CN1697842A - Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same - Google Patents
Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same Download PDFInfo
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- CN1697842A CN1697842A CNA2004800000330A CN200480000033A CN1697842A CN 1697842 A CN1697842 A CN 1697842A CN A2004800000330 A CNA2004800000330 A CN A2004800000330A CN 200480000033 A CN200480000033 A CN 200480000033A CN 1697842 A CN1697842 A CN 1697842A
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- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
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Abstract
The present invention relates to a catalyst system for preparing styrene polymer and a method of preparing styrene polymer using the same, more particularly to a catalyst system for preparing styrene polymer capable of preventing coagulation of polymer to the reactor by preventing gelation, offering high conversion ratio, simplifying polymer production and enabling product size control, and a method of preparing styrene polymer using the same.
Description
Technical field
The present invention relates to a kind ofly be used to prepare the catalyst system of styrene polymer and use this catalyst system to prepare the method for styrene polymer, especially relate to and a kind ofly can prevent that polymkeric substance from condensing, providing preparation that high conversion simplifies polymkeric substance and the catalyst system that is used to prepare styrene polymer that can control the product size on reactor, and use this catalyst system to prepare the method for styrene polymer by preventing gelation.
Background technology
Canadian Patent No.2,026,552 disclose a kind of use metalloscene catalyst preparation have between the method for styrene polymer of rule three-dimensional arrangement.
Usually, prepare method with styrene monomer and can be divided into slurry method (slurry method) and the monomeric substance law of direct polymerization (bulk method) that uses inert organic solvents with syndiotactic polymkeric substance.
In slurry method, because the gelation that takes place in the polymerization process of syndiotactic styrenic polymer in substance law can be prevented from, so can use the liquid-phase polymerization device that is equipped with conventional whisk.That is, need not specially designed device.In addition, so because product is can continuous production with the liquid form acquisition.Yet,, therefore just must carry out the process of separated from solvent and purifying because inert organic solvents should be at least 80% of reactant.In addition, because catalytic activity significantly reduces, this method is limited to Study of Catalyst, and test is unsuitable for large-scale preparation with other small-scale productions.
Because substance law does not need extra separated from solvent and purification process and good catalytic activity is provided, so the substance law of this monomer direct polymerization is mainly used.Yet this method can be owing to gelation causes polymkeric substance agglomerative problem on reactor wall.Therefore, need use to be the specially designed reactor of polymerization syndiotactic styrenic monomer, so just increase production cost and productivity is reduced.
Many reactors have been designed in order to solve gelation problems.For example, U.S. Patent No. 5,254,647 disclose the reactor (wiped surface reactor) that strike off on a kind of surface that is used to prepare syndiotactic styrenic polymer.This reactor uses two pairs to prevent the agglomerative conventional screw with low conversion range mix monomer, and wherein particle growth begins rapidly.Then, thus this monomer is transferred to powder bed type reactor with prepare syndiotactic styrene polymer with high conversion ratio.As a result, although the mixing efficiency of powder bed type reactor is low, but still can obtain the polymkeric substance of relative homogeneous.Yet the capacity and the operability of screw reactor are limited, and because polymerization is carried out with low-conversion, so high conversion is just necessary to use powder bed type reactor in order to obtain, and this has just increased production cost.
U.S. Patent No. 6,242,542 disclose by by polyphone or connect the method and apparatus that back-mixed reactors prepares syndiotactic styrenic polymer abreast.And U.S. Patent No. 5,484,862 disclose a kind of improved liquid phase powder bed type reactor.According to this patent, because horizontal agitator disperses the polymer powder as initiator in liquid monomer, so syndiotactic styrenic polymer can be made continuously.
Yet all routine techniquess all concentrate on and prevent gelation or destroy the agglomerative particle, and can not fundamentally solve condensing and adhesion problems in the polymerization.
Thus, need explore and to prevent polymer coagulation and can provide the cinnamic method of preparation of high conversion by fundamentally preventing gelation problems with regard to the utmost point by keeping polymerization catalyzed activity.
Summary of the invention
An object of the present invention is to provide a kind of catalyst system for preparing styrene polymer, this catalyst system can prevent in the inside reactor polymer coagulation, by keeping polymerization catalyzed activity that high conversion is provided, simplifying preparation process and polymer production and can the controlling polymers particle size by fundamentally preventing gelation problems.
