CN1086192C - Syndiotactic polymerization process of phenylethylene - Google Patents
Syndiotactic polymerization process of phenylethylene Download PDFInfo
- Publication number
- CN1086192C CN1086192C CN98122010A CN98122010A CN1086192C CN 1086192 C CN1086192 C CN 1086192C CN 98122010 A CN98122010 A CN 98122010A CN 98122010 A CN98122010 A CN 98122010A CN 1086192 C CN1086192 C CN 1086192C
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- CN
- China
- Prior art keywords
- phenylethylene
- polymerization process
- reaction
- organic solvent
- catalyzer
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
Abstract
The present invention relates to a syndiotactic polymerization process of phenylethylene. Before a polymerization reaction, a cyclopentadienyl titanium compound and alkylaluminoxyane in a reaction dosage are mixed together and put in an organic solvent for aging; then, a catalyst and the organic solvent are put together in a reactor for reaction, and phenylethylene is put in the reactor in advance. The process has the characteristics of no agglomeration of reaction products in the reaction process and stable reaction, and the present invention can be used for industrial production.
Description
The present invention relates to syndiotactic polymerization process of phenylethylene.
Styrene polymer can be divided into random polystyrene, isotactic polyphenylacetylene and syndiotactic polystyrene.The catalyzer that synthesis of syndiotactic polystyrene adopts organo-metallic titanium compound and poly-methylaluminoxane (MAO) to form usually.The organo-metallic titanium compound is mainly cyclopentadiene titanium compound.Utilizing metallocene catalyst to carry out the styrene syndiotactic mass polymerization is a kind of precipitation slurry polymerization, and system viscosity is very big.Reported all in its reaction process that three phases is arranged among document US 5032652, the EP 0390000.Fs: monomer, oligopolymer and superpolymer all exist with liquid state, and viscosity is lower; Subordinate phase: viscosity is especially big, need provide high shearing force could guarantee to react and carry out smoothly, otherwise reaction product can be lumpd; Phase III: superpolymer exists with solid-state dry powder, viscosity degradation, and it is less to react required shearing force.In order to tide over subordinate phase smoothly, present technology mainly contains following two kinds: described in first kind of technology such as EP 0379128, the CN 1045977A, provide superpower shearing force in subordinate phase.Superpower shearing force is mainly provided by the twin screw self-cleaning reactor in this two document.Double-screw reactor is by closely interlocking work between the gear, thereby extremely strong shearing force is provided, even therefore product produces little caking, is also pulverized by screw rod immediately, has guaranteed that reaction carries out smoothly.Using the shortcoming of double-screw reactor is that energy consumption is big especially, and every liter of styrene polymer product power demand has increased production cost greatly generally more than 1 kilowatt/liter.Second kind of technology is the fluidized-bed process that gasifies described in the employing document US 5306790.This technology is the syndiotactic polystyrene powder that adds still cumulative volume 60～70% in advance in reactor, Tonghua fluid technology continuously feeding, the viscosity of control reactant is more evenly carried out reaction, jump over subordinate phase, thereby avoided the caking situation of reaction product to take place.This technology requires a large amount of product seed material of pre-input in reactor on the one hand, the syndiotactic polystyrene product seed material that requires on the other hand to drop into needs strictness to remove impurity, and degree of drying is also higher, also strict to the control of benzene feedstock vinyl monomer input concentration, cross rare or overrich a little, just easily make product syndiotactic polystyrene caking; In addition use the required energy consumption of fluidized-bed process also bigger.The influence to catalyst activity of storage temperature, time is disclosed among flat 8-301916 of document JP and the flat 8-301917 of JP, but its purpose only is in order to preserve catalyzer, prevent the inactivation of catalyzer, there is no and relate to the situation that is used for reacting after the catalyzer ageing and reaction can prevent that product viscosity from increasing the situation of back caking.
Purpose of the present invention is exactly to exist in the reaction process in order to overcome in the existing document, reaction product is lumpd easily, or the bigger defective of using of reactor energy consumption, and a kind of new syndiotactic polymerization process of phenylethylene is provided, this technology has reacting balance, the characteristics of reaction product prevented from caking.
