CN1052486C - Titanium metallocene compounds - Google Patents
Titanium metallocene compounds Download PDFInfo
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- CN1052486C CN1052486C CN97106586A CN97106586A CN1052486C CN 1052486 C CN1052486 C CN 1052486C CN 97106586 A CN97106586 A CN 97106586A CN 97106586 A CN97106586 A CN 97106586A CN 1052486 C CN1052486 C CN 1052486C
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- CN
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- Prior art keywords
- cyclopentadienyl
- compound
- titanium
- metallocene
- phenyl
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- 239000010936 titanium Substances 0.000 title claims description 15
- 229910052719 titanium Inorganic materials 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 title abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000003609 titanium compounds Chemical class 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 5
- 229960004217 benzyl alcohol Drugs 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum 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
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
The present invention relates to a metallocene titanium compound with a novel structure, which has the general formula of R1Ti(OCH2R2)3, wherein R1 is cyclopentadienyl or substituted cyclopentadienyl; R2 is an aromatic hydrocarbon group containing 6 to 20 carbon atoms. A catalyst comprising the compound and alkylaluminoxane can be used for preparing a polystyrene polymer with high syndiotacticity, and has the characteristics of high catalytic activity and high catalytic efficiency; thus, the catalyst can be used for industrial production.
Description
The present invention relates to metallocene-titanium metal compound.
The homogeneous catalysis system that cyclopentadiene titanium compound and promotor methylaluminoxane (MAO) or boron fluorine cpd are formed is used for styrene polymerization and can obtains a normality at the syndiotactic polymer more than 95%.Melting point polymer height (reaching about 270 ℃), narrow molecular weight distribution, thermotolerance, chemical resistant properties and electrical property are good, and over-all properties can be compared with engineering plastics.The appearance of syndiotactic polystyrene has caused the concern of people to its catalyst system, particularly cyclopentadiene titanium compound, and has carried out extensive studies.It is CpTiCl that document EP 210615 and US5252693 etc. have reported structure
3The catalyst system of forming with promotor MAO is used for the situation of syndiotactic polymerization of phenylethylene, but its catalytic activity and catalytic efficiency are not high, and industrial application is undesirable.
The objective of the invention is for overcoming the shortcoming that above-mentioned document exists, a kind of metallocene-titanium metal compound of novel texture is provided, the catalyst system that this metallocene-titanium metal compound and alkylaluminoxane are formed can be successfully used to Syndiospecific Polymerization of Styrene, and have advantages of high catalytic activity and catalytic efficiency.
The objective of the invention is to realize by following technical scheme: a kind of metallocene-titanium metal compound, its structure has following general formula:
R
1Ti(OCH
2R
2)
3
R in the formula
1Be cyclopentadienyl, substituted cyclopentadienyl;
R
2For containing the aromatic hydrocarbon group of 6～20 carbon atoms.
R in the technique scheme
1Preferable range be cyclopentadienyl, pentamethyl-cyclopentadienyl; R
2Preferable range be phenyl.
The preparation technology of metallocene titanium compound of the present invention is by corresponding cyclopentadienyl titanous chloride and phenylcarbinol (HO-CH
2 In the presence of chlorine hydride absorbent, be that solvent reaction makes with the hydrocarbon polymer.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 hydrocarbon better, for example benzene, toluene etc.Concrete steps are: ethamine and phenylcarbinol mixing solutions are slowly dropped in the benzole soln of cyclopentadienyl titanous chloride, the mole ratio of cyclopentadienyl titanous chloride and phenylcarbinol is 1: 3.0～3.5, the mole ratio of cyclopentadienyl titanous chloride and ethamine is that 1: 3.0～3.5 temperature of reaction are 0～60 ℃, reaction times is 1～30 hour, solids removed by filtration, underpressure distillation removes and desolvates the crude product hexane extraction that obtains, after removing volatile matter, get orange-red mucus.
Compound of the present invention during as the Syndiospecific Polymerization of Styrene catalyzer, can obtain higher catalytic efficiency with alkylaluminoxane, and its catalytic efficiency is higher reaches 31.5 kg of polymer/gram titanium, has obtained effect preferably.This compound also can be used as alpha-olefin and cinnamic copolymerization simultaneously.
