CN1150154A - Preparation of cyclopentadienyl titanium trialkyl(aryl) oxy compound - Google Patents

Preparation of cyclopentadienyl titanium trialkyl(aryl) oxy compound Download PDF

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CN1150154A
CN1150154A CN 95113341 CN95113341A CN1150154A CN 1150154 A CN1150154 A CN 1150154A CN 95113341 CN95113341 CN 95113341 CN 95113341 A CN95113341 A CN 95113341A CN 1150154 A CN1150154 A CN 1150154A
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preparation
reaction
oxycompound
virtue
titanium
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CN1050608C (en
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陈德建
涂建军
欧阳建莹
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Abstract

A process for preparing cyclopentatitanium trialkyl aryloxy compounds by reaction of R1TiX3 with the alcohol corresponding to radical to be synthesized or the phenyl containing arylalkyl features that the reaction occurs at 0-60 deg.C and ordinary pressure, where amino salt is used as gas absorbent, and said compounds are obtained after recrystallization. Its advantages include short reaction time, high purity of product and reduced by-product. Said process can be used to prepare the catalyst for syndiotactic polymerization of styrene.

Description

The preparation of luxuriant titanium three alkane (virtue) oxycompound
The present invention relates to the preparation of organic luxuriant metal compound, particularly about the preparation of cyclopentadiene titanium compound.
Luxuriant titanium three alkane (virtue) oxycompound is one of main catalysis composition that is used for syndiotactic polymerization of phenylethylene, and it forms the high activated catalyst that syndiotactic polymerization of phenylethylene is used with methylaluminoxane MAO.The molecular structural formula of luxuriant titanium three alkane (virtue) oxycompound is R 1Ti (OR 2) 3R wherein 1Be many methyl cyclopentadienyls N=0～5 wherein.At document J.C.S.Dalton1982, reported CpTi (OPh) among P271～274 Steven R.Wade etc 3Synthetic method, wherein Ph is a phenyl, Cp is a cyclopentadienyl.This method is at synthetic CpTi (OPh) 3Be to be chlorine hydride absorbent in the process, pass through CpTiCl with the triethylamine 3Make with phenol reactant.But the shortcoming of this method is long reaction time, needs to stir 24 hours that the by product product purities many, behind complex crystallization of not clear structure are low, its CpTi (OPh) 3Fusing point Tm only is 92～93 ℃.Thereby as the catalyzer composition time, can influence activity of such catalysts and purity greatly.For the shortcoming that overcomes aforesaid method obtains a kind of highly purified luxuriant titanium three alkane (virtue) oxycompound, and in reaction process, pay produce less, the reaction times is short, we have invented a kind of new preparation method of preparation luxuriant titanium three alkane (virtue) oxycompound.
The objective of the invention is to realize by following technical scheme.In reaction process, by R 1TiX 3With the synthetic pairing alcohol of group of needs or contain the phenol of aryl, be gas absorbent with the amide, under normal pressure, 0～60 ℃ of reaction conditions of temperature, in the organic solvent that contains aromatic hydrocarbons, react, behind complex crystallization, make R 1Ti (OR 2) 3, R wherein 2Be alkyl, aryl, aralkyl, alkaryl; X is a halogen.
In this reaction process, entire reaction should be to carry out in the reaction system of anaerobic, anhydrous, nitrogen protection, and the better temperature range of reaction is 0～30 ℃, and X wherein is chlorine, bromine, iodine, R 2Be methyl, ethyl, butyl, phenyl, benzyl, tolyl, ethylbenzene base.Amide can be selected from least a or its mixture in sodium amide, Lithamide, the potassium amide.The organic solvent that contains aromatic hydrocarbons is selected from least a or its mixture in benzene, ethylbenzene, dimethylbenzene, the toluene.Under agitation condition, question response removed by filter salt after 0.5～4 hour, boiled off solvent aromatic hydrocarbons from filtrate, added this solid of extraction heat with exsiccant hexane or heptane again.Luxuriant titanium three alkane (virtue) oxycompound and the by product that contain solubility in the extraction liquid further separate and remove by product, get clear bright solution.After concentrating, cool off, placing, obtain luxuriant titanium three alkane of xanchromatic (virtue) oxycompound, wherein CpTi (OPh) 3Fusing point Tm after measured is 109 ℃.In the entire reaction course, the reaction yield of luxuriant titanium three alkane (virtue) oxycompound is 75%, and wherein accompanying drawing 1, and accompanying drawing 2 detects CpTi (OPh) for DSC 3Melting-point diagram.
The present invention makes reaction carry out to the product direction by after making gas absorbent with amide, has therefore shortened the reaction times greatly, at short reaction times internal reaction, suppressed the carrying out of pair reaction, thereby the by product growing amount is reduced greatly, degree of purity of production is enhanced.The product that makes with this method is a syndiotactic polymerization of phenylethylene efficient catalytic component.
Embodiment 1
1000 milliliters of reaction flasks that dropping funnel and induction stirring are held in both hands are housed, and through vacuumizing for several times, nitrogen replacement adds CpTiCl in bottle under nitrogen protection 3(12.1g, 55mmol), sodium amide (6.44g, 165mmol), 300 milliliters of dry benzene.In dropping funnel, add and contain phenol (15.51g, 100 milliliters of benzole solns 165mmol).30 ℃ of temperature, the normal pressure stirring adds reaction flask with phenol solution down, can be observed reaction solution colour-change and precipitation generation, stirs after 1 hour, removes by filter deposited salt, and concentrated filtrate gets the black viscous material at last.Extract complex crystallization with heptane, the cooling extraction liquid gets yellow needle-like crystal CpTi (OPh) 316.30 gram, its yield is 75.62%, and it is 109.4 ℃ that fusing point detects through DSC, sees accompanying drawing 1.