Another object of the present invention provides and can prevent in the inside reactor polymer coagulation with by keeping polymerization catalyzed activity that the method for preparing styrene polymer of high conversion is provided by fundamentally preventing gelation problems.
In order to reach these purposes, the invention provides the catalyst system of the preparation styrene polymer that comprises the metalloscene catalyst that is carried on the syndiotactic styrenic polymer and promotor.
The present invention also provides the described carried catalyst existence method for preparing styrene polymer of the monomeric step of polymerizing styrene down that is included in.
Description of drawings
Fig. 1 is the synoptic diagram of styrene polymer preparation facilities according to an embodiment of the invention.
Fig. 2 is the schematic representation of apparatus of continuous preparation styrene polymer according to an embodiment of the invention.
Embodiment
Below, the present invention will be by more detailed description.
The inventor is devoted to and can prevents in the inside reactor polymer coagulation with by keeping polymerization catalyzed activity that the method for preparing styrene polymer of high conversion is provided by fundamentally preventing gelation problems.In this case, the contriver finds because the gelation in the conventional mass polymerization can fundamentally be prevented, so in the presence of metalloscene catalyst and promotor are carried on carried catalyst on the syndiotactic styrenic polymer, can the not induce reaction polymer coagulation of device inside of the styrene polymer for preparing by the polymerizing styrene monomer.And the contriver also finds because can avoid the quick reduction of catalytic activity in the slurry polymerization, so the monomeric transformation efficiency of polymerizing styrene can keep high more a lot of than the transformation efficiency in the slurry polymerization in the present invention.
Of the present invention being characterized as comprises the metalloscene catalyst that is carried on the syndiotactic styrenic polymer and the catalyst system that is used to prepare styrene polymer of promotor.
Described carried catalyst be by in the presence of the promotor (based on metal content) of 100～2000 moles of styrene monomers that are included in the metal in the metalloscene catalyst with respect to 1 mole, 1 mole metalloscene catalyst (based on metal content) and 1～2000 mole by the polymerization preparation.
The styrene monomer that uses among the present invention is the raw material that comprises the structure of being represented by following Chemical formula 1:
PhCH＝CH
2
Wherein Ph is the phenyl group that is replaced by at least one hydrogen atom, halogen atom, carbon atom, Sauerstoffatom, phosphorus atom, sulphur atom or tin atom.
Described styrene monomer can be Vinylstyrene, trivinylbenzene, or aryl vinylbenzene for example ring-alkylated styrenes, halogenated styrenes, halogenated ring-alkylated styrenes, alkoxystyrene, vinyl biphenyl, ethenylphenyl naphthalene, ethenylphenyl pyrene, ethenylphenyl anthracene, trialkylsilkl vinyl biphenyl, alkyl silyl vinylbenzene, alkyl ester vinylbenzene, carboxymethyl vinylbenzene, vinylbenzenesulfonic acid ester, vinyl benzyl dialkoxy phosphide, p-Vinylstyrene and m-Vinylstyrene.Specifically, can use ring-alkylated styrenes for example vinylbenzene, vinyl toluene, ethyl group vinylbenzene, butylstyrene, p-vinyl toluene, p-t-butyl styrene and dimethyl styrene; Halogenated styrenes is fluorobenzene ethene, chloro-styrene and bromstyrol for example; Halogenated vinylbenzene is 1-chloro-4-methyl-benzene and bromo ethyl phenenyl ethene for example; Alkoxystyrene is methoxy styrene, phenetole ethene and butyl phenyl ether ethene for example; Vinyl biphenyl is 4-vinyl biphenyl and 3-vinyl biphenyl for example; The ethenylphenyl naphthalene is 1-(4-vinyl xenyl) naphthalene, 2-(4-vinyl xenyl) naphthalene, 1-(3-vinyl xenyl) naphthalene and 1-(2-vinyl xenyl) naphthalene for example; The ethenylphenyl pyrene is 1-(4-ethenylphenyl) pyrene and 2-(4-ethenylphenyl) pyrene for example; The ethenylphenyl anthracene is 1-(4-ethenylphenyl) anthracene and 2-(4-ethenylphenyl) anthracene for example; Trialkylsilkl biphenyl is 4-vinyl-4-trimethyl silyl biphenyl for example; Or alkyl silyl vinylbenzene for example o-trimethyl silyl vinylbenzene, m-triethyl-silyl vinylbenzene and p-triethyl-silyl vinylbenzene.
