CN1208354C - Metallocene titanium compound and use thereof - Google Patents
Metallocene titanium compound and use thereof Download PDFInfo
- Publication number
- CN1208354C CN1208354C CN 02111302 CN02111302A CN1208354C CN 1208354 C CN1208354 C CN 1208354C CN 02111302 CN02111302 CN 02111302 CN 02111302 A CN02111302 A CN 02111302A CN 1208354 C CN1208354 C CN 1208354C
- Authority
- CN
- China
- Prior art keywords
- titanium compound
- cyclopentadienyl
- metallocene titanium
- metallocene
- mmole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a metallocene titanium compound and a use thereof, which mainly solves the problems of low catalytic efficiency and difficult adaptability for industrial requirements when the existing metallocene titanium compounds are used for the syndiotactic polymerization of styrene. The present invention has the technical scheme that the metallocene titanium compound whose general structure formula is R1Ti(OR2R3)3 is adopted, wherein R1 is cyclopentadienyl or cyclopentadienyl containing one to five alkyls containing 1 to 4 carbon atoms; R2 is aryl containing 6 to 12 carbon atoms; R3 is halogen; oxygen atoms are connected between Ti and R2. Thus, the problems are favorably solved, and the present invention can be used for the industrial production of the syndiotactic polymerization of styrene.
Description
Technical field
The present invention relates to metallocene titanium compound and uses thereof.
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.Document US 5252693 and EP210615 have reported that structure is CpTiCl
3And Cp
*TiCl
3The catalyst system of forming with promotor MAO is used for the situation of syndiotactic polymerization of phenylethylene, and wherein Cp is a cyclopentadienyl, Cp
*Be the pentamethyl-cyclopentadienyl, but its catalytic activity and catalytic efficiency are not high, poor stability, industrial application value is little.Patent US4978730, US5023222, US5045517 and US5196490 have reported the high CpTi of present catalytic efficiency (OR)
3And Cp
*Ti (OR)
3Type catalyzer (R is an alkyl or aryl), specific activity had raising in the past, but from industry distance need be arranged still.
Summary of the invention
One of technical problem to be solved by this invention is that the cyclopentadiene titanium compound catalytic activity that overcomes in the document in the past still has the problem of gap from industrial requirement, and a kind of new metallocene titanium compound is provided.This compound and alkylaluminoxane are or/and the catalyst system that aluminum alkyls is formed when being used to prepare syndiotactic polystyrene, has the high characteristics of catalytic activity.Two of technical problem to be solved by this invention is purposes of above-mentioned metallocene titanium compound.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of metallocene titanium compound, and its structure has following general formula:
R
1Ti(OR
2R
3)
3
R in the formula
1For cyclopentadienyl or contain 1～5 C
1～4The cyclopentadienyl of alkyl;
R
2For containing the aryl of 6～12 carbon atoms;
R
3Be halogen;
Wherein Ti and R
2Between have Sauerstoffatom to link to each other.
In the technique scheme, R
1Preferred version is cyclopentadienyl or pentamethyl-cyclopentadienyl, and more preferably scheme is the pentamethyl-cyclopentadienyl.R
2Preferred version is phenyl, indenyl or xenyl, and more preferably scheme is a phenyl.R
3Preferred version is for being selected from fluorine, chlorine, bromine or iodine, and more preferably scheme is a chlorine.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: above-mentioned metallocene titanium compound is used for the preparation of syndiotactic polystyrene.
Metallocene titanium compound preparation technology of the present invention is in the presence of chlorine hydride absorbent to be that the reaction of solvent obtains with the hydrocarbon polymer by corresponding cyclopentadienyl titanous chloride and glycol ether.Chlorine hydride absorbent can be various aminated compoundss, and wherein trialkylamine is advisable, for example triethylamine.Hydrocarbon polymer can be aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbons better, benzene for example, toluene, dimethylbenzene etc.The mole ratio of cyclopentadienyl titanous chloride and hydroxyl is 1: 3.0～3.5, the mole ratio of cyclopentadienyl titanous chloride and triethylamine is 1: 3.0～4.0, temperature of reaction is 1～130 ℃, preferably 30～80 ℃, reaction times is 2～48 hours, best 6～24 hours, reaction process was preferably used intermittently heating operation.