The objective of the invention is to realize: a kind of syndiotactic polymerization process of phenylethylene by following technical scheme, with cyclopentadiene titanium compound and alkylaluminoxane is catalyzer, vinylbenzene is 0～90 ℃ in temperature, and pressure is to carry out mass polymerization under the condition of normal pressure to generate syndiotactic polystyrene.Before polyreaction, at first the catalyzer cyclopentadiene titanium compound of reaction institute expense and alkylaluminoxane are mixed and place the organic solvent ageing, the ageing temperature is 0～100 ℃, digestion time is 2～180 minutes, organic solvent and catalyzer is joined together to feed in advance in the cinnamic reactor then.
Organic solvent is selected from toluene, benzene, dimethylbenzene, hexane or heptane in the technique scheme, and the consumption of organic solvent is 1～5% of a whole reaction system volume.Before the polyreaction, it is 15～50 ℃ that catalyzer places organic solvent ageing temperature preferable range, and the digestion time preferable range is 5～30 minutes, and the cyclopentadiene titanium compound in the catalyst system therefor is selected from R
1Ti (OR
2OR
3)
3(referring to Chinese patent application 98122011.8), 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.Alkylaluminoxane in the catalyst system therefor for being selected from methylaluminoxane or/and triisobutyl aluminium.
In the technology of the present invention, because before polyreaction, at first the catalyzer cyclopentadiene titanium compound of reaction institute expense and alkylaluminoxane are mixed and place the organic solvent ageing, make catalyzer form a large amount of exposed effective active centers.With catalyzer and organic solvent join together drop in the cinnamic reactor in advance after, therefore the amount of organic solvent to the aftertreatment of reaction product, can not cause trouble as the devolatilization process owing to only account for 1～5% of reaction volume; The suitable dilute catalyst concentration of the adding of organic solvent prevents that catalyst concn is too high in addition.After catalyzer is put into reactor, play the active centre uniform distribution diffusion of katalysis, make each exposed effective active center all can produce chainpropagation, the degree that styrene monomer is contained descends, avoided the catalytic active center part too much to cause reaction too violent, the situation that causes caking phenomenon takes place, and has obtained effect preferably.In the ageing process of catalyzer, the oversize meeting of digestion time causes catalyst deactivation.Digestion time is too short, temperature of reaction is too high, and catalyst activity is too high, is unfavorable for that also successful reaction carries out.Because catalyst active center's homodisperse of technology of the present invention, therefore technology of the present invention need only use two ribbon stirring arm reactors can obtain uniform white powdery syndiotactic polystyrene product, its particle size diameter≤0.8 millimeter, the energy consumption of reaction process has also obtained reducing greatly simultaneously.
The invention will be further elaborated below by embodiment.[embodiment 1]
10 liters of stainless steel cauldrons, two ribbon stirring arms, 85 ℃ of following vacuum-dryings 3 hours, nitrogen replacement, temperature is reduced to 60 ℃, adds 3 liters of styrene monomers, earlier 0.18 mmole Cp
*Ti (O-C
6H
4-OCH
3)
3(Cp wherein
*Be the pentamethyl-cyclopentadienyl), 54 mmole methylaluminoxane, 54 mmole triisobutyl aluminiums are placed in 100 milliliters of toluene solutions 30 ℃ of following ageings 5 minutes, and then join in the reactor, 340 rev/mins of mixing speed, react very steady always, 3.5 hours reaction times, no caking phenomenon obtains white powder-like product syndiotactic polystyrene 921 grams at last, and particle size diameter is less than 0.70 millimeter.[embodiment 2]
10 liters of reactors, two ribbon stirring arms, 85 ℃ of following vacuum-dryings 3 hours, the high pure nitrogen displacement, temperature is reduced to 60 ℃, adds 3.5 liters of styrene monomers, and elder generation is 0.21 mmole Cp before the reaction
*Ti (OCH
3)
3, 63 mmole methylaluminoxane, 63 mmole triisobutyl aluminiums are placed in 110 milliliters of toluene solutions 20 ℃ of following ageings 15 minutes, and then join in the aforesaid reaction vessel, 340 rev/mins of mixing speed, react very steady always, termination reaction after 4 hours, no caking phenomenon obtains white powder-like product syndiotactic polystyrene 1103 grams, particle size diameter is less than 0.60 millimeter, and very easily washing is dry.[comparative example 1]
In reactor, add 3 liters of vinylbenzene and 54 mmole triisobutyl aluminiums, 54 mmole methylaluminoxane as different from Example 1 earlier, stir adding 0.18 mmole Cp after 5 minutes
*Ti (O-C
6H
4-OCH
3)
3, 340 rev/mins of rotating speeds, after 40 minutes, it is big that moment of torsion becomes suddenly, and reaction terminating gets a bulk of solid, is difficult to pulverize and aftertreatment.[comparative example 2]
Add 3.5 liters of vinylbenzene and 0.21 mmole Cp as different from Example 2 in the reactor earlier
*Ti (OCH
3)
3, stir and added 63 mmole triisobutyl aluminiums and 63 mmole methylaluminoxane in 15 minutes, 110 milliliters of toluene mixture liquid, the reaction mixing speed is 340 rev/mins, react after 45 minutes, moment of torsion is uprushed, termination reaction, many blocks of solid, be difficult to wash, drying.
