CN1657544A - Process for syndiotactic polymerization of styrene - Google Patents
Process for syndiotactic polymerization of styrene Download PDFInfo
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- CN1657544A CN1657544A CN 200410016387 CN200410016387A CN1657544A CN 1657544 A CN1657544 A CN 1657544A CN 200410016387 CN200410016387 CN 200410016387 CN 200410016387 A CN200410016387 A CN 200410016387A CN 1657544 A CN1657544 A CN 1657544A
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- phenylethylene
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Abstract
A process for the syndiotactic polymerization of styrene to prepare syndiotactic polystyrene features that the cyclopentadienyl titanium compound and alkylaluminium are used as catalyst, the catalyst is added at optimal reaction temp (5-40 deg.C) and the temp is raised to the optimal reaction temp within 10-60 min.
Description
Technical field
The present invention relates to syndiotactic polymerization process of phenylethylene.
Background technology
The homogeneous catalysis system that cyclopentadiene titanium compound and promotor methylaluminoxane (MAO) or boron fluorine cpd are formed is used for syndiotactic polymerization of phenylethylene and can obtains a normality at the syndiotactic polymer more than 96%.Melting point polymer is up to 270 ℃, and crystallization velocity is fast, chemically-resistant, and good heat resistance, narrow molecular weight distribution, dimensional stability is good, and has excellent electric performance, and its over-all properties can be compared with engineering plastics.The appearance of syndiotactic polystyrene (SPS) has caused people to its catalyst system, particularly the research of Primary Catalysts metallocene compound.Many highly active catalyzer are come out one after another, but have also brought technologic problem, and the syndiotactic polymerization of phenylethylene process is a precipitation polymerization process, show through laboratory test, along with reaction is carried out, system will generate the solid-liquid phase mixture, and further reaction will be carried out in the solid-liquid two-phase.But the existence of solid phase induces reaction easily and conducts heat inhomogeneously, and may make the polymers swell adhesion, control improper will the caking, is bonded at stirring rake, on thermopair and the reactor wall, makes reaction be difficult to continuation.Catalyst activity is big more, just easy more generation of said circumstances.This block produces and has not only stoped reaction further to be carried out, and brings the deuce to pay for the product aftertreatment, and therefore controls reaction speed how is easily washed exsiccant SPS particle, becomes the problem that at first will consider in the polymerization amplification process.Though domesticly in the exploitation of catalyzer, obtain certain progress, but because syndiotactic polymerization of phenylethylene is the heterogeneous precipitation process of a complexity, the syndiotactic polystyrene that generates is insoluble in vinylbenzene and the solvent, therefore with random polystyrene production very big difference is arranged, and because easy swelling part vinylbenzene of the polymkeric substance that generates and solvent very easily generate gel.
In bulk polymerisation process, the variation of polymerization system viscosity can roughly be divided into three phases: in the low sticking stage, vinylbenzene, oligopolymer and polymkeric substance are based on liquid phase, and system viscosity is lower, and power of agitator is less; The high sticking stage, along with polymeric carries out, the raising of transformation efficiency, and inter-adhesive between particle, it is maximum that power of agitator will reach, and this stage is polyreaction critical days, is easy to gel or caking.In the powder stage, after transformation efficiency further improved, whole polymerization system was powder bed substantially, and power of agitator substantially no longer changes.
Because syndiotactic polystyrene is a crystalline polymer, in polyreaction, is accompanied by high molecular crystallization, when the crystallization velocity of polymerization rate and macromolecular chain is complementary, can obtain SPS powder granule preferably.
Because the styrene catalyzed syndiotactic polymerization activity of metallocene catalyst is very high, speed is very fast, therefore general employing fluidized-bed reaction still (US5306790), but very high to equipment requirements.If adopt general vertical stirrer, often need add catalyzer in batches, and the catalyst levels span of control of fs narrower (patent EP390000).
Rise because most of metallocene catalyst catalytic activitys raise with polymerization temperature, when polymerization temperature was low, polymerization velocity was slack-off, reacting balance, but final catalyst efficiency is lower.
Summary of the invention
Technical problem to be solved by this invention is in the past in preparation syndiotactic polystyrene process, caking easily takes place and produce gel, and the problem that catalyst efficient is reduced provides a kind of method of new syndiotactic polymerization of phenylethylene.This method has reacting balance, can prevent effectively that caking and gel from producing the characteristics that catalytic efficiency does not fall.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of syndiotactic polymerization process of phenylethylene, with vinylbenzene is reaction raw materials, with cyclopentadiene titanium compound and alkylaluminoxane is catalyzer, vinylbenzene is 40～90 ℃ in temperature in reactor, pressure is to carry out bulk polymerization under the condition of normal pressure to generate syndiotactic polystyrene, wherein below catalyzer optimal reaction temperature T, drop into catalyzer during 5～40 ℃ of temperature, and in 10～60 minutes, make temperature rise to catalyzer optimal reaction temperature T.