Fig. 1 is R
1Be cyclopentadienyl, R
2The mass spectrum of compound during for phenyl.
Fig. 2 is R
1Be cyclopentadienyl, R
2The infrared spectrogram of compound during for phenyl.
Fig. 3 is R
1Be cyclopentadienyl, R
2The nuclear magnetic resonance of carbon figure of compound during for phenyl.
Fig. 4 is R
1Be cyclopentadienyl, R
2The hydrogen nuclear magnetic resonance figure of compound during for phenyl.
Work as R1Be cyclopentadienyl group, R2The general structure of compound is during for phenyl:Its data are respectively as follows:
Elementary analysis (element analyses)
Calcd for C
26H
26O
6Ti：C：71.90；H：6.03.Found：C：71.55；H：5.88
Hydrogen nuclear magnetic resonance spectrum [1H NMR(CDCl
2 TMS intern)]：
δ5.26(s，6H，(OCH
2)
3)，7.26(s，15H，Ph
3)，6.15(s，5H，Cp H).
Carbon13Nuclear magnetic resoance spectrum [13C NMR(CDCCl
3)]：
δ64.8(-OCH
2-)，142.0(Ph C-1)，128.1(Ph C-2，6)，127.5(Ph C-3，5)，
126.5(Ph C-4)，113.8-113.9(Cp C).
Mass spectrum [MS (m/z, % intensity)]:
39(40，CH
2CCH
+)，64(15，TiO
+)，65(42，C
5H
5 +)，77(20，C
6H
5)，
79(20，TiOCH
2 +)，91(100，CH
2Ph
+)，107(10，OCH
2Ph
+)，129(10，CpTiO
+)
169(10，M-Cp-(OCH
2Ph)
2-(CH
2Ph)
+)，220(5，M-(OCH
2Ph)
+ 2)，369(10，M-Cp′).
Infrared spectra (Infrared FTIR)
The wave number vibration
The luxuriant ring of 3057-3029 C-H stretching vibration, phenyl ring=C-H stretching vibration
2839 hydrocarbon key asymmetrical stretching vibration [VasC-11 (O-CH
2-C)]
1602-1496 phenyl ring skeletal vibration
Near the general frequency absorption band of luxuriant ring 1700
1096-1068 carbon-oxygen bond stretching vibration [V
C-0 (Ti)]
The plain bending of C-H vibration on the 1025 luxuriant rings
The eigen vibration of five adjacent hydrogen on 735 phenyl ring
561 titanium carbon bond stretching vibration (V
Ti-c)
463 titanyl key stretching vibration (V
Ti-o)
Below just the invention will be further elaborated [embodiment 1] by embodiment
The preparation of cyclopentadiene titanium compound
With 2.12g (9.66mmol) the cyclopentadienyl titanous chloride exsiccant of packing into; be subjected in the 250ml reaction flask of nitrogen protection; add 50ml exsiccant benzene; under nitrogen protection, drip 40ml lentamente again and contain 2.95g (29.0mmol with dropping funnel; 4.07ml) triethylamine and 3.13g (29.0mmol; 2.95ml) the exsiccant benzole soln of phenylcarbinol; be allowed to condition under 20 ℃ the temperature and react 24h; filter; drain solvent, use the n-hexane extraction of 50 ℃ of exsiccant again, constant temperature leaves standstill 2h; supernatant liquid is transferred in the container of dried and clean inflated with nitrogen; drain solvent, get orange red oily product 4.10g, yield 90%.The toluene solution that is made into 0.01M is standby.[embodiment 2]
The preparation of MAO
Be equipped with and add 33.6 Als of gram in the 500ml reactor of induction stirring through milling
2(SO
4)
318H
2O and 70ml toluene, under-10 ℃ of temperature, dripping 200ml concentration is the trimethyl aluminium toluene solution of 3.1M.Rate of addition is 5 ml/min, drips off in 60 minutes.Improve temperature of reaction then gradually, in 2h, make temperature reach 60 ℃, continue reaction 24h.Reaction mixture is removed solid after filtration, filtrate is taken out 1h with vacuum pump under 50 ℃, remove part toluene, under 30 ℃, take out 1h again, under 40 ℃, volatile matters such as toluene are removed at last, obtained 13.4g white solid MAO, productive rate about 33.5%, after measured, the average oligomerisation degree of methylaluminoxane (MAO) is 13.[embodiment 3]
