CN1128820C - Polyolefine catalyst containing pyrrole loop in its ligand and its preparing process and application - Google Patents
Polyolefine catalyst containing pyrrole loop in its ligand and its preparing process and application Download PDFInfo
- Publication number
- CN1128820C CN1128820C CN 00105805 CN00105805A CN1128820C CN 1128820 C CN1128820 C CN 1128820C CN 00105805 CN00105805 CN 00105805 CN 00105805 A CN00105805 A CN 00105805A CN 1128820 C CN1128820 C CN 1128820C
- Authority
- CN
- China
- Prior art keywords
- formula
- hydrogen
- catalyzer
- alkyl
- ligand
- 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 - Fee Related
Links
Abstract
The present invention relates to a polyolefine catalyst. The polyolefine catalyst has a general formula expression of LnMX<4 minus n>. In the expression, M is selected from the transitional metal of an IVB group, X is halogen, L is a ligand, and n is 1 or 2. The ligand L has a general formula expression of a formula (I). In the formula (I), p is an a formula or a b formula, wherein R is selected from hydrogen or an alkyl group of C1 to C18 and an aryl group of C6 to C14; R' is selected from the hydrogen or an alkyl group of C1 to C6; R1 to R3 can be the same or different and are respectively selected from the hydrogen or the alkyl group of C1 to C18 and the aryl group of C6 to C14. The catalyst is matched with cocatalyst alumina alkane to prepare polyolefine comprising polyethylene. The polyolefine catalyst has high catalytic activity.
Description
Technical field
The present invention relates to a kind of polyolefin catalyst and preparation method thereof and application, specifically, is a kind of olefinic polymerization that is used for, and contains the transition metal compound catalizer and preparation method thereof and application of pyrrole ring in the part.
Background technology
After metallocene catalyst successfully was used for polyolefin industry production, a kind of was the transition metal complex of part with the heteroatomic compound, and promptly Nonmetallocene polyolefine catalyst is developed rapidly.On metallocene 99 years can (MetCon ' 99), T.Fujita etc. have reported a kind of new olefine polymerization catalyst series (FI Catalysts) that is better than metallocene catalyst, this catalyst series uses salicylic alidehyde imine as the concentricity atom titanium of part, zirconium or hafnium coordination, catalytic activity to vinyl polymerization is very high, and can be by changing ligand structure and the promotor polymkeric substance of production from the low-molecular weight polymer to the ultra-high molecular weight arbitrarily.
USP5,539,124 disclose a kind of transition metal compound catalizer that contains pyrrole ring, this catalyzer uses pyrroles, indoles, carbazole or their alkyl substituent as part, with central atom titanium or zirconium coordination, under promotor methylaluminoxane (MAO) effect, make alpha-olefin, carry out homopolymerization or copolymerization as ethene.
Summary of the invention
The purpose of this invention is to provide the transition metal compound catalizer that contains pyrrole ring in a kind of part, this catalyzer has higher activity.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
It is Primary Catalysts that a further object of the present invention provides with above-mentioned catalyzer, the method for synthesis of polyolefins.
The present invention is part with the carbonyl derivative of pyroles heterogeneous ring compound with the condensation product that the amino benzenes compounds reaction generates, again with the halogenide of part and IVB group 4 transition metal, as TiCl
4, ZrCl
4Deng the generation catalyzer that reacts.
Specifically, catalyzer provided by the invention has following general expression: L
nMX
4-n, M is the transition metal that is selected from IVB family in the formula, preferred titanium or zirconium; X is a halogen, preferred chlorine; L is a part, and n is 1 or 2, and described ligand L has the general expression of formula (I):
In the formula (I), p is
Or
Wherein R is selected from hydrogen or C
1～C
3Alkyl, R ' is selected from hydrogen or C in the formula (I)
1～C
3Alkyl, R
1～R
3Can be identical or different, independently be selected from hydrogen or C separately
1～C
6Alkyl.
The preferred hydrogen of R in described formula (I) part and R ', R
1～R
3Can be identical or different, preferred hydrogen or C
1～C
3Alkyl, as methyl, ethyl, propyl group or sec.-propyl, comparatively preferred combination is R
1And R
2Be C
1～C
3Alkyl, as methyl, ethyl, propyl group or sec.-propyl, R
3Be hydrogen or C
1～C
3Alkyl.
