CN1704435A - Continuous method for preparing syndiotactic polyvinyl aromatic hydrocarbon - Google Patents
Continuous method for preparing syndiotactic polyvinyl aromatic hydrocarbon Download PDFInfo
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- CN1704435A CN1704435A CN 200410024730 CN200410024730A CN1704435A CN 1704435 A CN1704435 A CN 1704435A CN 200410024730 CN200410024730 CN 200410024730 CN 200410024730 A CN200410024730 A CN 200410024730A CN 1704435 A CN1704435 A CN 1704435A
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 21
- 229920006216 polyvinyl aromatic Polymers 0.000 title claims abstract description 19
- 238000011437 continuous method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012442 inert solvent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 35
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- 230000009466 transformation Effects 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000011218 segmentation Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 40
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000013461 design Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 230000007306 turnover Effects 0.000 description 4
- 238000001238 wet grinding Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
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- 238000002425 crystallisation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000008698 shear stress Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Abstract
The invention relates to a continuous method for preparing syndiotactic polyvinyl aromatic hydrocarbon by employing at least three tandem reactors, wherein vinyl aromatic hydrocarbon monomer, inert solvent and catalyst are continuously charged into a pre-polymerizing reactor for pre-polymerization, loading into a second reactor before the conversion rate at the exit of a first reactor reaches 5%, and loading into a third reactor before the conversion rate at the exit of a second reactor reaches 25-30%, thus achieving a final conversion rate of 60-85%.
Description
Technical field
The present invention relates to the continuation method of rule polyvinyl aromatic hydrocarbons between a kind of preparation.
Background technology
Be typically syndiotactic polystyrene (sPS) in the syndiotactic vinyl aromatic polymers the most, it is a kind of novel hypocrystalline thermoplastic engineering plastic, and its high fusing point (270 ℃) and degree of crystallinity have been 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.Adopt homogeneous catalysis system to prepare syndiotactic polystyrene in the previous patent mostly, no matter adopt which kind of catalyst system, syndiotactic polymerization of phenylethylene is because of being accompanied by the crystallisation process of polymkeric substance, belong to special precipitation polymerization, 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, power of agitator is sharply increased, will inevitably follow problems such as removing hot difficulty simultaneously, to such an extent as to reaction is difficult to normally carry out.
Relate to the more of special reaction device design in the present disclosed patent.As adopting the intermittent bulk polymerization among the EP328975, promptly in same reactor, to experience each stage that particle generates.This patent has compared various reactor types, stirring and scraper plate form to the polymeric effect from generating powder, reduce power consumption, improving the monomer conversion angle.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, the research on polymerization technique also can not show a candle to going deep into of extraordinary reactor more.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 the problems such as sticking still, sticking oar that prevent take place.Among the EP535582 poly-unit expanded to 1 cubic metre vertical forced fluidized bed, and successive polymerization.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, also strict to the control of benzene feedstock vinyl monomer input concentration, overrich a little, just easily make product syndiotactic polystyrene caking, in addition utilize the required energy consumption of fluidized-bed process of unreacted monomer gasification also bigger.JP08020602 points out by adding a small amount of pentane as heat-transfer medium, can improve final transformation efficiency to 71% effectively in 1000 liters of vertical forced fluidized bed polymerization techniques.
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.Disclose two stills series connection polymerization technique as Dao Er 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, play the effect that improves transformation efficiency.In the two stills series connection polymerization technique of JP08283312, first still is the twin shaft self-cleaning reactor, and two stills are 200 liters of forced fluidized beds, wherein add pentane to take away heat.EP584646 has proposed a kind of 6.3 liters of horizontal-type biaxial self-cleaning reactors, and catalyzer (or and monomer together) divides multistage to add with the temperature in the controlling reactor at axial different positions.BASF AG has proposed 22.8 liters of horizontal-type biaxial self-cleaning reactor list still technologies in USP5942589, and before reactor, installing the static mixer that strap clamp overlaps additional, the mixing solutions of Primary Catalysts solution and monomer, promotor enters reactor behind 20 ℃ of following premixs again in static mixer.Two screw rod differences in the reactor, one is the cleaning screw rod, and 24 rev/mins of rotating speeds, another root are driving screw, and rotating speed is 6 rev/mins, and the discharge end of screw rod directly connects twin screw extruder, and final transformation efficiency can be up to more than 90%, and the molecular weight of product narrowly distributing.But be to use single automatically cleaning still or two automatically cleaning reactor series connection, its shortcoming is that the effective volume of automatically cleaning still is limited, and facility investment is big, is unfavorable for large-scale industrial production.