Through vacuumize and the 250ml reaction flask of inflated with nitrogen in, add 10ml toluene successively, 10ml vinylbenzene, the cyclopentadiene titanium compound 0.2ml of embodiment 1 preparation, the MAO 0.21g of embodiment 2 preparations is at 65 ℃ of polymerization 2h, obtain the 6.3g polymkeric substance, catalytic efficiency is 31.5 kg of polymer/gram titanium, and normality is 97% between product, and fusing point is 259.0 ℃.[embodiment 4]
The preparation of cyclopentadiene titanium compound
With 2.08g (9.48mmol) the cyclopentadienyl titanous chloride exsiccant of packing into; be subjected in the 250ml reaction flask of nitrogen protection; add 50ml exsiccant benzene; under nitrogen protection, drip 40ml lentamente again and contain 2.88g (28.4mmol.3.9ml) triethylamine and 3.07g (28.4mmol with dropping funnel; 2.9ml) the exsiccant benzole soln of phenylcarbinol; be allowed to condition under 20 ℃ the temperature and react 24h; filter; drain solvent; use the n-hexane extraction of 45 ℃ of exsiccant again; constant temperature leaves standstill 2h, supernatant liquid is transferred in the container of dried and clean inflated with nitrogen, drains solvent; get orange red oily product 3.50g, yield 85%.The toluene solution that is made into 0.02M is standby.[embodiment 5]
Through vacuumize and the 250ml reaction flask of inflated with nitrogen in, add 10ml toluene successively, the cyclopentadiene titanium compound 0.11ml of embodiment 4 preparations, the MAO 0.22g of embodiment 2 preparations, vinylbenzene 10ml is at 65 ℃ of polymerization 2h, obtain the 6.7g polymkeric substance, catalytic efficiency is 30.5 kg of polymer/gram titanium, and normality is 96% between product, and fusing point is 258.7 ℃.
Claims (2)
1, a kind of metallocene-titanium metal compound, its structure has following general formula:
R
1Ti(OCH
2R
2)
3
R in the formula
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl:
R
2For containing the aromatic hydrocarbon group of 6～20 carbon atoms.
2, metallocene-titanium metal compound according to claim 1 is characterized in that R
2Be phenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106586A CN1052486C (en) | 1997-09-03 | 1997-09-03 | Titanium metallocene compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106586A CN1052486C (en) | 1997-09-03 | 1997-09-03 | Titanium metallocene compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1210108A CN1210108A (en) | 1999-03-10 |
| CN1052486C true CN1052486C (en) | 2000-05-17 |
Family
ID=5168812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106586A Expired - Fee Related CN1052486C (en) | 1997-09-03 | 1997-09-03 | Titanium metallocene compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1052486C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0601953A1 (en) * | 1992-11-03 | 1994-06-15 | Repsol Quimica S.A. | Process of hydrogenation in solution of the double bonds of polymers of conjugated dienes, and hydrogenated block copolymer produced |
| EP0753522A1 (en) * | 1995-07-12 | 1997-01-15 | Witco GmbH | Process for the preparation of cyclopentadienyl-titanium-trialkoxy derivatives |
-
1997
- 1997-09-03 CN CN97106586A patent/CN1052486C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0601953A1 (en) * | 1992-11-03 | 1994-06-15 | Repsol Quimica S.A. | Process of hydrogenation in solution of the double bonds of polymers of conjugated dienes, and hydrogenated block copolymer produced |
| EP0753522A1 (en) * | 1995-07-12 | 1997-01-15 | Witco GmbH | Process for the preparation of cyclopentadienyl-titanium-trialkoxy derivatives |
| US5625086A (en) * | 1995-07-12 | 1997-04-29 | Witco Gmbh | Process for the preparation of cyclopentadienyltrialkoxytitanium derivatives |
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| Publication number | Publication date |
|---|---|
| CN1210108A (en) | 1999-03-10 |
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