CN1252100C - Method of preparing syndiotectic polystyrene - Google Patents
Method of preparing syndiotectic polystyrene Download PDFInfo
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- CN1252100C CN1252100C CN 03150729 CN03150729A CN1252100C CN 1252100 C CN1252100 C CN 1252100C CN 03150729 CN03150729 CN 03150729 CN 03150729 A CN03150729 A CN 03150729A CN 1252100 C CN1252100 C CN 1252100C
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Abstract
The present invention relates to a method for preparing syndiotectic polystyrene, which mainly solves the problems of needing a reactor in a special structure or strong shearing, high energy consumption and low conversion rate existing in the prior art. The method for preparing syndiotectic polystyrene well solves the problems by adopting the technical schemes that a metallocene compound, triisobutylaluminium and alkylaluminium are used as catalysts; inert organic solvents are used as media; reaction temperature is from 10 to 100 DEG C; reaction pressure is normal pressure; the quantity of inert organic solvents is controlled. The method can be used for industrial production of syndiotactic polymerization of styrene.
Description
Technical field
The present invention relates to prepare the method for syndiotactic polystyrene.
Background technology
Syndiotactic polystyrene (sPS) is a kind of novel hypocrystalline thermoplastic engineering plastic, and its high fusing point (270 ℃) and degree of crystallinity are given good heat-resisting, water-fast, the chemical resistant properties of sPS, electrical insulating property and dimensional stability.Syndiotactic polystyrene can utilize forming process such as existing engineering plastics molding device is extruded, injection molding.Since coming out, syndiotactic polystyrene is the focus of paying close attention to both at home and abroad always.
Adopt homogeneous catalysis system to prepare syndiotactic polystyrene in the patent mostly, no matter adopt which kind of catalyst system, syndiotactic polymerization of phenylethylene belongs to special precipitation polymerization because of the crystallisation process event that is accompanied by polymkeric substance, exist complicated phase to alternate, therefore when carrying out the commercial run exploitation, be faced with many engineering problems, in earlier stage be prone to gel as mass polymerization, there is serious sticking oar in the polymerization process, sticking still problem, in case polymerization system transfers the wet-milling attitude to, the power of agitator utmost point is increased severely to be added, simultaneously must be accompanied by problems such as removing hot difficulty, to such an extent as to reaction is difficult to normally carry out.Therefore, how to guarantee that heat of polymerization in time removes, cutting down the consumption of energy is the key of syndiotactic polystyrene engineering development.
Relate to the more of special reaction device design in the present disclosed patent.As adopting the intermittent bulk polymerization among the EP328975, promptly the homogeneous phase before the polymerization has compared various reactor types, stirring and scraper plate form to the polymeric effect till final generation powder.In EP379128, adopt 1 liter of horizontal-type biaxial self-cleaning reactor.JP03020308 has invented a kind of 10 liters of spherical reactors, and it is consistent with reactor wall curvature that it stirs shape.DE19546096 and USP6121391 attempt preparing continuously syndiotactic polystyrene in twin screw extruder.
Tend to bulk polymerisation process in the industrial production, what relevant sPS prepared that patent adopts basically is mass polymerization more, and the research on polymerization technique also can not show a candle to going deep into of extraordinary reactor.Reactor is operated under the powder attitude among the USP5037907, monomer and catalyzer continuously feeding, and the continuous or intermittent take-off of syndiotactic polystyrene powder, successive reaction is controlled at the dry powder attitude can reduce the stirring power consumption effectively, and prevents generations such as sticking still, sticking oar.But this technology needs a large amount of seed powder of pre-input in reactor, impurity is removed in the syndiotactic polystyrene material strictness that requires to drop into, and degree of drying is also higher, and is also strict to the control of benzene feedstock vinyl monomer input concentration, overrich just easily makes product syndiotactic polystyrene caking a little; In addition use the required energy consumption of fluidized-bed process also bigger.The continuous processing of reporting in the patent except that continuous powder fluidized-bed process, single automatically cleaning reactor of general using or automatically cleaning still and the logotype of slot type stirring tank, and mostly adopt mass polymerization.Disclose two stills series connection polymerization technique as Dow Chemical Company in CN1045977A, first still is 1 liter of horizontal-type biaxial self-cleaning reactor, is used for forming powder, and two stills are slot type powder reactor, works to improve transformation efficiency.
