is 269.2 ℃.[embodiment 7]
The preparation of MAO
Be equipped with and add the Al of 41.3g in the 500ml reactor of induction stirring through milling 2(SO 4) 318H 2O and 80ml toluene, under-10 ℃ of temperature, dripping 200ml concentration is trimethyl aluminium (TMA) toluene solution of 3.1mol/L.Rate of addition is 5ml/min, and 60min drips off.Improve temperature of reaction then gradually, in 2h, reach 60 ℃, continue reaction 24h.Reaction mixture is solids removed by filtration under nitrogen protection, and partial solvent is removed in filtrate underpressure distillation under 30 ℃ of temperature, and evaporated under reduced pressure under 50 ℃ temperature gets 12.3g white solid MAO, productive rate 37.0% again. 1The content that H NMR measures TMA among the MAO is 20.0%, and cryoscopic method is surveyed the molecular weight 1210 of MAO.[embodiment 8]
To have two mouthfuls of flask vacuum-drying of airtight 100ml deoxygenation of charge cavity and gas introduction tube; add MAO 0.1lg, the toluene 10ml of embodiment 2 preparations and the organo-metallic titanium compound 0.1ml of EXAMPLE l preparation under the nitrogen protection successively, 30 ℃ of lower magnetic forces inject vinylbenzene 10ml after stirring 10min.Behind 80 ℃ of polymerization 2h, with 10% ethanol solution hydrochloride termination reaction, obtain polymkeric substance 2.1g, catalytic efficiency is 2.19 * 10 4GPS/gTi, polymericular weight M w=6.1 * 10 5, a normality is 98%, melt temperature is 269.1 ℃.

Claims (6)

1, a kind of catalyzer for preparing syndiotactic polystyrene comprises organic metal titanium compound I and alkylaluminoxane II:
Cp *Ti(OCH 2CH＝CR 1R 2) 3 I
Figure C9811085500021
Cp in the formula *Be the pentamethyl-cyclopentadienyl;
R 1For hydrogen or contain the alkyl of 1～16 carbon atom;
R 2For hydrogen or contain the alkyl of 1～16 carbon atom;
R 3For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40.
2, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R 1Be hydrogen.
3, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R 2Be hydrogen.
4, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R 3Be methyl.
5, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that the value of the oligomerisation degree n of alkylaluminoxane is 10～30.
6, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that aluminium among the alkylaluminoxane II is 50～2000 to the mole ratio of organo-metallic titanium compound I.
CN98110855A 1998-05-20 1998-05-20 Catalyst for preparing syndiotactic polystyrene Expired - Fee Related CN1076734C (en)

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Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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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