Catalyzer provided by the invention comparatively preferably has: pyrrole aldehyde contracts 2,6-diisopropyl benzene amido titanous chloride, and pyrrole aldehyde contracts 2,6-diisopropyl benzene amido tri-chlorination zirconium, pyrrole aldehyde contracts 2,6-dimethyl benzene amido titanous chloride, pyrrole aldehyde contracts 2,6-dimethyl benzene amido tri-chlorination zirconium, and pyrrole aldehyde contracts 2,4,6-triisopropyl anilino titanous chloride, pyrrole aldehyde contracts 2,4,6-triisopropyl anilino tri-chlorination zirconium, pyrrole aldehyde contracts 2,4,6-Three methyl Benzene amido titanous chloride, the pyrrole aldehyde 2 base tri-chlorination zirconium that contracts, the 3-indolecarboxaldehyde contracts 2,6-diisopropyl benzene amido titanous chloride, the 3-indolecarboxaldehyde contracts 2,6-diisopropyl benzene amido tri-chlorination zirconium, the 3-indolecarboxaldehyde contracts 2,6-dimethyl benzene amido titanous chloride, the 3-indolecarboxaldehyde contracts 2,6-dimethyl benzene amido tri-chlorination zirconium.
Preparation of catalysts method of the present invention may further comprise the steps:
(1) with the amino benzenes compounds of formula (II) and the carbonyl compound of formula (III)
The amount of mol ratio such as pressing adds in the methyl alcohol dissolves, and in the presence of the formic acid catalyzer, being heated to reflux temperature reacts then, in preferred 0.5～6.0 hour of reaction times, be cooled to room temperature then, with the solid filtering of separating out, remove and desolvate, get the described ligand compound of formula (I).The R of the described formula of above-mentioned preparation process (II) compound
1～R
3Can be identical or different, independently be selected from hydrogen or C separately
1～C
6Alkyl, the p of formula (III) compound is
Or
R is selected from hydrogen or C
1～C
3Alkyl, R ' is selected from hydrogen or C
1～C
3Alkyl.
(2) with the ligand compound that makes in the presence of ether solvents, with alkyl halide magnesium, lithium alkylide, sodium hydride or sodium Metal 99.5 reaction, generate the basic metal or the alkaline earth salt of title complex,
(3) in ether solvents, be MX with the basic metal of gained title complex or alkaline earth salt with general formula
4Transition metal halide reaction back form slurries, remove the ether solvents in the slurries, resistates with the toluene extraction, filter, remove the solvent in the filtrate, promptly get catalyzer, wherein MX
4M in the formula is an IVB family metal, and X is a halogen.
In the described method (2) and (3) step used ether solvents be ether or tetrahydrofuran (THF).
The mole number of alkyl halide magnesium, lithium alkylide, sodium hydride or sodium Metal 99.5 that described method (2) was reacted with title complex in the step should be 1.0～1.2 times of title complex.Preferably the alkali with the title complex reaction is alkyl halide magnesium or lithium alkylide.Alkyl halide magnesium preferable methyl magnesium chloride wherein, the preferred butyllithium of lithium alkylide.
The temperature of reaction in (1), (2) two steps should be controlled to be-10～40 ℃ in the described method, is preferably 0～25 ℃.The temperature of controlling these two steps mainly is in order to prevent that liberated heat is too much in the reaction process, to cause system temperature higher, causing synthetic product to decompose.
The MX of described method (3) in the step
4Preferred titanium tetrachloride or zirconium tetrachloride.MX during reaction
4With the mol ratio of title complex basic metal or alkaline earth salt be 1～2: 1, be preferably under the situation that waits mol ratio and react, temperature is 0～25 ℃.After reacting slurry was removed ether solvents, resistates extracted with toluene, also available benzene extraction.The liquid-solid volume ratio of extraction liquid and resistates is 50～100: 1 during extraction.
It is preferred 2 that (1) goes on foot the amino benzenes compounds of used formula (II) among the above-mentioned preparation method, 6-xylidine, 2,6-Diethyl Aniline, 2,6-dipropyl aniline, 2,6-diisopropyl aniline, 2,2,4,6-triisopropyl aniline, 2,4,6-triphenyl aniline.The preferred pyrrole aldehyde of carbonyl compound of used formula (III), 2-acetyl pyrrole, 3-indolecarboxaldehyde.