Vinylbenzene body syndiotactic polymerization is no matter be periodical operation or continuous processing, fundamentally do not solve the problem of removing heat and cutting down the consumption of energy, for guaranteeing that polymerization is carried out smoothly is cost with sacrifice efficient, high energy consumption often, and such reactor and polymerization technique are unfavorable for the industry amplification.Remove mass polymerization, the polymerization process that relates to other is also arranged in patent documentation.Select for use solubility parameters between 4～7 fluoride fat family alkane or to fluoridize aromatic hydrocarbon be dispersion medium as USP4950724, add suitable suspension dispersive agent, carry out syndiotactic polymerization of phenylethylene, obtained the pearl syndiotactic polystyrene.The difficult point of this method is the selection of dispersion medium and suspension dispersive agent, and this class chemical production is difficult and price is more expensive.A kind of dispersion polymerization process of syndiotactic polymerization of phenylethylene has also been proposed among the USP6235838,1,3-divinyl, vinylbenzene and 1, the segmented copolymer of the different components that the copolymerization of 1-Vinylstyrene generates is as the dispersion agent of polymerization system, add-on is about 2%, the sPS particle form that makes is good, and no polymkeric substance silts generation up.Above-mentioned suspension, dispersion polymerization all need to add the dispersion agent of special construction.
Summary of the invention
Technical problem to be solved by this invention be have reactor that need be by special construction in the existing document or shear by force, high energy consumption just can reach granulating, and the low problem of styrene conversion rate provides a kind of new method for preparing syndiotactic polystyrene.It is steady that this method has polymerization process, and polymerisate granulating effect is obvious, do not have block or sticking still, sticking oar phenomenon, and power of agitator is low, and it is easy to remove thermal capacitance, and product postprocessing is characteristics easily.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing syndiotactic polystyrene, with vinylbenzene is raw material, with the metallocene-titanium metal compound is Primary Catalysts, triisobutyl aluminium is or/and the oligomerisation degree is 6～40 alkylaluminoxane is promotor, aluminium in the triisobutyl aluminium is 50～400 to the titanium mole ratio in the metallocene-titanium metal compound, aluminium in the alkylaluminoxane is 50～2000 to the titanium mole ratio in the metallocene-titanium metal compound, with the inert organic solvents is medium, in temperature of reaction is 10～100 ℃, reaction pressure is that reaction generates syndiotactic polystyrene under the condition of normal pressure, and wherein the amount of inert organic solvents is 20～90% of a polymerization system gross weight.
In the technique scheme, the metallocene-titanium metal compound preferred version is for being selected from R
1Ti (OR
2)
3, R
1TiCl
3Or R
1Ti (OR
3OR
4)
3, R wherein
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl, R
2, R
3Or R
4Be selected from alkyl, aryl, aralkyl or the alkaryl of 1～12 carbon atom.The inert organic solvents preferred version is selected from 2, at least a in 2-dimethylbutane, 3-methylpentane, Skellysolve A, pentamethylene, methylcyclopentane, normal hexane, isohexane, hexanaphthene, 2-methyl hexane, heptane, octane-iso, benzene,toluene,xylene, ethylbenzene, chlorobenzene or the fluorobenzene, more preferably scheme is selected from least a in normal hexane, isohexane, hexanaphthene, 2-methyl hexane or the heptane.The temperature of reaction preferable range is 40～80 ℃, and the amount preferable range of inert organic solvents is 50～80% of a polymerization system gross weight.