Preferably, metalloscene catalyst be with respect to described styrene monomer with 0.01～10mol%, more preferably involved with 0.1～5mol%.If the content of metalloscene catalyst, then carries intravital catalyst content less than 0.1mol% and can become too low and enough catalytic activitys can not be provided.On the other hand, if its content has surpassed 5mol%, then vector contg becomes too low than the content of catalyzer, to such an extent as to supporting effect reduces greatly.
Any metalloscene catalyst that uses in the preparation of conventional syndiotactic styrenic polymer all can be used as the metalloscene catalyst that uses among the present invention.Generally speaking, IV family metallized metal [titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta)] compound is preferred for metalloscene catalyst.Be more preferably titanium compound.
For described promotor, can use alkylaluminoxane, alkylaluminium cpd or borate compound.Specifically, can stability in use by adding alkylaluminoxane that alkylaluminium cpd is improved for example methylaluminoxane (MAO) and the methylaluminoxane (MMAO) that improves; Alkylaluminium cpd is trimethyl aluminium, triethyl aluminum, chlorodimethylalumiu, diethylaluminum chloride, triisobutyl aluminium, three (n-butyl) aluminium, three (n-propyl group) aluminium and triisopropylaluminiuand (TIBAL) for example; Borate compound is borine for example, triphenylcarbenium four (pentafluorophenyl group) borate, o-cyano group-N-picoline nurse four (pentafluorophenyl group) borate, three (pentafluorophenyl group) boron, 1,1-dimethyl two luxuriant four (pentafluorophenyl group) borate (1,1-dimethylferroceniumtetra (pentafluorophenyl) borate) and benzyl dimethyl two luxuriant four (pentafluorophenyl group) borate.Especially, triisobutyl aluminium is preferably alkylaluminium cpd.
Preferably, described promotor is 1 mole of 1～2000 times of being included in metal in the metalloscene catalyst, more preferably 100～2000 times.If the content of promotor less than 1 mole, then is difficult to the activated metal cyclopentadienyl catalyst.Otherwise if it surpasses 2000 moles, excessive promotor is stayed in the supported catalyst solution, reduces to such an extent as to be difficult to the molecular-weight average of controlled polymerization speed and polymkeric substance.
In a word, the catalyzer that is used to prepare styrene polymer of the present invention comprises metalloscene catalyst and the promotor that is stated from the syndiotactic styrenic polymer.Preferably, described carried catalyst prepares in inert organic solvents and is disperseed with the concentration range of 0.00001～0.0005Ti mol/L.
Described inert organic solvents can be a pentane, hexane, and hexanaphthene, heptane, octane, nonane, decane, benzene, five fluoridize benzene or toluene.Preferably, be reflected at 0～120 ℃, more preferably carry out in 10～50 ℃ the temperature range.Preferably, the reaction times is 10～500 minutes, more preferably is 30～200 minutes.
If stirring can evenly carry out then reactor can be an Any shape.Especially, preferred fit has the stirred reactor that comes the external jacket of control reaction temperature by heat-transfer fluid.
The present invention also provides and has been included in the described catalyst system that is used to prepare styrene polymer and has the method that is used to prepare styrene polymer of the monomeric step of polymerizing styrene down.
Described styrene polymer can by adding comprise the metalloscene catalyst that is carried on the syndiotactic styrenic polymer and promotor be used to prepare the catalyst system of styrene polymer and in specified time, react or make by continuous adding raw material.
Preferably, described carried catalyst is the catalyzer that is scattered in the inert organic solvents.In addition, preferably, the volume of described styrene monomer is more preferably 0.5～5 times for 0.1～50 times of the organic molten agent volume of the inertia of using in the carried catalyst in preparation.If the volume of described styrene monomer is less than 0.1 times, then polymerization activity reduces fast.On the other hand, if its volume surpasses 50 times, gelation will be inevitable.
