CN1285627C - Process for preparing syndiotactic polystyrene - Google Patents
Process for preparing syndiotactic polystyrene Download PDFInfo
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- CN1285627C CN1285627C CN 200410017717 CN200410017717A CN1285627C CN 1285627 C CN1285627 C CN 1285627C CN 200410017717 CN200410017717 CN 200410017717 CN 200410017717 A CN200410017717 A CN 200410017717A CN 1285627 C CN1285627 C CN 1285627C
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- reactor
- syndiotactic polystyrene
- described method
- preparing
- preparing syndiotactic
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- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000003756 stirring Methods 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000217 alkyl 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
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 claims description 4
- 238000012662 bulk polymerization Methods 0.000 claims description 3
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 3
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 238000001879 gelation Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 235000010210 aluminium Nutrition 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000008698 shear stress Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The present invention relates to a method of preparing syndiotectic polystyrene, which mainly solves the problems of easy adhesion on reactor walls, easy caking and easy gelation of the reaction process of syndiotactic polystyrene existing in the prior art. The present invention well solves the problems by adopting the technical schemes that a reactor with a double spiral stirring paddle is adopted in the preparing process of the syndiotactic polystyrene, wherein the lower part of the reactor forms the shape of a truncated cone; the part of a double spiral stirring paddle corresponding to the lower part adopts a tapered double spiral stirring paddle. The present invention can be used for the industrial production of preparing the syndiotactic polystyrene.
Description
Technical field
The present invention relates to a kind of method for preparing syndiotactic polystyrene.
Background technology
Easily crystallization of syndiotactic polystyrene (sPS), thereby its solubleness in styrene monomer or other inert solvent is very low.In the body of asking stereospecific polymerized styrene or few solvent preparation process, in a single day polymerization takes place, and reaction system will soon be heterogeneous by all being phase-changed into, and experience homogeneous phase solution, sPS suspension, wet-milling and dry powder four-stage successively, and the phase span of whole process is very big.
So far, homogeneous catalyst system is adopted in the polymerization of syndiotactic polystyrene mostly, because of the crystallization and the particulate of the simultaneous polymkeric substance of monomer polymerization forms, so polyreaction belongs to special precipitation polymerization, the exploitation of commercial run is faced with many engineering problems, as: 1) polymerization is prone to gel in earlier stage, even forms block, and this requires reactor not have the dead band substantially; 2) the easy sticking still that polymkeric substance takes place in the polymerization process, this requires the reacting appliance self-cleaning function simultaneously; 3) in case polymerization system transfers the wet-milling attitude to, external phase disappears, and power of agitator can extremely acutely rise, and simultaneous is removed problems such as hot difficulty, to such an extent as to polyreaction is difficult to normally carry out, therefore requires reactor that rational stirring power configuration is arranged and removes by the use of thermal means; During 4) along with the further raising of polymerisation conversion, material becomes the dry powder body gradually, and this will ask the whipping appts of reactor can be suitable for fluidisation operation of powder.
For the such polymerization process that relates to full phase operation of preparation syndiotactic polystyrene, how to avoid or reduce the adhesion of polymkeric substance as far as possible at reactor wall, prevent the generation of gel, block, improve final transformation efficiency, this need think better of the pattern of agitator when reactor design, promptly use can both high efficient mixed for viscous liquid and powder whipping device.Relate to the poly-unit for preparing syndiotactic polystyrene in the present disclosed patent and mainly contain two kinds of patterns of vertical and horizontal automatically cleaning.Adopt the intermittent bulk polymerization among the EP328975, compared various reactor types (having vertical and horizontal), stirring pattern (as planetary blade, two ribbons etc.) and scraper plate form sPS polymeric effect.In EP379128, adopt 1 liter of horizontal-type biaxial self-cleaning reactor, and be equipped with three kinds of different self-cleaning type stirring rakes.USP5037907 has introduced a kind of 100L groove type reactor with the multilayer scraper plate, and the upper end of multilayer agitator also is provided with the top scraper plate, to reduce the top bur; Also designed a kind of novel powder drawing mechanism simultaneously.Except that the reactor that above two classes are used always, JP03020308 has invented a kind of 10 liters of spherical reactors, and it is consistent with reactor wall curvature that it stirs shape, to reduce the bonding in the reactor.DE19546096 and USP6121391 also attempt preparing continuously syndiotactic polystyrene in twin screw extruder.