Claims (6)
1, a kind of syndiotactic polymerization process of phenylethylene, with cyclopentadiene titanium compound and alkylaluminoxane is catalyzer, vinylbenzene is 0～90 ℃ in temperature, pressure is to carry out mass polymerization under the condition of normal pressure to generate syndiotactic polystyrene, it is characterized in that before polyreaction, at first the catalyzer cyclopentadiene titanium compound of reaction institute expense and alkylaluminoxane are mixed and place the organic solvent ageing, the ageing temperature is 0～100 ℃, digestion time is 2～180 minutes, organic solvent and catalyzer is joined together drop in advance in the cinnamic reactor then.
2, according to the described syndiotactic polymerization process of phenylethylene of claim 1, it is characterized in that organic solvent is selected from toluene, benzene, dimethylbenzene, hexane or heptane, the consumption of organic solvent is 1～5% of a whole reaction system volume.
3,, it is characterized in that the ageing temperature is 15～50 ℃ according to the described syndiotactic polymerization process of phenylethylene of claim 1.
4,, it is characterized in that digestion time is 5～30 minutes according to the described syndiotactic polymerization process of phenylethylene of claim 1.
5,, it is characterized in that cyclopentadiene titanium compound is selected from R according to the described syndiotactic polymerization process of phenylethylene of claim 1
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.
6,, it is characterized in that alkylaluminoxane is that methylaluminoxane is or/and triisobutyl aluminium according to the described syndiotactic polymerization process of phenylethylene of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122010A CN1086192C (en) | 1998-11-18 | 1998-11-18 | Syndiotactic polymerization process of phenylethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122010A CN1086192C (en) | 1998-11-18 | 1998-11-18 | Syndiotactic polymerization process of phenylethylene |
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| Publication Number | Publication Date |
|---|---|
| CN1253956A CN1253956A (en) | 2000-05-24 |
| CN1086192C true CN1086192C (en) | 2002-06-12 |
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ID=5227497
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98122010A Expired - Fee Related CN1086192C (en) | 1998-11-18 | 1998-11-18 | Syndiotactic polymerization process of phenylethylene |
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| Country | Link |
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| CN (1) | CN1086192C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093140C (en) * | 1999-06-24 | 2002-10-23 | 中国石油化工集团公司 | Catalyst for preparing syndiotactic poly styrene |
| CN1314717C (en) * | 2004-05-28 | 2007-05-09 | 中国石油化工股份有限公司 | Continuous method for preparing syndiotactic polyvinyl aromatic hydrocarbon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0271875A2 (en) * | 1986-12-15 | 1988-06-22 | Montedison S.p.A. | Process for producing crystalline vinyl aromatic polymers having a predominantly syndiotactic structure |
| US5023304A (en) * | 1989-03-28 | 1991-06-11 | Idemitsu Kosan Co., Ltd. | Process for producing styrene-based polymer |
| US5484862A (en) * | 1995-03-10 | 1996-01-16 | The Dow Chemical Company | Liquid phase powder bed syndiotactic vinylaromatic polymerization |
-
1998
- 1998-11-18 CN CN98122010A patent/CN1086192C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0271875A2 (en) * | 1986-12-15 | 1988-06-22 | Montedison S.p.A. | Process for producing crystalline vinyl aromatic polymers having a predominantly syndiotactic structure |
| US5023304A (en) * | 1989-03-28 | 1991-06-11 | Idemitsu Kosan Co., Ltd. | Process for producing styrene-based polymer |
| US5484862A (en) * | 1995-03-10 | 1996-01-16 | The Dow Chemical Company | Liquid phase powder bed syndiotactic vinylaromatic polymerization |
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| CN1253956A (en) | 2000-05-24 |
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