Preferably, described promotor is 1 mole of 10～1000 times of being carried on metallocenes on the carried catalyst.As the promotor that in the preparation of carried catalyst, uses, if this cocatalyst content less than 10 times, then metallocene supported catalyst can not be activated.In addition, if the content of this promotor surpasses 1000 times, then be difficult to controlled polymerization speed and be difficult to increase the molecular-weight average of polymkeric substance.
Preferably, the polymerization of described styrene polymer is at 0～120 ℃, more preferably carries out in 50～90 ℃ temperature range.And preferably, stir speed (S.S.) is controlled in 100～1000rpm in the polymerization.
Preferably, the average particle size particle size of product styrene polymer is that 0.05～1mm and weight average molecular weight are 10,000～2,000,000, more preferably 100,000～1,000,000.
Described styrene polymer has 10～100%, is preferably 20～70% transformation efficiency.Preferably, pass through C
13NMR analyzes, and the syndiotacticity of described styrene polymer is at least 75%, more preferably is at least 90%.
Now, according to Fig. 1 and Fig. 2, the preparation of carried catalyst of the present invention and styrene polymer is described.Fig. 1 is the synoptic diagram of styrene polymer preparation facilities according to an embodiment of the invention, and Fig. 2 is the schematic representation of apparatus of continuous preparation styrene polymer according to an embodiment of the invention.
As shown in Figure 1, the inert organic solvents 5 of purifying is added into by heat-transfer fluid 1 and is added in the stirring reaction apparatus under specified temp.Pure styrene monomers 2 of weighing then, and promotor 3 mix and join in the reactor.After the stirring, the metalloscene catalyst 4 that is diluted in the inert organic solvents is added into.Then, under agitation make metalloscene catalyst and be carried on carried catalyst on the syndiotactic styrenic polymer.Next step, the temperature of control heat-transfer fluid is to set the temperature of inside reactor.Then, add the styrene monomer 2 and the promotor of purifying, and under agitation reaction is carried out the specific time.Add the methyl alcohol termination reaction, and reaction mixture obtains styrene polymer with drying after filtration.
Fig. 2 is the schematic representation of apparatus of continuous preparation styrene polymer according to an embodiment of the invention, and wherein two stirred reactors link in proper order.The carried catalyst for preparing among Fig. 1 is transferred among second reactor b with continuous preparation syndiotactic styrenic polymer.More specifically, the supported catalyst solution 10 for preparing among the reactor a is transferred among the reactor b by pump 11.Simultaneously, with styrene monomer 8 blended methylaluminoxane 7 with among the predetermined flow velocity inflow reactor b.Controlling reaction time makes when finishing in being aggregated in reactor b, and reaction product 9 can be collected by successive.Because inert organic solvents 1, styrene monomer 2, promotor 3 and metalloscene catalyst 4 with predetermined flow velocity inflow reactor a in, among the supported catalyst solution inflow reactor b for preparing among the reactor a, can be made continuously so have the liquid phase benzene ethene polymers of high conversion.
Below, the present invention will be carried out more detailed description by embodiment.Yet embodiment subsequently only is used for the understanding of the present invention, and the present invention is not limited by following examples.
The inside of 1L reactor remain on 75 ℃ and by vacuumize the cleaning one day.Inside reactor purifies three times with high-purity argon gas.Then, reactor is set in 25 ℃.The purifying n-heptane of 250ml is added in the reactor, subsequently the methylaluminoxane of the purified styrene monomers of 0.5ml and 2.6ml (MAO, Albemarle; 4.68wt%AL) solution is added into reactor.Stir after 10 minutes, the pentamethyl-cyclopentadienyl trimethoxy that adds the usefulness dilution with toluene of 4.0ml closes titanium (Cp
*Ti (OME)
3) solution (0.005M).Behind about 1 hour of the stirring reaction, when reaction mixture becomes muddiness, temperature of reaction is elevated to 70 ℃ kept 10 minutes.Become 70 ℃ of homogeneous when the inside reactor temperature after, add the purified styrene monomers of 250ml, add methylaluminoxane (MAO, the Albemarle of 3.9ml then; 4.68wt%AL) solution.Reaction was carried out 2 hours under stirring with 600rpm.Add a spot of methyl alcohol with termination reaction.The liquid polymerization product collects by the valve of reactor bottom.Thereby product is with the excessive methanol wash that contains small amount of hydrochloric acid and obtain the styrene polymer of 73.7g in vacuum chamber in 80 ℃ of dryings.