Control transformation efficiency by the add-on of control reaction temperature, catalyst proportion and organic solvent in the technology of the present invention, reaction is carried out smoothly, obtain meeting necessarily required granulating syndiotactic polystyrene.The adding of inert organic solvents helps the homodisperse of catalyzer on the one hand, can prevent the sticking still that causes reaction too acutely to cause owing to the catalyzer partial concn is too high, the generation of caking phenomenon, because monomer concentration is compared mass polymerization and decreased, therefore delayed polymerization rate simultaneously; Inert solvent is again the good heat transfer medium on the other hand, makes reaction smoothly, carry out reposefully thereby can remove heat of polymerization timely and effectively.Because the polymerization process prevented from caking, make the reaction can be steadily easy to operate, so the reactor power consumption be compared greatly and is reduced with mass polymerization.Technology of the present invention just can be carried out in general agitated slurry groove type reactor.
Among the present invention, owing to added the usage quantity of suitable solvent, the purpose that makes the solvent use is not only in order to remove heat, reaction can be reacted as solution homogeneous phase method, can be used to particle form and make the polymerization process balance, avoided block or sticking still, mucilage phenomenon, made simultaneously that to remove heat more easy.The inventor unexpectedly invents simultaneously, and technical scheme of the present invention can make power of agitator descend greatly on the one hand, is about 40～60% of former power of agitator, and cinnamic transformation efficiency can improve greatly simultaneously, reaches as high as 88.9%, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times adds 1500 milliliters of styrene monomers, 1500 milliliters of hexanes.Stir after 30 minutes, contain 29.25 mmole triisobutyl aluminiums, 48.75 mmole MAO with the syringe injection, 0.195 the metallocene-titanium catalyst toluene solution of mmole embodiment 1, at 300 rev/mins of following stirring reactions after 4 hours, 1.9 kilowatts of wherein maximum powers of agitator, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1050 restrains, greater than 0.8 millimeter saccharoid, 50 grams, styrene conversion rate 81.5%, between normality 97%, primary crystallization degree 40%, molecular weight distribution 1.9.
[embodiment 2]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times adds 1000 milliliters of styrene monomers, 2000 milliliters of hexanes.Stir after 30 minutes, contain 29.25 mmole triisobutyl aluminiums, 48.75 mmole MAO with the syringe injection, 0.195 the metallocene-titanium catalyst toluene solution of mmole embodiment 1, at 300 rev/mins of following stirring reactions after 4 hours, 1.4 kilowatts of wherein maximum powers of agitator, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 730 restrains, greater than 0.8 millimeter saccharoid, 10 grams, styrene conversion rate 82.2%, between normality 97%, primary crystallization degree 41%, molecular weight distribution 1.9.
[embodiment 3]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times adds 750 milliliters of styrene monomers, 2250 milliliters of hexanes.Stir after 30 minutes, contain 29.25 mmole triisobutyl aluminiums, 48.75 mmole MAO with the syringe injection, 0.195 the metallocene-titanium catalyst toluene solution of mmole embodiment 1, at 300 rev/mins of following stirring reactions after 4 hours, 1.2 kilowatts of wherein maximum powers of agitator, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 540 restrains, greater than 0.8 millimeter saccharoid, 5 grams, styrene conversion rate 80.7%, between normality 97%, primary crystallization degree 43%, molecular weight distribution 1.9.
[embodiment 4]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times adds 500 milliliters of styrene monomers, 2500 milliliters of hexanes.Stir after 30 minutes, contain 29.25 mmole triisobutyl aluminiums, 48.75 mmole MAO with the syringe injection, 0.195 the metallocene-titanium catalyst toluene solution of mmole embodiment 1, at 300 rev/mins of following stirring reactions after 4 hours, 1.1 kilowatts of wherein maximum powers of agitator, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 400 restrains, greater than 0.8 millimeter saccharoid, 0 gram, styrene conversion rate 88.9%, between normality 98%, primary crystallization degree 44%, molecular weight distribution 1.8.
[embodiment 5]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times adds 1000 milliliters of styrene monomers, 2000 milliliters of heptane.Stir after 30 minutes, contain 29.25 mmole triisobutyl aluminiums, 48.75 mmole MAO with the syringe injection, 0.195 the metallocene-titanium catalyst toluene solution of mmole embodiment 1, at 300 rev/mins of following stirring reactions after 4 hours, 1.42 kilowatts of wherein maximum powers of agitator, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 726 restrains, greater than 0.8 millimeter saccharoid, 11 grams, styrene conversion rate 81.9%, between normality 97%, primary crystallization degree 42%, molecular weight distribution 1.9.