Although horizontal reactor has self-cleaning advantage, it is no dead band in the whole reactor, the mechanical shearing that the everywhere can both be stirred, help avoiding the generation of gel, but because its complex structure, the Assembly And Disassembly difficulty is big, the manufacturing cost height, and exist the problem of powder discharging and clear still difficulty.Therefore, from the angle that industry is amplified, when carrying out syndiotactic polystyrene scale operation, be good to select vertical stirred tank reactor for use.
Summary of the invention
Technical problem to be solved by this invention is to exist in the conventional art in the reaction process of preparation syndiotactic polystyrene, and reactor wall easily adheres to, the problem of caking and gel, and a kind of new method for preparing syndiotactic polystyrene is provided.This method has in preparation syndiotactic polystyrene process can prevent effectively that reactor wall from producing the characteristics of gel, caking and wall sticking phenomenon.
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 reaction raw materials, with cyclopentadiene titanium compound and alkylaluminoxane is catalyzer, vinylbenzene is 0~90 ℃ in temperature in reactor, pressure is to carry out bulk polymerization under the condition of normal pressure to generate syndiotactic polystyrene, wherein used reactor comprises motor, reactor shell, reactor jacket, two ribbon stirring rakes and bottom, reactor jacket is positioned at the reactor outside and is close to reactor shell, two ribbon stirring rakes are fixed in and are positioned at reactor vertically placement vertically on the stir shaft, the stir shaft two ends link to each other with bottom with motor respectively, wherein the reactor shell bottom is truncated cone-shaped, frustum cone height is 10~70% of a reactor shell height, the round platform partial volume accounts for 10~70% of reactor cubic capacity, the angle theta of the round platform conical surface and bottom horizontal plane is 30 °~80 °, and two ribbon stirring rakes partly are conical double ribbon band stirring rake at round platform.
In the technique scheme, the cyclopentadiene titanium compound preferred version is for being selected from R
1Ti (OR
2OR
3)
3, R
1Ti (OR
4)
3Or R
1TiCl
3, R wherein
1Be cyclopentadienyl or substituted cyclopentadienyl, preferred version is cyclopentadienyl (Cp) or pentamethyl-cyclopentadienyl (Cp
*); R
2, R
3Or R
4Be selected from alkyl, aryl, aralkyl or the alkaryl of 1~12 carbon atom, preferred version is the alkyl that is selected from 1~4 carbon atom, aryl, aralkyl or the alkaryl of 6~10 carbon atoms; Alkylaluminoxane is that methylaluminoxane (MAO) is or/and triisobutyl aluminium.The frustum cone height preferred version is for being 20~40% of reactor shell height; The preferable range that the round platform partial volume accounts for the reactor cubic capacity is 15~45%.The preferable range of the angle theta of the round platform conical surface and bottom horizontal plane is 40 °~60 °; Between two ribbon stirring rake outer rims and reactor wall is greater than between 0~15 millimeter apart from preferable range, and more preferably scope is greater than between 0~8 millimeter.