Except stirring, made styrene polymer with similarly to Example 1 method with 1000rpm.
Except using triisobutyl aluminium (1M) toluene solution and methylaluminoxane (MAO, Albemarle; The solution of 4.68wt%AL) 50: 50 (based on al mole ratios) replaces methylaluminoxane (MAO, Albemarle; 4.68wt%AL) solution has made the styrene polymer of 65.2g as beyond the promotor with method similarly to Example 1.
5L and 20L stirred reactor link in proper order as shown in Figure 2.Inside reactor remain on 75 ℃ and by vacuumize the cleaning one day.Inside reactor purifies three times with high-purity argon gas.Then, the 5L reactor is set as 25 ℃ and 20L reactor and is set as 70 ℃.
The purifying n-heptane of 3600ml joins in the 5L reactor, subsequently the methylaluminoxane of the purified styrene monomers of 10.3ml, 55.0ml (MAO, Albemarle; 4.68wt%AL) the pentamethyl-cyclopentadienyl trimethoxy of the usefulness dilution with toluene of solution and 56.0ml closes titanium (Cp
*Ti (OME)
3) solution (0.0075M) added reactor continuously.Stirring reaction continues after about 1 hour, and reaction soln is transferred in the 20L reactor with pump.
The purifying n-heptane that adds 3600ml adds the methylaluminoxane of 82.5ml after 10 minutes again.Reaction is stirred with 600rpm and is carried out.After one hour, in the reactor at 5L under above-mentioned the same terms, the supported catalyst solution of 3600ml was produced through 1 hour.After one hour (reaction is back 2 hours in the reactor of 20L), the supported catalyst solution for preparing in the 5L reactor, the styrene monomer of purifying and methylaluminoxane solution flow in the 20L reactor with the flow velocity of 30ml/min, 30ml/min and 0.70ml/min respectively, and the while polymerisate is collected and the liquid level of 20L reactor keeps constant.Then, the n-heptane of purifying, the styrene monomer of purifying, methylaluminoxane solution and close titanium with the pentamethyl-cyclopentadienyl trimethoxy of dilution with toluene and hold liquid (0.0075M) and flow in the reactor of 5L with the flow velocity of 30ml/min, 0.10ml/min, 0.45ml/min and 0.45ml/min respectively, thus prepare carried catalyst and styrene polymer continuously.The total time of normal operate continuously is 10 hours.The styrene polymer weighed that obtains is 4.78kg.
Comparative Examples
The inside of 1L reactor remain on 70 ℃ and by vacuumize the cleaning one day.Inside reactor purifies three times with high-purity argon gas.Then, reactor is set in 25 ℃.The purifying n-heptane of 250ml is added in the reactor, subsequently the methylaluminoxane of the purified styrene monomers of 250ml and 6.5ml (MAO, Albemarle; 4.68wt%AL) solution is added in the reactor.Stir after 10 minutes, the pentamethyl-cyclopentadienyl trimethoxy that adds the usefulness dilution with toluene of 4.0ml closes titanium (Cp
*Ti (ME)
3) solution (0.005M).After 3 hours, add a spot of methyl alcohol at the 600rpm stirring reaction with termination reaction.Collect polymerisate, and with the excessive methanol wash that contains small amount of hydrochloric acid, thereby the styrene polymer that distills and in vacuum chamber, obtain 43.7g in 80 ℃ of dryings.
Test example 1
Mean diameter, transformation efficiency, molecular-weight average and the syndiotacticity of the styrene polymer of embodiment 1～4 and Comparative Examples preparation have been measured.It the results are shown in the following table 1.