[comparative example 1]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times, add 3 liters of styrene monomers, stir after 30 minutes, contain 29.25 mmole triisobutyl aluminiums with the syringe injection, 48.75 mmole MAO, the metallocene-titanium catalyst toluene solution of 0.195 mmole embodiment 1 is at 300 rev/mins of following stirring reactions after 4 hours, 2.5 kilowatts of wherein maximum powers of agitator, stirring rake and reactor encrustation are more serious, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry that powder solid 1210 restrains, greater than 0.8 millimeter saccharoid, 200 grams, styrene conversion rate 52.2%, a normality 97%, primary crystallization degree 34%, molecular weight distribution 2.4.
[comparative example 2]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times adds 2850 milliliters of styrene monomers, 150 milliliters of hexanes.Stir after 30 minutes, contain 29.25 mmole triisobutyl aluminiums with the syringe injection, 48.75 mmole MAO, 0.195 the metallocene-titanium catalyst toluene solution of mmole embodiment 1, at 300 rev/mins of following stirring reactions after 4 hours, 2.4 kilowatts of wherein maximum powers of agitator, stirring rake and reactor encrustation are more serious, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry that powder solid 1290 restrains, greater than 0.8 millimeter saccharoid, 150 grams, styrene conversion rate 53.3%, a normality 97%, primary crystallization degree 35%, molecular weight distribution 2.1.
Can find out that from above-mentioned narration characteristics of the present invention are as follows:
1, power of agitator is low, reactor is required not bery harsh.
2, the styrene conversion rate is risen to more than 80%.
3, no block generates.
4, degree of crystallinity is high by 40%, only has 35% during body.
5, molecular weight distribution narrower＜2.0, during body＞2.2.
Claims (6)
1, a kind of method for preparing syndiotactic polystyrene, with vinylbenzene is raw material, with the metallocene-titanium metal compound is Primary Catalysts, triisobutyl aluminium is or/and the oligomerisation degree is 6～40 alkylaluminoxane is promotor, aluminium in the triisobutyl aluminium is 50～400 to the titanium mole ratio in the metallocene-titanium metal compound, aluminium in the alkylaluminoxane is 50～2000 to the titanium mole ratio in the metallocene-titanium metal compound, with the inert organic solvents is medium, in temperature of reaction is 10～100 ℃, reaction pressure is that reaction generates syndiotactic polystyrene under the condition of normal pressure, and wherein the amount of inert organic solvents is 20～90% of a polymerization system gross weight.
2, according to the described method for preparing syndiotactic polystyrene of claim 1, it is characterized in that metallocene-titanium metal compound is selected from R
1Ti (OR
2)
3, R
1TiCl
3Or R
1Ti (OR
3OR
4)
3, R wherein
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl, R
2, R
3Or R
4Be selected from alkyl, aryl, aralkyl or the alkaryl of 1～12 carbon atom.
3, according to the described method for preparing syndiotactic polystyrene of claim 1, it is characterized in that inert organic solvents is selected from 2, at least a in 2-dimethylbutane, 3-methylpentane, Skellysolve A, pentamethylene, methylcyclopentane, normal hexane, isohexane, hexanaphthene, 2-methyl hexane, heptane, octane-iso, benzene,toluene,xylene, ethylbenzene, chlorobenzene or the fluorobenzene.
4,, it is characterized in that inert organic solvents is selected from least a in normal hexane, isohexane, hexanaphthene, 2-methyl hexane or the heptane according to the described method for preparing syndiotactic polystyrene of claim 3.
5,, it is characterized in that temperature of reaction is 40～80 ℃ according to the described method for preparing syndiotactic polystyrene of claim 1.
6, according to the described method for preparing syndiotactic polystyrene of claim 1, the amount that it is characterized in that inert organic solvents is 50～80% of a polymerization system gross weight.
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| CN 03150729 CN1252100C (en) | 2003-09-03 | 2003-09-03 | Method of preparing syndiotectic polystyrene |
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