The syndiotactic polymerization of phenylethylene of homogeneous catalysis, because of the requirement of polyreaction and dual regulation and control of polymer beads form and full phase converging operation, the stirring of reactor should provide good material circulation and fluidisation, can provide strong shear-stress again.The circulation of two ribbon stirring rake, fluidisation and shearing action are good, and be during high sticking material and powder stir comparatively ideal stir pattern.Because the bulk density of syndiotactic polystyrene powder granule is generally at 0.25~0.4 gram per centimeter
3, this just makes the initial charge of converging operation need be controlled at below 1/3 of reactor cumulative volume, generally is selected in 0.25~0.3.In order to make initial mixing of materials even, and promote the sPS crystallization, avoid gel, prevent caking that initial reaction stage just should provide strong stirring intensity.Though satisfying, two ribbon stirring rakes mix and strong requirement of shearing, but during low sticking, high rotating speed, the ribbon stirring rake easily forms bigger solid rotating part, promptly forms very big whirlpool, can cause the caking or the skinning that cause owing to the polymerization system volumetric shrinkage at the liquid-gas interface place like this.To be designed to truncated cone-shaped at the bottom of the still, help reducing the solid rotating part, make that finally the bur at the liquid-gas interface place reduces.Reactor of the present invention is particularly suitable for the semi continuous operation of continuous dropping, final discharging.Because the still bottom is truncated cone-shaped, and is equipped with conical double ribbon band stirring rake, make the liquid that drips remain sufficient shearing, overcome the difficulty that common elipse head is operated when hanging down liquid level.When syndiotactic polymerization of phenylethylene enters the wet-milling attitude, because friction resistance increases, to stir power consumption and increase severely, the stir shaft bottom tends to because stressed excessive and occur rocking.The bottom of stirring rake is designed to conical double ribbon band stirring rake among the present invention, and it is not enough effectively to overcome this point that adopts common double ribbon still, has obtained better technical effect.
It is very convenient that this design of the reactor that uses in the inventive method, the Powdered sPS discharging that generates when syndiotactic polystyrene is prepared become.The bottom is truncated cone-shaped, and certain pitch angle is arranged, and material is easy to be transported under action of gravity or under certain stirring action the bottom, and the kettle cover of opening the bottom gets final product discharging, need not special powder drawing mechanism, and is easy to operate.
Description of drawings
1 is agitator motor in the accompanying drawing 1, and 2 is reactor, and 3 is two ribbon stirring rakes, 4 is reactor jacket, and 5 are taper ribbon stirring rake, and 6 is bottom, θ is the angle of the round platform conical surface and bottom horizontal plane, and a1 is the reactor upper height, and a2 is a reactor lower part truncated cone-shaped height.
The invention will be further elaborated below by embodiment, wherein the distance of two ribbon paddle outer rims and reactor wall Be 14 millimeters from embodiment 1~2, embodiment 3~4 is 8 millimeters, and embodiment 5~6 is 3 millimeters.
Embodiment
[embodiment 1]
On 10 liters of mechanical stirring kettles (height of round platform part accounts for 33% of total still height, and volume accounts for 30% of still cumulative volume, and tiltangle is 50 °) that the present invention describes, 90 ℃ of bakings earlier were cooled to 60 ℃, N after 8 hours
2Pump drainage 3 times adds styrene monomer 2375 grams, stirs after 30 minutes, injects with syringe to contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.264 mmole Cp*Ti (O-C
6H
4-OCH
3)
3The metallocene-titanium catalyst toluene solution, at 300 rev/mins of following stirring reactions, moment of torsion and power of agitator rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Power of agitator rises to the highest 2678 watts by initial 2375 watts.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry powder solid 1757 grams that get, styrene conversion rate 74%, normality 98% between polymkeric substance, weight-average molecular weight Mw=46 * 10
4
[embodiment 2]
On 100 liters of mechanical stirring kettles (height of round platform part accounts for 40% of total still height, and volume accounts for 30% of still cumulative volume, and tiltangle is 60 °) that the present invention describes, 120 ℃ of vapor bakings were cooled to 60 ℃, N after 8 hours earlier
