CN1285355A - Cyclopentadiene titanium compound - Google Patents
Cyclopentadiene titanium compound Download PDFInfo
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- CN1285355A CN1285355A CN 99113996 CN99113996A CN1285355A CN 1285355 A CN1285355 A CN 1285355A CN 99113996 CN99113996 CN 99113996 CN 99113996 A CN99113996 A CN 99113996A CN 1285355 A CN1285355 A CN 1285355A
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- titanium compound
- cyclopentadiene titanium
- cyclopentadienyl
- och
- cyclopentadiene
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Abstract
The present invention relates to a cyclopentadienyl titanium compound, its general formula is R.Ti(OR2OR3)3, where R, is cyclopentadiene group containing 0-5 methyls, R2 is paraffin group containing 2-4 carbon atoms and R3 is alkyl containing 1-4 carbon atoms. The catalytic system formed from said invented compound and alkylaluminoxane and/or alkylaluminium can be used for preparing high syndiotactic polystyrene, and features high catalytic efficiency, can be used in industrial production.
Description
The present invention relates to cyclopentadiene titanium compound, particularly about glycol ether type cyclopentadiene titanium compound.
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, good heat resistance, and 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 cyclopentadiene titanium compound.Document US 5252693 and EP210615 have reported that structure is CpTiCl
3Or 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 substituted 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), activity had had raising more in the past, but the industrial production using value is still little.
To the objective of the invention is that there is the defective that the catalyst system catalytic activity is low, catalytic efficiency is low in document in order overcoming in the past, a kind of novel cyclopentadiene titanium compound to be provided.The catalyst system that this cyclopentadiene titanium compound and alkylaluminoxane and/or aluminum alkyls are formed can be successfully used to Syndiospecific Polymerization of Styrene, and have following characteristics: high catalytic activity and catalytic efficiency.
The objective of the invention is to realize by following technical scheme: a kind of cyclopentadiene titanium compound, its structure has following general formula:
R
1Ti(OR
2OR
3)
3
R in the formula
1For containing the cyclopentadienyl of 0～5 methyl;
R
2For containing the alkane group of 2～4 carbon atoms;
R
3For containing the alkane group of 1～4 carbon atom;
Wherein Ti and R
2Between, R
2With R
3Between all have Sauerstoffatom to link to each other.
R in the technique scheme
2Preferable range be ethyl; R
3Preferable range be methyl; R
1Preferable range be cyclopentadienyl or pentamethyl-cyclopentadienyl.
The preparation method of cyclopentadiene titanium compound of the present invention is that solvent reaction obtain with the hydrocarbon polymer by corresponding cyclopentadienyl titanous chloride and glycol ether in the presence of chlorine hydride absorbent.Chlorine hydride absorbent can be various aminated compoundss, wherein is advisable with trialkylamine, for example triethylamine.Hydrocarbon polymer can be aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbons better, for example benzene,toluene,xylene etc.The mole ratio of cyclopentadienyl titanous chloride and glycol ether 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, preferably 6～24 hours, reaction process was preferably used intermittently heating operation.
During as the Syndiospecific Polymerization of Styrene catalyzer, its catalytic efficiency can reach 9.04 * 10 to compound of the present invention with alkylaluminoxane and/or aluminum alkyls
4Gram polymkeric substance/gram titanium has been obtained good effect.
The invention will be further elaborated below by embodiment.[embodiment 1]
The preparation of cyclopentadiene titanium compound (I)
In the there-necked flask of 250 milliliters of exsiccant, N
2Pump drainage 3 times adds the 3.47 single luxuriant titanium of gram trichlorine and 70 milliliters of benzene, and from 0 milliliter of benzene of top Dropwise 5, the mixture of 3.8 milliliters of ethylene glycol monomethyl ethers and 6.6 milliliters of triethylamines dripped off after 45 minutes, was heated to the benzene reflux temperature, reacted after 6 hours, stopped heating.Be chilled to room temperature, filter, filtrate is drained, and extracts repeatedly with toluene, hexane solution, drains, and gets yellow liquid 4.4 grams, productive rate 82%.The data of its infrared spectrum and hydrogen nuclear magnetic resonance spectrogram are as follows after measured:
Work as R
1Be cyclopentadienyl, R
2Be ethyl, R
3Structural formula of compound is during for methyl:
Ultimate analysis (element analysis)
C
14H
26O
6Ti：
Calcd．For
C?49.70％
H?7.69％
Found
C?49.46％
H?7.66％
Proton nmr spectrum (HNMR CDCl
3TMS intern)
δ?6.25-6.50(s，5H，CpH)
δ?4.25-4.50(m，6H，-Ti-(O-CH
2-)
3)