In addition, one 130 liters liquid phase powder bed reactor list still continuous polymerization techniques have been proposed, powder overflow discharging among the USP5484862.WO9910394 points out that back-mixing is favourable to the preparation powder-like product, thereby adopts the combination of continuous stir reactor can improve catalytic efficiency, as long as enough shearings and mixing are arranged, reactor can adopt vertical or horizontal, and stirring rake can adopt multiple whipped form.
In a word, a lot of about the patent of reactor and polymerization technique both at home and abroad, and still have recent years the patent of this respect to occur, and the production technology of this explanation sPS is perfect not enough, and reactor remains further to be optimized.Comprehensive a lot of technical superioritys in the patent, FA technology or reactor are still few in number.For guaranteeing that polymerization carries out smoothly, have in addition with sacrifice efficient, high energy consumption is a cost, such reactor and polymerization technique are unfavorable for that industry amplifies and scale operation.
Summary of the invention
Technical problem to be solved by this invention be exist in the existing document conduct heat in the reaction process poor, power of agitator is big, the problem that the reactor utilization ratio is low provides the continuation method of advising polyvinyl aromatic hydrocarbons between a kind of new preparation.This method can not only solve heat transfer, the stirring problem in the polymerization technology well, improves the utilization ratio of reactor greatly, and open, shut-down operation is easy, and can solve industrial scale-up problem.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the continuation method of rule polyvinyl aromatic hydrocarbons between a kind of preparation, use at least three placed in-line reactors, temperature be less than 45 ℃ of conditions under, the raw material vinyl aromatic monomer, inert solvent and metallocene catalyst are joined respectively continuously carries out prepolymerization in first prepolymerization reactor, reached before 5% at the first reactor outlet transformation efficiency, first reactor stream enters second reactor, when second reactor outlet transformation efficiency reaches 25～30%, second reactor stream enters the preparation of finishing the powdery syndiotactic vinyl aromatic polymers in the 3rd reactor, and make that final transformation efficiency is 60～85%, continuous or the intermittent take-off of the 3rd reactor reaction product, wherein the temperature of reaction of second reactor is 45 ℃～65 ℃, and the temperature of reaction of the 3rd reactor is 65 ℃～85 ℃.
In the technique scheme, a rule polyvinyl aromatic hydrocarbons preferred version is a syndiotactic polystyrene; The degree of syndiotacticity preferable range of syndiotactic vinyl aromatic polymers is greater than 70%.Metallocene catalyst comprises Primary Catalysts and promotor, and the Primary Catalysts preferred version is a cyclopentadiene titanium compound, is selected from R
1Ti (OR
4)
3, R
1TiCl
3Or R
1Ti (OR
2OR
3)
3, R wherein
1For cyclopentadienyl or contain the substituted cyclopentadienyl of 1～5 methyl, R
2, R
3Or R
4Be the alkyl, aryl, aralkyl or the alkaryl that are selected from 1～12 carbon atom, R
1Preferred version is the pentamethyl-cyclopentadienyl, R
2Preferred version is a phenyl, R
3Preferred version is the alkyl of 1～4 carbon atom, R
4Be the alkyl of 1～4 carbon atom or aryl, aralkyl or the alkaryl of 6～12 carbon atoms; Promotor is alkylaluminoxane or alkylaluminoxane and triisobutyl aluminium.The inert solvent preferred version is for being selected from lower boiling C
3～C
8Alkane, naphthenic hydrocarbon or aromatic hydrocarbons, more preferably scheme is a hexane, the consumption preferable range of inert solvent is 5～50% of a whole reaction system volume.Preferred version of the present invention is for using three placed in-line reactors, first reactor is a vertical reactor, and second reactor is the self-cleaning type reactor, and the 3rd reactor is the conical vertical reactor, its used stirring rake bottom is the taper ribbon of no central shaft, and top is two ribbons.The control preferred version of second temperature of reactor is realized for setting jacket temperature by the segmentation of self-cleaning type reactor.