2Pump drainage 3 times adds 9 kilograms of styrene monomers, and hexanaphthene stirs after 30 minutes for 23.4 kilograms, injects with syringe to contain 520 mmole triisobutyl aluminiums, 520 mmole MAO, 2.6 mmole Cp*Ti (O-C
6H
4-OCH
3)
3The metallocene-titanium catalyst toluene solution, at 135 rev/mins of following stirring reactions, moment of torsion and stir current rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 8.1 amperes by initial 7.4 amperes.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry 7 kilograms of the powder solids that get, styrene conversion rate 78%, normality 99% between polymkeric substance, weight-average molecular weight Mw=32 * 10
4
[embodiment 3]
On 100 liters of mechanical stirring kettles (height of round platform part accounts for a1=30 centimetre, and a2=60 centimetre, tiltangle is 40 °) that the present invention describes, 120 ℃ of vapor bakings were cooled to 60 ℃, N after 8 hours earlier
2Pump drainage 3 times adds 9 kilograms of styrene monomers, and hexanaphthene stirs after 30 minutes for 23.4 kilograms, injects with syringe to contain 520 mmole triisobutyl aluminiums, 520 mmole MAO, 2.6 mmole Cp*Ti (OCH
3)
3The metallocene-titanium catalyst toluene solution, at 135 rev/mins of following stirring reactions, moment of torsion and stir current rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 8.3 amperes by initial 7.6 amperes.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry 7.3 kilograms of the powder solids that get, styrene conversion rate 80%, normality 99% between polymkeric substance, weight-average molecular weight Mw=34 * 10
4
[embodiment 4]
On 100 liters of mechanical stirring kettles (volume of bottom round platform part is 25 liters, and upper volume is 75 liters, and tiltangle is 65 °) that the present invention describes, 120 ℃ of vapor bakings were cooled to 60 ℃, N after 8 hours earlier
2Pump drainage 3 times adds 9 kilograms of styrene monomers, and hexanaphthene stirs after 30 minutes for 23.4 kilograms, injects with syringe to contain 520 mmole triisobutyl aluminiums, 520 mmole MAO, 2.6 mmole Cp*Ti (Oph)
3The metallocene-titanium catalyst toluene solution, at 135 rev/mins of following stirring reactions, moment of torsion and stir current rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 8.7 amperes by initial 7.7 amperes.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry 6.9 kilograms of the powder solids that get, styrene conversion rate 77%, normality 98% between polymkeric substance, weight-average molecular weight Mw=32 * 10
4
[embodiment 5]
On 100 liters of mechanical stirring kettles (height of round platform part accounts for a1=20 centimetre, and a2=80 centimetre, tiltangle is 30 °) that the present invention describes, 120 ℃ of vapor bakings were cooled to 60 ℃, N after 8 hours earlier
2Pump drainage 3 times adds 9 kilograms of styrene monomers, and hexanaphthene stirs after 30 minutes for 23.4 kilograms, injects with syringe to contain 520 mmole triisobutyl aluminiums, 520 mmole MAO, 2.6 mmole Cp*Ti (OCH
2CH
2OCH
3)
3The metallocene-titanium catalyst toluene solution, at 135 rev/mins of following stirring reactions, moment of torsion and stir current rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 7.9 amperes by initial 7.1 amperes.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry 7.5 kilograms of the powder solids that get, styrene conversion rate 81%, normality 99% between polymkeric substance, weight-average molecular weight Mw=36 * 10
4
[embodiment 6]
On 10 liters of mechanical stirring kettles (height of bottom round platform part is a1=10 centimetre, and upper height is a1=30 centimetre, and tiltangle is 45 °) that the present invention describes, 90 ℃ of bakings earlier were cooled to 60 ℃, N after 8 hours
2Pump drainage 3 times adds styrene monomer 2375 grams, stirs after 30 minutes, injects with syringe to contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.264 mmole Cp*Ti (O-C
6H
4-F)
3The metallocene-titanium catalyst toluene solution, at 300 rev/mins of following stirring reactions, moment of torsion and power of agitator rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Power of agitator rises to the highest 2689 watts by initial 2344 watts.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry powder solid 1777 grams that get, styrene conversion rate 754%, normality 98% between polymkeric substance, weight-average molecular weight Mw=48 * 10
4
[comparative example 1]
Polymerizing condition is identical with embodiment 1, and different is to adopt conventional drum shaped reaction device, and polymerization process post torque and power of agitator rise very fast, and stirring rake shakes when high conversion.Power of agitator rises to the highest 2898 watts by initial 2375 watts.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry powder solid 1660 grams, the styrene conversion rate 69% of getting.
