CN1086190C - Cyclopentadienyl titanium compound for syndiotactic polymerization of phenylethylene - Google Patents
Cyclopentadienyl titanium compound for syndiotactic polymerization of phenylethylene Download PDFInfo
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- CN1086190C CN1086190C CN98122011A CN98122011A CN1086190C CN 1086190 C CN1086190 C CN 1086190C CN 98122011 A CN98122011 A CN 98122011A CN 98122011 A CN98122011 A CN 98122011A CN 1086190 C CN1086190 C CN 1086190C
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- phenylethylene
- cyclopentadienyl
- titanium compound
- syndiotactic polymerization
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- 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
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a cyclopentadienyl titanium compound with a novel structure, which has the general formula of R1Ti(OR2OR3)3, wherein R1 is cyclopentadienyl or substituted cyclopentadienyl, R2 is a benzyl radical, R3 is alkane or arene radical containing 1 to 6 carbon atoms. A catalytic system composed of the compound and alkylaluminoxane can be used for preparing polystyrene with high syndiotacticity; the catalytic system not only has good catalytic efficiency, but also has high stability, and thus, the catalytic system can be used for industrial production.
Description
The present invention relates to be used for the cyclopentadiene titanium compound of syndiotactic polymerization of phenylethylene.
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%.This polymkeric substance has fusing point up to 270 ℃, and crystallization velocity is fast, and chemically-resistant, resistance toheat are good, narrow molecular weight distribution, and the advantage that dimensional stability is good, and have excellent electric performance, 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
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 the pentamethyl-cyclopentadienyl), but its catalytic activity and catalytic efficiency are not high, poor stability, industrial application value is little.Patent CN97106586.1 has reported Compound C p (Cp
*) Ti (OCH
2-C
6H
5)
3Though catalytic activity had had raising, less stable more in the past.
The objective of the invention is when overcoming in the past that compound is used for the syndiotactic polymerization of phenylethylene reaction in the document, high and the good stability of catalytic efficiency can not simultaneous shortcoming, a kind of novel cyclopentadiene titanium compound that is used for syndiotactic polymerization of phenylethylene is provided, it is good stability not only, and when being used for syndiotactic polymerization of phenylethylene, the catalytic efficiency height.
The objective of the invention is to realize by following technical scheme: a kind of cyclopentadiene titanium compound that is used for syndiotactic polymerization of phenylethylene, its structure has following general formula: R
1Ti (OR
2OR
3)
3
R in the formula
1Be cyclopentadienyl or substituted cyclopentadienyl;
R
2Be benzyl;
R
3Be alkane group or the aromatic hydrocarbon group that contains 1～6 carbon atom.
R in the technique scheme
1Preferable range be the pentamethyl-cyclopentadienyl, R
3Preferable range be methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl or phenyl, R
3Preferred range be methyl.Ti and R in the cyclopentadiene titanium compound
2Between, R
2With R
3Between all have Sauerstoffatom to link to each other, preferable compound structure is R
2Be benzyl, R
3Be methyl.
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 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, 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 1.2 * 10 to compound of the present invention with alkylaluminoxane
5G polymkeric substance/g titanium, and after placing six months, the catalytic efficiency of catalyzer does not still descend, and has obtained effect preferably.
Work as R
1Be cyclopentadienyl, R
2Be benzyl, R
3Structural formula of compound is during for methyl:
Fig. 1 is the mass spectrum of cyclopentadiene titanium compound (1).
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of cyclopentadiene titanium compound (1).
Fig. 3 is the infrared spectrum of cyclopentadiene titanium compound (1).
Fig. 4 is the nuclear magnetic resonance of carbon spectrogram of cyclopentadiene titanium compound (1).