Table 1
| Project | Embodiment | Comparative Examples | |||
| ??1 | ??2 | ??3 | ??4 | ||
| Mean diameter (mm) | ??0.5 | ??0.1 | ??1 | ??0.5 | ??0.1～2 |
| Transformation efficiency (%) | ??32.5 | ??33.1 | ??28.8 | ??29.4 | ??19.3 |
| Average molecular mass | ??587,000 | ??534,000 | ??551,000 | ??511,000 | ??488,000 |
| Syndiotacticity | 99% or higher | 99% or higher | 99% or higher | 99% or higher | 99% or higher |
| Productive rate | 99% or higher | 99% or higher | 99% or higher | 99% or higher | ??75％ |
In embodiment 1～4, be bonded at reaction product on the wall of reactor and agitator less than 1% of total amount.On the other hand, about 25% product is bonded on the wall of reactor and agitator because of gelation in Comparative Examples.In other words, be 99% or when higher, the productive rate of Comparative Examples only is about 75% at the productive rate of embodiment 1～4.That is to say that catalyst system of the present invention has prevented polymer beads condensing on reactor wall by preventing gelation at all.
In addition, catalyst system of the present invention is by keeping polymerization catalyzed activity to make providing high transformation efficiency, having simplified the preparation of reaction and polymkeric substance.In addition, catalyst system of the present invention has reduced the danger of electrostatic burst and the problem that has reduced the generation dust that is caused by powder transfer by the particle size of control final product.
Although the description that the present invention is detailed in addition according to specific embodiment does not all deviate from the spirit and scope of the invention in the accessory claim scope to professional and technical personnel's correction.
Claims (18)
1, a kind of metalloscene catalyst that is carried on the syndiotactic styrenic polymer and catalyst system that is used to prepare styrene polymer of promotor of comprising.
2, the catalyst system that is used to prepare styrene polymer of claim 1 is characterized in that described carried catalyst is prepared by the polymerization of styrene monomer in the presence of metalloscene catalyst and promotor.
3, the catalyst system that is used to prepare styrene polymer of claim 1 is characterized in that described carried catalyst comprises 100～2000 moles styrene monomer with respect to 1 mole of metal that is included in the metalloscene catalyst and based on the promotor of 1～2000 mole of metal content.
4, the catalyst system that is used to prepare styrene polymer of claim 2, it is characterized in that described styrene monomer is one or more compounds with structure of being represented by following Chemical formula 1, this compound is selected from and comprises ring-alkylated styrenes, halogenated styrenes, halogenated ring-alkylated styrenes, alkoxystyrene, vinyl biphenyl, the ethenylphenyl naphthalene, the ethenylphenyl pyrene, the ethenylphenyl anthracene, trialkylsilkl vinyl biphenyl, alkyl silyl vinylbenzene, alkyl ester vinylbenzene, carboxymethyl vinylbenzene, the vinylbenzenesulfonic acid ester, vinyl benzyl dialkoxy phosphide, Vinylstyrene, cinnamic group of trivinylbenzene and aryl:
Chemical formula 1
PhCH＝CH
2
Wherein Ph is the phenyl group that is replaced by at least one hydrogen atom, halogen atom, carbon atom, Sauerstoffatom, phosphorus atom, sulphur atom or tin atom.
5, the catalyst system that is used to prepare styrene polymer of claim 1 is characterized in that described metalloscene catalyst is one or more compounds that comprise the IV family metal that is selected from the group of being made up of titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb) and tantalum (Ta).
6, the catalyst system that is used to prepare styrene polymer of claim 1 is characterized in that described promotor is one or more compounds that are selected from the group of being made up of alkylaluminoxane, alkylaluminium cpd and borate compound.
7, the catalyst system that is used to prepare styrene polymer of claim 6 is characterized in that described alkylaluminoxane is the methylaluminoxane (MMAO) of methylaluminoxane (MAO) or improvement.
8, the catalyst system that is used to prepare styrene polymer of claim 6 is characterized in that described alkylaluminium cpd is one or more compounds that are selected from the group that comprises trimethyl aluminium, triethyl aluminum, chlorodimethylalumiu, diethylaluminum chloride, triisobutyl aluminium, three (n-butyl) aluminium, three (n-propyl group) aluminium and triisopropylaluminiuand (TIBAL).
9, the catalyst system that is used to prepare styrene polymer of claim 6, it is characterized in that described borate compound is that one or more are selected from and comprise borine, triphenylcarbenium four (pentafluorophenyl group) borate, o-cyano group-N-picoline nurse four (pentafluorophenyl group) borate, three (pentafluorophenyl group) boron, 1, the compound that 1-dimethyl two luxuriant four (pentafluorophenyl group) borates and benzyl dimethyl two luxuriant four (pentafluorophenyl groups) are boratory group.