[comparative example 2]
Polymerizing condition is identical with embodiment 3, and different is to adopt general baffle plate stirring rake, and polymerization process post torque and power of agitator rise very fast, and stirring rake shakes when high conversion.Owing to there is big block product to occur, polyreaction has to finish ahead of time.Product is block and powder, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry that solid 1160 restrains styrene conversion rate 48%.
[comparative example 3]
Polymerizing condition is identical with embodiment 2, and different is to adopt conventional drum shaped reaction device, and polymerization process post torque and stir current rise very fast, and stirring rake shakes when high conversion.Stir current rises to the highest 10.1 amperes by initial 7.4 amperes.Product was powder when reaction finished, with ethanol-hydrochloric acid soln stopped reaction, and washing, dry 6.4 kilograms of the powder solids that get, styrene conversion rate 71%, normality 99% between polymkeric substance.
Claims (9)
1, a kind of method for preparing syndiotactic polystyrene, with vinylbenzene is reaction raw materials, with cyclopentadiene titanium compound and alkylaluminoxane is catalyzer, vinylbenzene is 0~90 ℃ in temperature in reactor, pressure is to carry out bulk polymerization under the condition of normal pressure to generate syndiotactic polystyrene, wherein used reactor comprises motor, reactor shell, reactor jacket, two ribbon stirring rakes and bottom, reactor jacket is positioned at the reactor outside and is close to reactor shell, two ribbon stirring rakes are fixed in and are positioned at reactor vertically placement vertically on the stir shaft, the stir shaft two ends link to each other with bottom with motor respectively, it is characterized in that the reactor shell bottom is truncated cone-shaped, frustum cone height is 10~70% of a reactor shell height, the round platform partial volume accounts for 10~70% of reactor cubic capacity, the angle theta of the round platform conical surface and bottom horizontal plane is 30 °~80 °, and two ribbon stirring rakes partly are conical double ribbon band stirring rake at round platform.
2, according to the described method for preparing syndiotactic polystyrene of claim 1, it is characterized in that cyclopentadiene titanium compound is selected from R
1Ti (OR
2OR
3)
3, R
1Ti (OR
4)
3Or R
1TiCl
3, R wherein
1Be cyclopentadienyl or substituted 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 2, it is characterized in that R
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl; R
2, R
3Or R
4Be selected from the alkyl of 1~4 carbon atom, aryl, aralkyl or the alkaryl of 6~10 carbon atoms.
4,, it is characterized in that alkylaluminoxane is that methylaluminoxane is or/and triisobutyl aluminium according to the described method for preparing syndiotactic polystyrene of claim 1.
5,, it is characterized in that frustum cone height is 20~40% of a reactor shell height according to the described method for preparing syndiotactic polystyrene of claim 1.
6,, it is characterized in that the round platform partial volume accounts for 15~45% of reactor cubic capacity according to the described method for preparing syndiotactic polystyrene of claim 1.
7, according to the described method for preparing syndiotactic polystyrene of claim 1, the angle theta that it is characterized in that the round platform conical surface and bottom horizontal plane is 40 °~60 °.
8,, it is characterized in that distance between two ribbon stirring rake outer rims and reactor wall is for greater than between 0~15 millimeter according to the described method for preparing syndiotactic polystyrene of claim 1.
9, the described according to Claim 8 method for preparing syndiotactic polystyrene is characterized in that distance between two ribbon stirring rake outer rims and reactor wall is for greater than between 0~8 millimeter.
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CN102633918B (en) * | 2012-05-02 | 2013-11-13 | 中国科学院长春应用化学研究所 | Catalyst for preparing syndiotactic polystyrene and preparation method of syndiotactic polystyrene |
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