During as the Syndiospecific Polymerization of Styrene catalyzer, its catalytic efficiency reaches as high as 510 kg of polymer/gram titanium to compound of the present invention, has obtained better technical effect with alkylaluminoxane.
Work as R
1Be pentamethyl-cyclopentadienyl, R
2Be phenyl, R
3Structural formula of compound is during for chlorine:
Learn that through hydrogen nuclear magnetic resonance spectrogram and infrared spectra map analysis structure is the said structure formula.
Its data are as follows:
Ultimate analysis (element analysis)
C
28H
27O
3Cl
3Ti：
Calcd.For
C 59.42％
H 4.77％
Cl?18.83％
Found
C 59.25％
H 4.79％
Cl?18.71％
The proton nmr spectrum
[HNMR?CDCl
3?TMS?intern]
δ6.75～7.25(m，12H，-(OPhHCl)
3)
δ1.90～2.15(s，15H，Cp-CH
3)
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Preparation of Catalyst
In the there-necked flask of 250 milliliters of exsiccant, N
2Pump drainage 3 times adds the 1.016 single luxuriant titanium of gram pentamethyl-trichlorine and 70 milliliters of benzene, from 30 milliliters of benzene of top dropping, 1.35 the mixture of gram para-chlorophenol and 1.1 gram triethylamines dripped off after 45 minutes, normal-temperature reaction is after 1 hour, reheat reacts after 2 hours to the benzene reflux temperature, stops heating, normal-temperature reaction 10 hours, reacting by heating is 2 hours once more, filters, filtrate is drained, and uses toluene, hexane solution recrystallization repeatedly, drains, get yellow crystals 1.74 grams, yield 88%.
[embodiment 2]
Preparation of Catalyst
In the there-necked flask of 250 milliliters of exsiccant, N
2Pump drainage 3 times adds the 2.10 single luxuriant titanium of gram pentamethyl-trichlorine and 70 milliliters of benzene, from 0 milliliter of benzene of top Dropwise 5,2.79 the mixture of gram para-chlorophenol and 2.4 gram triethylamines drips off reacting by heating 4 hours after 45 minutes, normal-temperature reaction is 10 hours again, reacting by heating 4 hours is once more filtered at last, and filtrate is drained, use hexane extraction, drain, get yellow crystals 3.5 grams, productive rate 85%.
[embodiment 3]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.2 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.4 mmole, the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 1 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.53 restrains, catalytic activity 443 kg of polymer/(the gram titanium. hour), a normality 96%, Mw=37 * 10
4
[comparative example 1]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected MAO 0.6 mmole with syringe after 20 minutes in 60 ℃ of oil baths, and the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 1 is after 30 minutes, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 0.852 restrains, catalytic activity 35 kg of polymer/(the gram titanium. hour), between normality 95%, Mw=46 * 10
4
[embodiment 4]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.2 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.6 mmole, the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.78 restrains, catalytic activity 474 kg of polymer/(the gram titanium. hour), a normality 96%, Mw=30 * 10
4
[embodiment 5]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.4 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.4 mmole, the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 4.07 restrains, catalytic activity 510 kg of polymer/(the gram titanium. hour), a normality 96%, Mw=27 * 10
4
[comparative example 2]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times adds 10 milliliters of commercial benzene vinyl monomers, and induction stirring was injected triisobutyl aluminium 0.4 mmole, MAO 0.4 mmole, Cp with syringe after 20 minutes in 60 ℃ of oil baths
*TiCl
30.001 mmole reaction (Cp after 10 minutes
*Be the pentamethyl-cyclopentadienyl), with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 0.41 restrains, catalytic activity 51 kg of polymer/(the gram titanium. hour), a normality 94%, Mw=15 * 10
4
[embodiment 6]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 2375 grams, stirs after 30 minutes, contain 52.8 mmole triisobutyl aluminiums with the syringe injection, 105.6 mmole MAO, the metallocene-titanium catalyst toluene solution of 0.264 mmole embodiment 1 is at 300 rev/mins of following stirring reactions after 3 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1950 restrains catalyst efficiency 154 kg of polymer/(gram titanium), between normality 97%, Mw=34 * 10
4
Claims (8)
1, a kind of metallocene titanium compound, its structure has following general formula:
R
1Ti(OR
2R
3)
3
R in the formula
1For cyclopentadienyl or contain 1～5 C
1～4The cyclopentadienyl of alkyl;
R
2For containing the aryl of 6～12 carbon atoms;
R
3Be halogen;
Wherein Ti and R
2Between have Sauerstoffatom to link to each other.