Its data are respectively as follows:
Elementary analysis-(element analysis)
C
29H
32O
6Ti：
Calcd.For C 66.41％
H 6.11％
Found C 65.77％
H 6.11％
Mass spectrum [MS (m/e, %intensity)]
523(1.26，M-1
+)
459(1.57，M-Cp
+)
386[5.86，M-(OCH
2C
6H
4OCH
3)
+]
137(2.09，OCH
2C
6H
4OCH
3 +)
121(100，
+CH
2C
6H
4OCH
3)
91(5.02，C
6H
5CH
2 +)
77(9.68，C
6H
5 +)
65(3.30，C
5H
5 +)
64(1.91，Ti-O
+)
The proton nuclear magnetic resonance spectrum [
1HNMR CDCl
3TMS intern]
δ3.76(d，9H，-OCH
3)
δ6.74-7.2(m，12H，-C
6H
4-)
δ6.25(d，5H，CpH)
δ5.30[d，6H，-OCH
2-)
Carbon nuclear nmr spectrum [
13CNMR CDCl
3]
113.7 (Cp-C)
127.8 (ph，C-2，6)
128.5 (ph，C-3，5)
134.5 (ph，C-4)
158.5 (ph，C-1)
78.1 (-CH
2-O-，C)
55.2 (-OCH
3，C)
Infrared spectra (Infrand FTIR)
The wave number vibration
3104 luxuriant ring C-H stretching vibrations
3032 phenyl ring C-H stretching vibrations
3000～2836-OCH
2-middle C-H asymmetrical stretching vibration
The frequency multiplication district of c h bond out-of-plane deformation vibration on 1613,1885 phenyl ring
1462 luxuriant ring skeletal vibrations
1248 ph-O-CH
3The asymmetric stretching vibration of middle C-O-C
The plain bending of C-H vibration on the 931 luxuriant rings
C-H out-of-plane deformation vibration on 813 phenyl ring
Stretching vibration (the V of 547 Ti-C keys
Ti-C)
The invention will be further elaborated below by embodiment, below among the embodiment Cp be cyclopentadienyl, Cp
*Be the pentamethyl-cyclopentadienyl.[embodiment 1]
In the there-necked flask of exsiccant 250ml, N
2Pump drainage 3 times adds single luxuriant titanium of 3.94 gram trichlorines and 120ml benzene, from top dropping 60ml benzene, 7.45 the mixture of gram p-methoxybenzyl alcohol and 7.8ml triethylamine 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 is filtered, and filtrate is drained, extract repeatedly with toluene, hexane solution, drain, get faint yellow product 6.6 grams, productive rate 70%.[embodiment 2]
In the there-necked flask of exsiccant 250ml, N
2Pump drainage 3 times, add 4.0 single luxuriant titanium of gram pentamethyl-trichlorines and 150ml benzene, above Dropwise 5 0ml benzene, the mixture of 5.73 gram p-methoxybenzyl alcohols and 6.3ml triethylamine, dripped off in 45 minutes, after the normal-temperature reaction 2 hours, be heated to 80 ℃ of reactions 10 hours, filter, filtrate is drained, extract repeatedly with toluene, hexane, get orange product 5.6 grams, productive rate 68%.[embodiment 3]
On the 2L mechanical stirring kettle, after 3 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times with dry 10 minutes of rare triisobutylaluminum toluene solution washing, adds styrene monomer 500ml again, 5mmol triisobutyl aluminium (TiBA), and 5mml MAO stirred after 10 minutes, injected with syringe to contain 0.025mmol CpTi (OCH
2-C
6H
4-OCH
3)
3(compound of embodiment 1) toluene solution, stirring reaction stopped with ethanol-hydrochloric acid after 2 hours under 400rpm, and washing is dry that powder solid 143 restrains 262.5 ℃ of fusing points, Mw=6.13 * 10
4, catalytic activity 5.98 * 10
4GPs/gTi.[embodiment 4]
On the 2L mechanical stirring kettle, after 3 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier
2Pump drainage 3 times with dry 10 minutes of rare triisobutylaluminum toluene solution washing, adds styrene monomer 500ml again, 10mmol triisobutyl aluminium (TiBA), and 10mmol MAO stirred after 10 minutes, injected 0.025mmol Cp with syringe
*Ti (OCH
2-C
6H
4-OCH
3)
3(compound of embodiment 2) toluene solution, stirring reaction with ethanol-hydrochloric acid soln termination reaction, washed after 1 hour under 400rpm, and is dry that powder solid 148 restrains 268.5 ℃ of fusing points, molecular weight Mw=8.23 * 10
5, catalytic activity 1.23 * 10
5GPs/gTi.[embodiment 5]
The 0.01MCp that newly prepares
*Ti (O-C
6H
5)
3Solution, Cp