The present invention mainly controls the outlet transformation efficiency by the feed composition and the residence time of material in reactor of control reaction temperature, material, thereby reaction is carried out smoothly, obtains meeting necessarily required granulating syndiotactic polystyrene.
During preparation syndiotactic polystyrene (sPS), because the easy crystallization of syndiotactic polystyrene makes that the solubleness of sPS in vinylbenzene and other inert solvent is very low.Polymerization Once you begin, polymerization system will soon be heterogeneous by all being phase-changed into.In the whole polymerization process, system has experienced this four-stage of rare homogeneous phase solution → suspension → wet-milling → dry powder successively, and the phase span of whole process is very big.The present invention is designed to three sections with continuous polymerization technique, is respectively pre-polymerization section+interlude+powder section.
Shear-stress is topmost factor, as long as enough powers of agitator are provided, polymerization is carried out smoothly.Two ribbon oars can provide strong shearing action, and the ribbon oar be during powder stirs comparatively ideal stir pattern.The inventor finds that two ribbon oars press down, turn on the later stage one of key that effectively reduces power consumption, preparation powdery sPS when operation is the body batchwise polymerization in earlier stage.
The inventor finds to adopt in the batchwise polymerization temperature-programmed technique, is tangible to the improvement of the performance of the regulation and control of polymerization process and final product.But mainly realize in the periodical operation, have empirical by initial setting or artificial manual regulation temperature.Connect sectional temperature-controlled same the realization in the continuous processing of the present invention to the regulation and control of polymerization process and the improvement of final product performance by three stills.
One of problem that a lot of patents both at home and abroad do not have fine solution is the mixing in early stage, though considered premix such as static mixer in some patent, effect is not fine yet.Pre-polymerization section temperature is controlled at below 45 ℃ among the present invention, and purpose is to reduce initial reaction speed, the slow release of controlled polymerization heat.Adopt press operation under two ribbons simultaneously, and control outlet transformation efficiency is lower than about 5%.This stage mainly finishes catalyst mix, active centre and forms, causes and increase, and forms primary particle, promptly carries out pre-polymerization, and material goes out with the realization operate continuously by on advancing down simultaneously.
The advantage of automatically cleaning reactor is to be applicable to the high strong occasion of shearing of gluing, need.In the quadravalence section of sPS bulk polymerisation process, have the wet-milling stage only and be horizontal automatically cleaning still (single shaft, twin shaft automatically cleaning still or directly the use forcing machine) advantage can brought into play, other several stages is a poor efficiency, or even disadvantageous (as the formation to the active centre).Similar forcing machine is the same, and the automatically cleaning still is suitable for the sticking system of height that the residence time requires relative weak point, and wet-milling requires to shear by force to the dry powder transit time in the sPS mass polymerization, and transit time is short especially.Therefore the inventor thinks transformation efficiency 5%～30% this section is placed on and carries out comparatively suitablely in the horizontal automatically cleaning still, and particularly polymerization temperature is controlled at 45 ℃～65 ℃ requirement and can be undertaken by the sectional splint cover of automatically cleaning still piecemeal that heat temperature raising is more suitable.If use the automatically cleaning still separately, its shortcoming is that the effective volume of automatically cleaning still is limited, and investment is big, is unfavorable for amplifying and large-scale industrial production, so it only is used as crucial transition section.
When interlude outlet transformation efficiency 25～30% the time, wet powder enters the powder section under the conveying of screw rod.The present invention is designed to taper with the 3rd section reactor lower part, and its main purpose is to prevent to rock, and is convenient to fluidisation and powder discharging.Taper still and to be equipped with the bottom be that the stirring fluidization that is suitable for very much powder is operated for the conical double ribbon band oar of no central shaft.Give full play to the fluidization operation, further improve the transformation efficiency of sPS, must guarantee that there has not been continuous liquid phase in the material that enters vertical taper still, styrene monomer absorption swelling is in particle, and having arrived the polymerization that the taper still carries out is the monomeric polymerization of sPS particle interior liquid.
