CN1065872C - Cyclopentadiene titanium compound - Google Patents
Cyclopentadiene titanium compound Download PDFInfo
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- CN1065872C CN1065872C CN98110853A CN98110853A CN1065872C CN 1065872 C CN1065872 C CN 1065872C CN 98110853 A CN98110853 A CN 98110853A CN 98110853 A CN98110853 A CN 98110853A CN 1065872 C CN1065872 C CN 1065872C
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- CN
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- Prior art keywords
- titanium compound
- cyclopentadiene titanium
- cyclopentadienyl
- cyclopentadiene
- compound according
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- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 title claims description 19
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- -1 arene radical Chemical group 0.000 abstract 2
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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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, R2 is an arene radical containing 6 to 12 carbon atoms, and R3 is alkyl or arene radical containing 1 to 12 carbon atoms. A catalytic system composed of the compound and alkylaluminoxane and/or alkylaluminium can be used for preparing polystyrene with high syndiotacticity; the catalytic system has the characteristics of high catalytic efficiency, high stability, etc. and can be used for industrial production.
Description
The present invention relates to cyclopentadiene titanium compound, particularly about polyvalent alcohol (phenol) 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, and Cp* is a substituted cyclopentadienyl, but its catalytic activity and catalytic efficiency are not high, poor stability, and 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.
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 to overcome in the past, a kind of novel cyclopentadiene titanium compound is 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 have certain industrial application value.
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
1Be cyclopentadienyl;
R
2For containing the aromatic hydrocarbon group of 6～12 carbon atoms;
R
3Be alkane group or the aromatic hydrocarbon group that contains 1～12 carbon atom.
R in the technique scheme
2Preferable range be phenyl: R
3Preferable range be methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl or phenyl, can the neighbour of phenyl ring, or contraposition, preferred range is a methyl; Ti and R
2Between, R
2With R
3Between all link to each other by Sauerstoffatom.
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 6.26 * 10 to compound of the present invention with alkylaluminoxane and/or aluminum alkyls
4G polymkeric substance/g titanium has been obtained good effect.
Work as R
1Be cyclopentadienyl, R
2Be phenyl, 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 DSC spectrogram of cyclopentadiene titanium compound (1).
Its data are as follows respectively:
Ultimate analysis (element analysis)
C
26H
26O
6Ti：
Calcd．For
C 64．76％
H 5．40％
Found
C 64．56％
H 5．48％
Dsc analysis
Tm=127．8℃
Mass spectrum [MS (m/e, %intensity)]
483(21．06，M+1)
482(59．56，M)
417(11．71，M-Cp
+)
359[(100，M-(OC
6H
4OCH
3)
+]
236[27．09，M-(OC
6H
4OCH
3)
2 +]
123(15．92，CH
3OC
6H
4O
+)
113(2．84，CpTi
+)
64(5．4，TiO
+)
65(3．52，C
5H
5 +)
Hydrogen nuclear magnetic resonance spectrum [
1HNMR CDCl
3TMS intern]
δ6．75-6．95[m，12H，-(OPhHO)
3-]
δ6．35-6．45[s，5H，CpH]
δ3．70-3．90[d，9H，-(OCH
3)
3-]
The invention will be further elaborated below by embodiment.
[embodiment 1]
Preparation of Catalyst
In the there-necked flask of exsiccant 250ml, N
2Pump drainage 3 times adds single luxuriant titanium of 2.54 gram trichlorines and 70ml benzene, from top Dropwise 5 0ml benzene, 4.31 the mixture of gram p methoxy phenol and 8.2ml 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, reacting by heating is 2 hours once more, filters, filtrate is drained, and uses toluene, hexane solution recrystallization repeatedly, drains, get yellow crystals 4.9 grams, productive rate 90%.
[embodiment 2]
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, the 10mmol triisobutyl aluminium, and 10mmol MAO stirred after 10 minutes, contained 0.05ml CpTi (O-C with what syringe injection embodiment 1 made
6H
4-OCH
3)
3Toluene solution, stirring reaction with ethanol-hydrochloric acid soln stopped reaction, washed after 1 hour under 400rpm, and is dry that powder solid 150 restrains a normality 96%, M
w=7.18 * 10
4, its catalytic efficiency is 62.63 kg of polymer/gram titanium, catalytic activity is 62.63 kg of polymer/gram titanium hour.
Claims (5)
1, a kind of cyclopentadiene titanium compound, its structure has following general formula: R
1Ti (OR
2OR
3)
3
R in the formula
1Be cyclopentadienyl;
R
2For containing the aromatic hydrocarbon group of 6～12 carbon atoms;
R
3Be alkane group or the aromatic hydrocarbon group that contains 1～12 carbon atom.
2, cyclopentadiene titanium compound according to claim 1 is characterized in that Ti and R
2Between, R
2With R
3Between all link to each other by Sauerstoffatom.
3, cyclopentadiene titanium compound according to claim 1 is characterized in that R
2Be phenyl.
4, cyclopentadiene titanium compound according to claim 1 is characterized in that R
3Be methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl or phenyl, can the neighbour of phenyl ring, or contraposition.
5, cyclopentadiene titanium compound according to claim 4 is characterized in that R
3Be methyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110853A CN1065872C (en) | 1998-05-20 | 1998-05-20 | Cyclopentadiene titanium compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110853A CN1065872C (en) | 1998-05-20 | 1998-05-20 | Cyclopentadiene titanium compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235977A CN1235977A (en) | 1999-11-24 |
| CN1065872C true CN1065872C (en) | 2001-05-16 |
Family
ID=5220869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110853A Expired - Fee Related CN1065872C (en) | 1998-05-20 | 1998-05-20 | Cyclopentadiene titanium compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1065872C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539878A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing syndiotactic polystyrene polymer with doublet broad molecular weight distribution |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994004142A1 (en) * | 1992-08-19 | 1994-03-03 | Ehud Keinan | Novel metallocenes as anti-tumor drugs |
-
1998
- 1998-05-20 CN CN98110853A patent/CN1065872C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994004142A1 (en) * | 1992-08-19 | 1994-03-03 | Ehud Keinan | Novel metallocenes as anti-tumor drugs |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1235977A (en) | 1999-11-24 |
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