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 or pentamethyl-cyclopentadienyl; R
2, R
3Or R
4Be selected from alkyl, aryl, aralkyl or the alkaryl of 1～12 carbon atom, preferred version is to be selected from the alkyl of 1～4 carbon atom or aryl, aralkyl or the alkaryl of 6～10 carbon atoms; Alkylaluminoxane is that methylaluminoxane is or/and triisobutyl aluminium.When being 10～25 ℃ of temperature below the optimal reaction temperature T, drops into catalyzer charging time preferred version catalyzer.Make temperature rise to the time of catalyzer optimal reaction temperature T in 20～40 minutes.Benzene feedstock ethene preferred version for before dropping into reactor at catalyzer, the catalyzer input dropped into reactor simultaneously or after the catalyzer input before being warmed up to catalyzer optimum temps T, more preferably scheme be benzene feedstock ethene before catalyzer drops into reactor or the catalyzer input drop into reactor simultaneously.
The present invention adopts: when catalyzer is used for the best polymerization temperature of syndiotactic polymerization of phenylethylene is T
1The time, temperature when control adds catalyzer in the reactor system and catalyzer add the time that the back system is warming up to well-defined reaction temp, and temperature-rise period is generally guaranteed the established technical scheme of polymkeric substance initiating particle.Heating-up time is oversize, often cause catalyst efficiency to reduce, and molecular weight of product distributes wide; Heating-up time is too short, does not reach the formation initiating particle, still has block and produces.Adopt method of the present invention, stable polymerization reaction not only, catalyzer can once feed intake, and catalyst efficiency do not fall substantially, and molecular weight of product distributes and keeps stable, has obtained better technical effect.The present invention is particularly suitable for the disposable batch reactor that feeds intake, and is particularly suitable for mass polymerization.
The invention will be further elaborated below by embodiment, but be not limited to scope of the present invention.
Embodiment
[embodiment 1]
On 10 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, and 40 ℃ of the interior temperature of system this moment contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.214 mmole Cp with the syringe injection
*Ti (OC
6H
4)
3The metallocene-titanium catalyst toluene solution, Cp wherein
*Be the pentamethyl-cyclopentadienyl, after catalyzer adds, progressively chuck heating, about 30 minutes, make in the system temperature to 70 ℃ of polymerization temperatures, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1950 restrains, block does not have substantially, catalyst efficiency 154 kg of polymer/(gram titanium), between normality 97%, molecular weight distribution mw/mn=2.12, wherein Mw is a weight-average molecular weight, Mn is a number-average molecular weight.
[embodiment 2]
On 10 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, and 45 ℃ of the interior temperature of system this moment contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.214 mmole Cp with the syringe injection
*Ti (OC
6H
4)
3The metallocene-titanium catalyst toluene solution, after catalyzer added, progressively chuck heating made in the system temperature to 70 ℃ of polymerization temperatures about 40 minutes, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1920 restrains, block does not have substantially, catalyst efficiency 151 kg of polymer/(gram titanium), a normality 97%, molecular weight distribution mw/mn=2.15.
[comparative example 1]
On 10 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, and the interior temperature of system this moment directly is controlled at 70 ℃, injects with syringe to contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.214 mmole Cp
*Ti (OC
6H
4)
3The metallocene-titanium catalyst toluene solution, at 300 rev/mins of following stirring reactions, after 30 minutes, have block to occur in the reactor, reaction has to stop, product almost can not aftertreatment.
[comparative example 2]
On 10 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, and the interior temperature of system this moment directly is controlled at 40 ℃, injects with syringe to contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.214 mmole Cp
*Ti (OC
6H
4)
3The metallocene-titanium catalyst toluene solution, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1020 restrains, block does not have substantially, catalyst efficiency is lower, have only 52 kg of polymer/(gram titanium), a normality 96%, molecular weight distribution mw/mn=2.11.
[comparative example 3]
Identical with embodiment 1 condition, different is that chuck extended to 90 minutes from 30 minutes heat-up time, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1710 restrains, block does not have substantially, catalytic efficiency 135 kg of polymer/(gram titanium), a normality 96%, but molecular weight distribution mw/mn=2.82.