Embodiment 2
1000 milliliters of reaction flasks that dropping funnel and induction stirring are held in both hands are housed, and through vacuumizing for several times, nitrogen replacement adds CH in bottle under nitrogen protection 3CpTiCl 3(12.84g, 55mmol).Sodium amide (6.44g, 165mmol), 300 milliliters of dry benzene.In dropping funnel, add and contain phenol (15.51g, 100 milliliters of benzole solns 165mmol).10 ℃ of temperature, the normal pressure stirring adds reaction flask with phenol solution down, can be observed reaction solution colour-change and precipitation generation, stirs after 0.5 hour, removes by filter deposited salt, and concentrated filtrate gets the black viscous material at last.Extract complex crystallization with heptane, the cooling extraction liquid gets CH 3CpTi (OPh) 316.81 gram, its yield is 75.30%, and it is 93.6 ℃ that fusing point detects through DSC.
Embodiment 3
1000 milliliters of reaction flasks that dropping funnel and induction stirring are held in both hands are housed, and through vacuumizing for several times, nitrogen replacement adds (CH in bottle under nitrogen protection 3) 2CpTiBr 3(20.94g, 55mmol), potassium amide (9.09g, 165mmol), 300 milliliters of dry benzene and toluene mixture liquid.In dropping funnel, add and contain methylphenol (17.82g, 100 milliliters of benzene 165mmol) and toluene mixture liquid.40 ℃ of temperature, under normal pressure stirs, methylphenol solution is added in the reaction flask, can be observed the reaction solution colour-change and generate with precipitation, stir after 1.5 hours, remove by filter deposited salt, concentrated filtrate gets the black viscous material at last.Extract complex crystallization with heptane, the cooling extraction liquid gets (CH 3) 2CpTi (OPhCH 3) 319.09 gram, its yield is 75.13%, and it is 150.2 ℃ that fusing point detects through DSC.
Embodiment 4
1000 milliliters of reaction flasks that dropping funnel and induction stirring are held in both hands are housed, and through vacuumizing for several times, nitrogen replacement adds (CH in bottle under nitrogen protection 3) 3CpTiBr 3(21.71g, 55mmol), potassium amide (9.09g, 165mol), 300 milliliters of dry dimethylbenzene.In dropping funnel, add and contain ethylphenol (20.13g, 165mmol) xylene solution is 100 milliliters.50 ℃ of temperature, under normal pressure stirs, ethylphenol solution is added in the reaction flask, can be observed the reaction solution colour-change and generate with precipitation, stir after 25 hours, remove by filter deposited salt, concentrated filtrate gets the black viscous material at last.Extract complex crystallization with heptane, the cooling extraction liquid gets (CH 3) 3CpTi (OPhC 2H 5) 321.35 gram, its yield is 74.95%.
Comparative example 1
1000 milliliters of reaction flasks that dropping funnel and induction stirring are held in both hands are housed, and through vacuumizing for several times, nitrogen replacement adds CpTiCl in bottle under nitrogen protection 3(12.1g, 55mmol), triethylamine (16.70,165mmol), 300 milliliters in dry ethylbenzene.In dropping funnel, add and contain phenol (15.51g, 100 milliliters of ethylbenzene solutions 165mmol).In temperature of reaction is 30 ℃, and the normal pressure stirring adds phenol solution in the reaction flask down, can be observed reaction solution colour-change and precipitation generation, stirs after 24 hours, removes by filter deposited salt, and concentrated filtrate gets the black viscous material at last.Extract complex crystallization with heptane, the cooling extract CpTi (OPh) 315.18 gram, its yield is 70.15%, and fusing point is 104.1 ℃ after testing, sees accompanying drawing 2.
Comparative example 2
1000 milliliters of reaction flasks that dropping funnel and induction stirring are held in both hands are housed, and through vacuumizing for several times, nitrogen replacement adds CH in bottle under nitrogen protection 3CpTiCl 3(12.84 grams, 55mmol), triethylamine (16.70 grams, 165mmol), 300 milliliters of dry toluene.In dropping funnel, add contain phenol (15.51,100 milliliters of toluene solutions 165mmol).10 ℃ of temperature, normal pressure stirs down, and phenol solution is added reaction flask, stirs after 24 hours, removes by filter deposited salt, and concentrated filtrate gets the black viscous material at last.Extract complex crystallization with heptane, the cooling extraction liquid gets crystal CH 3CpTi (OPh) 315.68 gram, its yield is 70.24%, and it is 89.3 ℃ that fusing point detects through DSC.
Comparative example 3
1000 milliliters of reaction flasks that dropping funnel and induction stirring are held in both hands are housed, and through vacuumizing for several times, nitrogen replacement adds (CH in bottle under nitrogen protection 3) 2CpTiBr 3(20.94 grams, 55mmol), triethylamine (16.70 grams, 165mmol), 300 milliliters of dry benzene.In dropping funnel, add and contain methylphenol (17.82 grams, 100 milliliters of benzole solns 165mmol).40 ℃ of temperature, normal pressure stirs down, and ethanolic soln is added reaction flask, stirs after 24 hours, removes by filter deposited salt, and concentrated filtrate gets the black viscous material at last.Extract complex crystallization with heptane, the cooling extraction liquid gets crystal CpTi (OPhCH 3) 317.81 gram, its yield is 70.09%, and it is 146.4 ℃ that fusing point detects through DSC.