δ?3.25-3.50(m，15H，-(CH
2-O-CH
3)
3-)
Mass spectrum [MS (m/z, %intensity)]
273(100，M-Cp
+)
263(55，M-OCH
2CH
2OCH
3 +)
59(39，-OCH
2CH
2O
+-)
198(7，M-Cp-OC
2H
4OCH
3 +)
188[10，M-2(OCH
2CH
2OCH
3 +)]
113(6，CpTi
+)
65 (5, Cp
+) [embodiment 2]
The preparation of cyclopentadiene titanium compound (II)
In the there-necked flask of 250 milliliters of exsiccant, N
2Pump drainage 3 times adds the 2.31 single luxuriant titanium of gram pentamethyl-trichlorine and 50 milliliters of benzene, from 0 milliliter of benzene of top Dropwise 5,1.89 gram ethylene glycol monomethyl ether and 3.3 milliliters of triethylamines, drip off after 45 minutes, be heated to the reaction of benzene reflux temperature after 6 hours, stop heating, filter, filtrate is drained, and extracts repeatedly with hexane, drains, get yellow liquid 2.5 grams, productive rate 78%.The data of its infrared spectrum and hydrogen nuclear magnetic resonance spectrogram are as follows after measured:
Work as R
1Be pentamethyl-cyclopentadienyl, R
2Be ethyl, R
3Structural formula of compound is during for methyl:
Ultimate analysis (element analysis)
C
19H
36O
6Ti：
Calcd．For
C?55.88％
H?8.82％
Found
C?55.82％
H?8.76％
Proton nmr spectrum (HNMR CDCl
3TMS intern) δ 1.90-2.10 (m, 15H, Cp
*H) δ 4.25-4.50 (m, 6H ,-Ti-(O-CH
2-)
3) δ 3.25-3.50 (m, 15H ,-(CH
2-O-CH
3)
3
Mass spectrum [MS (m/z, %intensity)] 408 (56.7, M
+) 333 (100, M-OCH
2CH
2OCH
3 +) 258 (11, M-2 (OCH
2CH
2OCH
3 +) 135 (6, Cp
*+) [embodiment 3]
Add 10 milliliters of toluene in 100 milliliters of reaction flasks, 10 milliliters of vinylbenzene add the Cp-Ti-(OCH that methylaluminoxane MAO 1.8 mmoles and 3 micromole embodiment 1 prepare
2-CH-OCH
3)
3, stir down polymerizations 1 hour at 60 ℃, be ethanol-HCl solution termination reaction of 10% with weight percent concentration, washing and filtering gets sPS 6.7 and restrains catalytic efficiency 4.65 * 10
4Gram sPS/ gram Ti, a normality 97.3%, 258.3 ℃ of fusing points, molecular weight Mw=5.70 * 10
4, molecular weight distribution 2.35.[embodiment 4]
On 2 liters of mechanical stirring kettles, after 3 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times is used dry 10 minutes of rare triisobutyl aluminium (TiBA) toluene solution washing again, adds 500 milliliters of styrene monomers, 7 mmole TiBA, and 7 mmole MAO stirred after 10 minutes, injected with syringe to contain the Cp that 0.035 mmole embodiment 2 makes
*Ti (OCH
2-CH
2-OCH
3)
3Toluene solution at 400 rotating speeds/minute stirring reaction after 1.5 hours, is that ethanol-hydrochloric acid soln of 10% stops with weight percent concentration, washing, dry powder solid 152 grams, catalytic efficiency 9.04 * 10
4Gram sPS/ gram Ti.Between normality 97%, 269.5 ℃ of fusing points, molecular weight Mw=6.73 * 10
5, molecular weight distribution 2.12.
Claims (4)
1, a kind of cyclopentadiene titanium compound, its structure has following general formula: R
1Ti (OR
2OR
3)
3
R in the formula
1For containing the cyclopentadienyl of 0～5 methyl;
R
2For containing the alkane group of 2～4 carbon atoms;
R
3For containing the alkane group of 1～4 carbon atom;
Wherein Ti and R
2Between, R
2With R
3Between all have Sauerstoffatom to link to each other.
2, cyclopentadiene titanium compound according to claim 1 is characterized in that R
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl.
3, cyclopentadiene titanium compound according to claim 1 is characterized in that R
2Be ethyl.
4, cyclopentadiene titanium compound according to claim 1 is characterized in that R
3Be methyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113996A CN1098271C (en) | 1999-08-19 | 1999-08-19 | Cyclopentadiene titanium compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113996A CN1098271C (en) | 1999-08-19 | 1999-08-19 | Cyclopentadiene titanium compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1285355A true CN1285355A (en) | 2001-02-28 |
| CN1098271C CN1098271C (en) | 2003-01-08 |
Family
ID=5277128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113996A Expired - Lifetime CN1098271C (en) | 1999-08-19 | 1999-08-19 | Cyclopentadiene titanium compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098271C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244137B (en) * | 2008-02-28 | 2011-05-04 | 郑明刚 | Medicament for treating pulmonitis, and high fever, lower fever, and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5583185A (en) * | 1992-11-03 | 1996-12-10 | Repsol Quimica S.A. | Process for hydrogenation in solution of the double bonds of conjugated dienes, and hydrogenated block copolymer produced |
-
1999
- 1999-08-19 CN CN99113996A patent/CN1098271C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244137B (en) * | 2008-02-28 | 2011-05-04 | 郑明刚 | Medicament for treating pulmonitis, and high fever, lower fever, and preparation method |
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| Publication number | Publication date |
|---|---|
| CN1098271C (en) | 2003-01-08 |
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