2, according to the described metallocene titanium compound of claim 1, it is characterized in that R
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl.
3, according to the described metallocene titanium compound of claim 2, it is characterized in that R
1Be the pentamethyl-cyclopentadienyl.
4, according to the described metallocene titanium compound of claim 1, it is characterized in that R
2Be phenyl, indenyl or xenyl.
5, according to the described metallocene titanium compound of claim 4, it is characterized in that R
2Be phenyl.
6, according to the described metallocene titanium compound of claim 1, it is characterized in that R
3Be selected from fluorine, chlorine, bromine or iodine.
7, according to the described metallocene titanium compound of claim 6, it is characterized in that R
3Be chlorine.
8, be used for the preparation of syndiotactic polystyrene according to the described metallocene titanium compound of claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111302 CN1208354C (en) | 2002-04-10 | 2002-04-10 | Metallocene titanium compound and use thereof |
| US10/410,036 US6921734B2 (en) | 2002-04-10 | 2003-04-09 | Titanocene complexes and its catalyst for preparing syndiotactic polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111302 CN1208354C (en) | 2002-04-10 | 2002-04-10 | Metallocene titanium compound and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1450089A CN1450089A (en) | 2003-10-22 |
| CN1208354C true CN1208354C (en) | 2005-06-29 |
Family
ID=28680535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02111302 Expired - Lifetime CN1208354C (en) | 2002-04-10 | 2002-04-10 | Metallocene titanium compound and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1208354C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436485C (en) * | 2006-12-29 | 2008-11-26 | 浙江大学 | Method for catalyzing water phase polymerization by metallocene catalyst |
| CN103421131B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | High activity double center indene metallocene titanium composition |
| CN103421130B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | High activity double center metallocene titanium composition |
-
2002
- 2002-04-10 CN CN 02111302 patent/CN1208354C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1450089A (en) | 2003-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4157033B2 (en) | Novel multinuclear semimetallocene catalyst and method for producing styrenic polymer using the same | |
| CN1208354C (en) | Metallocene titanium compound and use thereof | |
| CN1130394C (en) | Catalyst for preparation of syndiotactic polystyrene | |
| CN1233667C (en) | Metallocene titanium compound and use thereof | |
| CN1176928C (en) | Metallocene-titanium metal compound and uses thereof | |
| CN1176926C (en) | Cyclopentadienyl titanium compound | |
| CN1176927C (en) | Metallocene titanium compound | |
| CN1241959C (en) | Catalyst for preparing syndiotactic polysterol | |
| CN1259327C (en) | Cyclopentadienyl metal titanium compound and its use | |
| CN1098271C (en) | Cyclopentadiene titanium compound | |
| CN1207315C (en) | Catalyst for preparing syndiotacti polystyrene | |
| CN1252101C (en) | Catalyst for preparing syndiotactic polystyrene | |
| CN1065872C (en) | Cyclopentadiene titanium compound | |
| CN1065870C (en) | Metallocene compound | |
| CN1093140C (en) | Catalyst for preparing syndiotactic poly styrene | |
| CN1116310C (en) | Metallocene titanium compound and its preparing process | |
| CN1076733C (en) | Catalyst for preparing syndiotactic polystyrene | |
| CN1076732C (en) | Carried catalyst for homogeneous syndiotactic polymerization of styrene | |
| CN1116320C (en) | Catalyst for syndiotatic phenylethylene polymerization | |
| CN1086190C (en) | Cyclopentadienyl titanium compound for syndiotactic polymerization of phenylethylene | |
| CN1117106C (en) | Syndiotactic poly styrene polymer | |
| CN1209389C (en) | Syndiotactic polystyrene sythesizing 2-hydroxy benzophenone titanium catalyst and its preparing method | |
| CN1211404C (en) | Cyclopentadienyl titanium compound | |
| US6921734B2 (en) | Titanocene complexes and its catalyst for preparing syndiotactic polystyrene | |
| CN1467232A (en) | Catalyst for preparing syndiotactic polystyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050629 |
|
| CX01 | Expiry of patent term |