Claims (6)

1. the preparation method of luxuriant titanium three alkane (virtue) oxycompound, its molecular structural formula is R 1Ti (OR 2) 3, by R 1TiX 3Be 0～60 ℃ in normal pressure, temperature, contain to react in the organic solvent of aromatic hydrocarbons and make with alcohol or the phenol that contains aryl, it is characterized in that in the reaction process with amide as gas absorbent, wherein R 2Be alkyl, aryl, alkaryl, aralkyl, X is a halogen, and Ti is a titanium, R 1Be many methyl cyclopentadienyls
Figure A9511334100021
N=0～5 wherein.
2. the preparation method of luxuriant titanium three alkane according to claim 1 (virtue) oxycompound is characterized in that R 1Ti (OR 2) 3R in the molecular structural formula 2Be methyl, ethyl, butyl, phenyl, tolyl, ethylbenzene base, benzyl.
3. the preparation method of luxuriant titanium three alkane according to claim 1 (virtue) oxycompound is characterized in that R 1TiX 3X is chlorine, bromine, iodine in the molecular structural formula.
4. the preparation method of luxuriant titanium three alkane according to claim 1 (virtue) oxycompound is characterized in that temperature of reaction is 0～30 ℃.
5. the preparation method of luxuriant titanium three alkane according to claim 1 (virtue) oxycompound is characterized in that the amide as gas absorbent is at least a or its mixture that is selected from sodium amide, Lithamide, the potassium amide.
6. the preparation method of luxuriant titanium three alkane according to claim 1 (virtue) oxycompound is characterized in that, the organic solvent of aromatic hydrocarbons is at least a or its mixture that is selected from benzene,toluene,xylene, the ethylbenzene.
CN95113341A 1995-11-15 1995-11-15 Preparation of cyclopentadienyl titanium trialkyl(aryl) oxy compound Expired - Fee Related CN1050608C (en)

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