From the taper still intermittently or the powder that comes out continuously, also can connect forcing machine, remove unreacted monomer and granulation in the material by forcing machine, the material after coming out promptly can be used as the sPS pellet.Even can also in this section, add modification bodies such as glass, rubber, and directly carrying out modification enhancing, toughness reinforcing, the product that comes out promptly can be used as commodity selling.
Inventor's research is also found suitably to add inert solvent such as hexane etc., can not only promote the sPS granulating, and can improve heat transfer.The amount that adds inert solvent accounts for 5%～50% of whole reaction system volume, and preferable range is 10～40%.The purpose that adds inert solvent mainly contains three: (1) metallocene Primary Catalysts consumption is less relatively, need suitably dilute just to help operate continuously, has played thinner during batching; (2) in the pre-polymerization stage that prepolymerization kettle carries out, suitable inert solvent has promoter action to granulating, has played the effect of conditioning agent; (3) to join in the vertical taper reactor effect the most obvious for inert, the design polymerization temperature is between 65 ℃～85 ℃, slightly operate under the negative pressure, utilize solvent gasification zone heat, improved the heat transfer problem in this stage, the design of the still of taper simultaneously, under the effect of stirring and rare gas element vaporization, fluidised effect is better.
The continuation method of rule polyvinyl aromatic hydrocarbons between preparation provided by the invention.Problems such as the heat transfer between having solved well in the rule polyvinyl aromatic hydrocarbons polymerization technology, stirring, the utilization ratio of reactor improves greatly, open, shut-down operation becomes and is easy to, and the industrial scale-up problem of reactor also obtained good solution, obtained better technical effect.
Description of drawings
Accompanying drawing 1 is the process flow sheet of the inventive method.
1 is prepolymerization kettle in the accompanying drawing 1, and 2 is common double ribbon stirring rake, and 3 is the self-cleaning type reactor, and 4 is reactor jacket, and 5 is the screw rod extruder, and 6 is cone-shaped reactor, and 7 is the two ribbons of standard, and 8 are two ribbons of no central shaft.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Three reactors that the present invention describes are respectively 10 liters of vertical prepolymerization kettles, 10 liters of horizontal-type biaxial automatically cleaning stills and 100 liters of vertical taper reactors and form.Earlier vacuumize baking after 8 hours, be cooled to 60 ℃, use N under 90 ℃ of three reactors and the corresponding pipelines
2After purging 3 times, open feed valve, make that the flow of styrene monomer is 16 liters/hour, the flow of inert solvent hexane is 4 liters/hour, metallocene-titanium catalyst Cp
*Ti (O-C
6H
4-OCH
3)
3Flow be 1.4 mmoles/hour, methylaluminoxane MAO be 210 mmoles/hour, triisobutyl aluminium TIBA flow be 140 mmoles/hour.Open simultaneously and stir, 10 liters of prepolymerization kettle mixing speed are press operation under 300 rev/mins and the ribbon, two screw rod differences in the self-cleaning reactor, one is the cleaning screw rod, 30 rev/mins of rotating speeds, another root is a driving screw, and rotating speed is 8 rev/mins, and the mixing speed of 100 liters of taper stills is to turn over operation on 100 rev/mins and the ribbon.The pre-polymerization temperature in the kettle is set in 40 ℃, and the design temperature of five sections chucks is respectively 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ in the self-cleaning reactor; 100 liters of taper reacting kettle jacketing temperature are set in 70 ℃.Continuously operation is after 2 hours, opens bleeder valve and opens once every 10 minutes.Material is half hour in the residence time of prepolymerization kettle, the residence time in 10 liters of horizontal-type biaxial automatically cleaning stills is about 30 minutes, and the powder discharging speed is 3.5 kilograms/10 minutes, and monomeric final transformation efficiency is 70%, normality 99% between polymkeric substance, weight-average molecular weight Mw=38 * 10
4, polymerization process is steady, and product is powder, and each reactor wall does not have fouling.