10, the catalyst system that is used to prepare styrene polymer of claim 1 is characterized in that described carried catalyst is scattered in one or more and is selected from and comprises pentane, hexane, hexanaphthene, heptane, octane, nonane, decane, benzene, five and fluoridize the inert organic solvents of the group of benzene and toluene.
11, the catalyst system that is used to prepare styrene polymer of claim 1 is characterized in that described carried catalyst is scattered in the inert organic solvents with the concentration range of 0.00001～0.0005Ti mol/L.
12, a kind of method for preparing styrene polymer, there is the monomeric step of polymerizing styrene down in the carried catalyst that is included in claim 1.
13,, it is characterized in that described carried catalyst is scattered in one or more and is selected from and comprises pentane, hexane, hexanaphthene, heptane, octane, nonane, decane, benzene, five and fluoridize the inert organic solvents of the group of benzene and toluene according to the method that is used to prepare styrene polymer of claim 12.
14,, it is characterized in that described carried catalyst is scattered in the inert organic solvents with the concentration range of 0.00001～0.0005Ti mol/L according to the method that is used to prepare styrene polymer of claim 12.
15,, it is characterized in that described styrene monomer is added into 0.1～50 times volume of inert organic solvents volume according to the method that is used to prepare styrene polymer of claim 12.
16,, it is characterized in that described carried catalyst comprises 100～2000 moles styrene monomer with respect to 1 mole of metal that is included in the metalloscene catalyst and based on the promotor of 1～2000 mole of metal content according to the method that is used to prepare styrene polymer of claim 12.
17,, it is characterized in that described being aggregated in 0～120 ℃ the temperature range carry out according to the method that is used to prepare styrene polymer of claim 12.
18,, it is characterized in that carrying out under the described stirring velocity that is aggregated in 100～1000rpm according to the method that is used to prepare styrene polymer of claim 12.
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| CN105440187A (en) * | 2014-08-14 | 2016-03-30 | 中国科学院长春应用化学研究所 | Functional highly-syndiotactic polystyrene and preparation method thereof |
| CN106084101A (en) * | 2016-06-06 | 2016-11-09 | 宁波大学 | A kind of preparation method of low entanglement polyethylene |
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| KR100690352B1 (en) * | 2005-04-02 | 2007-03-12 | 주식회사 엘지화학 | Method of producing styrenic polymers using high speed catalytic dispersion technology |
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| US6096677A (en) * | 1997-10-17 | 2000-08-01 | Sri International | Supported metallocene catalysts |
| CN1076732C (en) * | 1998-03-30 | 2001-12-26 | 中国石油化工总公司 | Carried catalyst for homogeneous syndiotactic polymerization of styrene |
| US20010047065A1 (en) * | 1999-06-03 | 2001-11-29 | Sun-Chueh Kao | Method for preparing a supported catalyst system and its use in a polymerization process |
| KR100328866B1 (en) * | 1999-07-02 | 2002-03-20 | 유현식 | Polymerization process of syndiotactic polystyrene derivatives using microfluidization |
-
2004
- 2004-02-04 KR KR1020040007310A patent/KR100561076B1/en not_active IP Right Cessation
- 2004-02-05 CN CNB2004800000330A patent/CN1303110C/en not_active Expired - Fee Related
- 2004-02-05 AT AT04708517T patent/ATE528325T1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440187A (en) * | 2014-08-14 | 2016-03-30 | 中国科学院长春应用化学研究所 | Functional highly-syndiotactic polystyrene and preparation method thereof |
| CN105440187B (en) * | 2014-08-14 | 2019-02-12 | 中国科学院长春应用化学研究所 | A kind of high syndiotactic polytyrene of functionalization and preparation method thereof |
| CN106084101A (en) * | 2016-06-06 | 2016-11-09 | 宁波大学 | A kind of preparation method of low entanglement polyethylene |
| CN106084101B (en) * | 2016-06-06 | 2018-08-10 | 宁波大学 | A kind of preparation method of low entanglement polyethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE528325T1 (en) | 2011-10-15 |
| KR100561076B1 (en) | 2006-03-16 |
| KR20040071080A (en) | 2004-08-11 |
| CN1303110C (en) | 2007-03-07 |
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