*Be the pentamethyl-cyclopentadienyl, press embodiment 4 conditions, carry out syndiotactic polymerization of phenylethylene, get powder solid 136g, catalytic efficiency is 1.13 * 10
5GPs/gTi.[embodiment 6]
The 0.01MCp of new configuration
*Ti (OCH
2-C
6H
5)
3Catalyst solution (Cp
*Be the pentamethyl-cyclopentadienyl), carry out syndiotactic polymerization of phenylethylene by embodiment 4 conditions, get powder solid 140g, catalytic efficiency is 1.16 * 10
5GPs/gTi.[embodiment 7]
The 0.01MCp for preparing
*Ti (OCH
2-C
6H
4-OCH
3)
3Solution normal temperature was placed 6 months, pressed embodiment 4 conditions, carried out syndiotactic polymerization of phenylethylene, got powder solid 146g, and catalytic efficiency is 1.22 * 10
5GPs/gTi.[comparative example 1]
Normal temperature is placed 6 months 0.01MCp
*Ti (O-C
6H
5)
3Catalyst solution carries out syndiotactic polymerization of phenylethylene by polymerization embodiment 3 conditions, gets powder solid 46g, and catalytic efficiency is 3.84 * 10
4GPs/gTi.[comparative example 2]
Normal temperature is placed 6 months 0.01MCp
*Ti (OCH
2-C
6H
5)
3Catalyst solution (Cp
*Be the pentamethyl-cyclopentadienyl), carry out syndiotactic polymerization of phenylethylene by embodiment 6 conditions, get powder solid 92g, catalytic efficiency is 7.69 * 10
4GPs/gTi.
Claims (4)
1, a kind of cyclopentadiene titanium compound that is used for syndiotactic polymerization of phenylethylene, its structure has following general formula: R
1Ti (OR
2OR
3)
3
R in the formula
1Be cyclopentadienyl or substituted cyclopentadienyl;
R
2Be benzyl;
R
3Be alkane group or the aromatic hydrocarbon group that contains 1～6 carbon atom.
2, the cyclopentadiene titanium compound that is used for syndiotactic polymerization of phenylethylene according to claim 1 is characterized in that R
1Be the pentamethyl-cyclopentadienyl.
3, the cyclopentadiene titanium compound that is used for syndiotactic polymerization of phenylethylene according to claim 1 is characterized in that R
3Be methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl or phenyl.
4, the cyclopentadiene titanium compound that is used for syndiotactic polymerization of phenylethylene according to claim 3 is characterized in that R
3Be methyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122011A CN1086190C (en) | 1998-11-18 | 1998-11-18 | Cyclopentadienyl titanium compound for syndiotactic polymerization of phenylethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122011A CN1086190C (en) | 1998-11-18 | 1998-11-18 | Cyclopentadienyl titanium compound for syndiotactic polymerization of phenylethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1253957A CN1253957A (en) | 2000-05-24 |
| CN1086190C true CN1086190C (en) | 2002-06-12 |
Family
ID=5227498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98122011A Expired - Lifetime CN1086190C (en) | 1998-11-18 | 1998-11-18 | Cyclopentadienyl titanium compound for syndiotactic polymerization of phenylethylene |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988010275A1 (en) * | 1987-06-17 | 1988-12-29 | The Dow Chemical Company | Catalyst and process for preparation of syndiotactic polystyrene |
| JPH02102206A (en) * | 1988-10-11 | 1990-04-13 | Asahi Chem Ind Co Ltd | Manufacture of stereoregular polystyrene |
-
1998
- 1998-11-18 CN CN98122011A patent/CN1086190C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988010275A1 (en) * | 1987-06-17 | 1988-12-29 | The Dow Chemical Company | Catalyst and process for preparation of syndiotactic polystyrene |
| JPH02102206A (en) * | 1988-10-11 | 1990-04-13 | Asahi Chem Ind Co Ltd | Manufacture of stereoregular polystyrene |
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| Publication number | Publication date |
|---|---|
| CN1253957A (en) | 2000-05-24 |
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