[embodiment 2]
Three reactors that the present invention describes are respectively 10 liters of vertical prepolymerization kettles, 10 liters of horizontal-type biaxial automatically cleaning stills and 100 liters of vertical taper reactors and form.Earlier vacuumize baking after 8 hours, be cooled to 60 ℃, use N under 90 ℃ of three reactors and the corresponding pipelines
2After purging 3 times, open feed valve, make that the flow of styrene monomer is 10 liters/hour, the flow of inert solvent hexane is 3 liters/hour, metallocene-titanium catalyst Cp
*Ti (O-C
6H
4-OCH
3)
3Flow be 1.2 mmoles/hour, methylaluminoxane MAO be 200 mmoles/hour, triisobutyl aluminium TIBA flow be 120 mmoles/hour.Open simultaneously and stir, 10 liters of prepolymerization kettle mixing speed are press operation under 300 rev/mins and the ribbon, two screw rod differences in the self-cleaning reactor, one is the cleaning screw rod, 30 rev/mins of rotating speeds, another root is a driving screw, and rotating speed is 8 rev/mins, and the mixing speed of 100 liters of taper stills is to turn over operation on 100 rev/mins and the ribbon.The pre-polymerization temperature in the kettle is set in 30 ℃, and the design temperature of five sections chucks is respectively 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ in the self-cleaning reactor; 100 liters of taper reacting kettle jacketing temperature are set in 75 ℃.Continuously operation is after 2 hours, opens bleeder valve and opens once every 20 minutes.Material is half hour in the residence time of prepolymerization kettle, the residence time in 10 liters of horizontal-type biaxial automatically cleaning stills is about 45 minutes, and the powder discharging speed is 4 kilograms/20 minutes, and monomeric final transformation efficiency is 78%, normality 99% between polymkeric substance, weight-average molecular weight Mw=37 * 10
4, polymerization process is steady, and product is powder, and each reactor wall does not have fouling.
[comparative example 1]
Two reactors that the present invention describes are respectively 10 liters of horizontal-type biaxial automatically cleaning stills and 100 liters of vertical taper reactors are formed.Earlier vacuumize baking after 8 hours, be cooled to 60 ℃, use N under 90 ℃ of two reactors and the corresponding pipelines
2After purging 3 times, open feed valve, make that the flow of styrene monomer is 16 liters/hour, the flow of inert solvent hexane is 4 liters/hour, metallocene-titanium catalyst Cp
*Ti (O-C
6H
4-OCH
3)
3Flow be 1.4 mmoles/hour, methylaluminoxane MAO be 210 mmoles/hour, triisobutyl aluminium TIBA flow be 140 mmoles/hour.Open to stir simultaneously, two screw rod differences in the self-cleaning reactor, one is the cleaning screw rod, and 30 rev/mins of rotating speeds, another root are driving screw, and rotating speed is 8 rev/mins, and the mixing speed of 100 liters of taper stills is to turn over operation on 100 rev/mins and the ribbon.The design temperature of five sections chucks is respectively 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ in the self-cleaning reactor; 100 liters of taper reacting kettle jacketing temperature are set in 70 ℃.Continuously operation is after 2 hours, opens bleeder valve and opens once every 10 minutes.The residence time of material in 10 liters of horizontal-type biaxial automatically cleaning stills is about 30 minutes, and the powder discharging speed is 3.5 kilograms/10 minutes, and monomeric final transformation efficiency is 55%, and normality 99% between polymkeric substance, weight-average molecular weight Mw=36 * 10
4,, therefore cause batch mixing inequality in horizontal-type biaxial automatically cleaning still owing to there be not first 10 liters of vertical prepolymerization kettle, power of agitator changes greatly, materials conversion rate is inhomogeneous when entering the 3rd polymerization reaction kettle, and polymerization process is not steady, and block 5% is arranged in the final product.