[embodiment 3]
On 10 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, and 35 ℃ of the interior temperature of system this moment contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.214 mmole Cp with the syringe injection
*Ti (OC
6H
4-F)
3The metallocene-titanium catalyst toluene solution, after catalyzer added, progressively chuck heating made in the system temperature to 75 ℃ of polymerization temperatures about 40 minutes, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1991 restrains, block does not have substantially, catalyst efficiency 156 kg of polymer/(gram titanium), a normality 99%, molecular weight distribution mw/mn=2.16.
[embodiment 4]
On 10 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, and 30 ℃ of the interior temperature of system this moment contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.428 mmole Cp with the syringe injection
*TiCl
3The metallocene-titanium catalyst toluene solution, after catalyzer added, progressively chuck heating made in the system temperature to 55 ℃ of polymerization temperatures about 35 minutes, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1533 restrains, block does not have substantially, catalyst efficiency 62 kg of polymer/(gram titanium), a normality 96%, molecular weight distribution mw/mn=2.11.
[embodiment 5]
On 10 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, and 45 ℃ of the interior temperature of system this moment contain 52.8 mmole triisobutyl aluminiums, 105.6 mmole MAO, 0.214 mmole Cp with the syringe injection
*Ti (OC
6H
4-OCH
3)
3The metallocene-titanium catalyst toluene solution, after catalyzer added, progressively chuck heating made in the system temperature to 80 ℃ of polymerization temperatures about 40 minutes, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1901 restrains, block does not have substantially, catalyst efficiency 148 kg of polymer/(gram titanium), a normality 98%, molecular weight distribution mw/mn=2.17.
[comparative example 4]
Identical with embodiment 3 conditions, different is at the very start 75 ℃ of reactions, and 300 rev/mins of following stirring reactions had big block to occur after 40 minutes, and reaction has to stop.
[comparative example 5]
Identical with embodiment 3 conditions, different is always 35 ℃ of reactions, 300 rev/mins of following stirring reactions are after 4 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1132 restrains, block does not have substantially, catalyst efficiency 89 kg of polymer/(gram titanium), a normality 97%, molecular weight distribution mw/mn=2.09.
Claims (8)
1, a kind of syndiotactic polymerization process of phenylethylene, with vinylbenzene is reaction raw materials, with cyclopentadiene titanium compound and alkylaluminoxane is catalyzer, vinylbenzene is 40～90 ℃ in temperature in reactor, pressure is to carry out bulk polymerization under the condition of normal pressure to generate syndiotactic polystyrene, drop into catalyzer when it is characterized in that below catalyzer optimal reaction temperature T 5～40 ℃ of temperature, and in 10～60 minutes, make temperature rise to catalyzer optimal reaction temperature T.
2,, 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.
3, according to the described syndiotactic polymerization process of phenylethylene 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 or 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 syndiotactic polymerization process of phenylethylene of claim 1.
5,, drop into catalyzer when it is characterized in that below catalyzer optimal reaction temperature T 10～25 ℃ of temperature according to the described syndiotactic polymerization process of phenylethylene of claim 1.
6,, it is characterized in that in 20～40 minutes, making temperature to rise to the catalyzer optimal reaction temperature according to the described syndiotactic polymerization process of phenylethylene of claim 1.
7, according to the described syndiotactic polymerization process of phenylethylene of claim 1, it is characterized in that benzene feedstock ethene before catalyzer drops into reactor, the catalyzer input dropped into reactor simultaneously or after the catalyzer input before being warmed up to catalyzer optimum temps T.
8, according to the described syndiotactic polymerization process of phenylethylene of claim 7, it is characterized in that vinylbenzene before catalyzer drops into reactor or the catalyzer input drop into reactor simultaneously.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410016387 CN1277851C (en) | 2004-02-18 | 2004-02-18 | Process for syndiotactic polymerization of styrene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410016387 CN1277851C (en) | 2004-02-18 | 2004-02-18 | Process for syndiotactic polymerization of styrene |
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| Publication Number | Publication Date |
|---|---|
| CN1657544A true CN1657544A (en) | 2005-08-24 |
| CN1277851C CN1277851C (en) | 2006-10-04 |
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|---|---|---|---|
| CN 200410016387 Expired - Fee Related CN1277851C (en) | 2004-02-18 | 2004-02-18 | Process for syndiotactic polymerization of styrene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633918A (en) * | 2012-05-02 | 2012-08-15 | 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 |
-
2004
- 2004-02-18 CN CN 200410016387 patent/CN1277851C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633918A (en) * | 2012-05-02 | 2012-08-15 | 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 |
| 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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| Publication number | Publication date |
|---|---|
| CN1277851C (en) | 2006-10-04 |
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