[comparative example 2]
100 liters of vertical taper reactors of the reactor that the present invention describes are formed.Vacuumize baking after 8 hours under 90 ℃ of reactor and the corresponding pipelines, be cooled to 60 ℃, use N
2After purging 3 times, open feed valve, make that the flow of styrene monomer is 16 liters/hour, the flow of inert solvent hexane is 4 liters/hour, metallocene-titanium catalyst Cp
*Ti (O-C
6H
4-OCH
3)
3Flow be 1.4 mmoles/hour, methylaluminoxane MAO be 210 mmoles/hour, triisobutyl aluminium TIBA flow be 140 mmoles/hour.Open to stir simultaneously, the mixing speed of 100 liters of taper stills is to turn over operation on 140 rev/mins and the ribbon.100 liters of taper reacting kettle jacketing temperature are set in 70 ℃.Continuously operation is after 2 hours, opens bleeder valve and opens once every 10 minutes.Monomeric final transformation efficiency is 52%, and normality 99% between polymkeric substance, weight-average molecular weight Mw=34 * 10
4, owing to do not have first 10 liters of vertical prepolymerization kettle and second horizontal-type biaxial automatically cleaning still, all processes are all finished in 100 liters of vertical taper reactors, therefore power of agitator changes greatly, polymerization process is not steady, and block 10% is arranged in the final product, and fouling is serious on reactor wall and the stirring rake.
Claims (9)
1, the continuation method of rule polyvinyl aromatic hydrocarbons between a kind of preparation, use at least three placed in-line reactors, temperature be less than 45 ℃ of conditions under, the raw material vinyl aromatic monomer, inert solvent and metallocene catalyst are joined respectively continuously carries out prepolymerization in first prepolymerization reactor, reached before 5% at the first reactor outlet transformation efficiency, first reactor stream enters second reactor, when second reactor outlet transformation efficiency reaches 25～30%, second reactor stream enters the preparation of finishing the powdery syndiotactic vinyl aromatic polymers in the 3rd reactor, and make that final transformation efficiency is 60～85%, continuous or the intermittent take-off of the 3rd reactor reaction product, wherein the temperature of reaction of second reactor is 45 ℃～65 ℃, and the temperature of reaction of the 3rd reactor is 65 ℃～85 ℃.
2, according to the continuation method of rule polyvinyl aromatic hydrocarbons between the described preparation of claim 1, rule polyvinyl aromatic hydrocarbons is syndiotactic polystyrene between it is characterized in that.
3, according to the continuation method of rule polyvinyl aromatic hydrocarbons between the described preparation of claim 1, the degree of syndiotacticity that it is characterized in that syndiotactic vinyl aromatic polymers is greater than 70%.
4, according to the continuation method of rule polyvinyl aromatic hydrocarbons between the described preparation of claim 1, it is characterized in that metallocene catalyst comprises Primary Catalysts and promotor, Primary Catalysts is a cyclopentadiene titanium compound, is selected from R
1Ti (OR
4)
3, R
1TiCl
3Or R
1Ti (OR
2OR
3)
3, R wherein
1For cyclopentadienyl or contain the substituted cyclopentadienyl of 1～5 methyl, R
2, R
3Or R
4Be the alkyl, aryl, aralkyl or the alkaryl that are selected from 1～12 carbon atom, promotor is alkylaluminoxane or alkylaluminoxane and triisobutyl aluminium.
5, according to the continuation method of rule polyvinyl aromatic hydrocarbons between the described preparation of claim 4, it is characterized in that R
1Be pentamethyl-cyclopentadienyl, R
2Be phenyl, R
3Be the alkyl of 1～4 carbon atom, R
4Be the alkyl of 1～4 carbon atom or aryl, aralkyl or the alkaryl of 6～12 carbon atoms.
6, according to the continuation method of rule polyvinyl aromatic hydrocarbons between the described preparation of claim 1, it is characterized in that inert solvent is selected from lower boiling C
3～C
8Alkane, naphthenic hydrocarbon or aromatic hydrocarbons, the consumption of inert solvent is 5～50% of a whole reaction system volume.
7, according to the continuation method of rule polyvinyl aromatic hydrocarbons between the described preparation of claim 6, it is characterized in that inert solvent is a hexane.
8, according to the continuation method of advising polyvinyl aromatic hydrocarbons between the described preparation of claim 1, it is characterized in that using three placed in-line reactors, first reactor is a vertical reactor, second reactor is the self-cleaning type reactor, the 3rd reactor is the conical vertical reactor, its used stirring rake bottom is the taper ribbon of no central shaft, and top is two ribbons.
9, the continuation method of rule polyvinyl aromatic hydrocarbons between described according to Claim 8 preparation is characterized in that the control of second temperature of reactor realizes by self-cleaning type reactor segmentation setting jacket temperature.
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