Catalyzer provided by the invention is applicable to the Primary Catalysts of olefinic polymerization, and also need add alkylaluminoxane or aluminum alkyls during polymerization is promotor.The condition of olefinic polymerization is 10～110 ℃, preferably 20～80 ℃, polymerization under 0.1～1.0MPa, aluminium during polymerization in the promotor and the transition metal mol ratio in the Primary Catalysts are 100～10000: 1, preferred 200～3000: 1, more preferably 1500～2000: 1.The preferred olefinic monomer of polymerization is an alpha-olefin, as ethene.Polymerization can be the homopolymerization or the copolymerization of alpha-olefin, as ethylene homo or ethene and other alpha-olefin, as the copolymerization of hexene-1 or butene-1.
The promotor that uses during polymerization is selected from alkylaluminoxane or aluminum alkyls, as methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium.Described alkylaluminoxane can be linear or cyclic, and preferred aikyiaiurnirsoxan beta is a methylaluminoxane.
Pyrrole ring in the catalyzer provided by the invention and transition metal atoms form the structure that is similar to metallocene, lone-pair electron on the side chain nitrogen and transition metal atoms effect simultaneously forms coordinate bond, play the effect of constrained geometry configuration, the aromatic substituent that connects on the side chain nitrogen also influences to some extent to the sterie configuration and the electron distributions of catalyzer.When catalyzer provided by the invention is used for olefinic polymerization, have higher activity, and the polymkeric substance that generates has wider molecular weight distribution.
Embodiment
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
This examples preparation pyrrole aldehyde contracts 2,6-diisopropyl benzene amido titanous chloride.
A, preparation part pyrrole aldehyde contract 2, the 6-diisopropyl aniline.
(1) with 2.3 gram (0.024mol) pyrrole aldehyde (Sweden, ACR S company) and 4.3 the gram (0.024mol) 2,6-diisopropyl aniline (Sweden, ACR S company) joins in 5 ml methanol, splash into several formic acid and make catalyzer, be heated to reflux temperature reaction 6 hours under stirring, be cooled to room temperature, promptly have a large amount of crystal to produce.Filter, solid obtains title complex with 6 ml methanol washing 3 times.
B, preparation polymerizing catalyst.
(2) following operation all uses the Schlenk instrument to carry out under the high pure nitrogen protection.0.317 gram (1.25mmol) part is dissolved with 10 milliliters of tetrahydrofuran (THF)s, be cooled to 0 ℃, and (German Fluka company produces slowly to drip 0.42 milliliter of methylmagnesium-chloride under this temperature, the tetrahydrofuran solution of 22 heavy %) and the mixture of 10 milliliters of tetrahydrofuran (THF)s, reacted 1 hour, system temperature is risen to the Grignard reagent (the chlorination magnesium salts of part) that room temperature reaction formed part in 6 hours.
(3) 0.14 milliliter of (1.25mmol) titanium tetrachloride is dissolved in 20 milliliters of tetrahydrofuran (THF)s forms solution, this solution is cooled to 0 ℃, slowly splash in the above-mentioned part Grignard reagent that makes, and under this temperature, reacted 1 hour, be heated to the tetrahydrofuran (THF) reflux temperature, the reaction system color becomes brown by yellow.Drain tetrahydrofuran (THF) under the decompression, add 50 milliliters of toluene in resistates, stir extraction 6 hours, remove by filter insoluble white solid, gained filtrate is under reduced pressure drained toluene, gets deep yellow solid catalyst A.
Ultimate analysis shows that the content of each element in the catalyst A is: carbon 48.9% (50.1%), hydrogen 5.4% (5.2%), nitrogen 6.7% (6.9%), titanium 11.9% (11.7%), chlorine 26.3% (26.1%), data are theoretical value in the bracket, down together.Infrared spectrum is presented at 1627.7cm
-1The characteristic peak of C=N appears in the place.
Example 2
This examples preparation pyrrole aldehyde contracts 2,6-diisopropyl benzene amido tri-chlorination zirconium.
Method by example 1 prepares catalyzer, and different is to replace titanium tetrachloride with 0.29 gram (1.25mmol) zirconium tetrachloride in the reaction of (3) step, and filtrate decompression produces faint yellow solid after draining toluene, is catalyst B.
Ultimate analysis shows that the content of each element in the catalyst B is: carbon 45.1% (45.39%), hydrogen 5.0% (4.6%), nitrogen 6.0% (6.2%), zirconium 19.9% (20.2%), chlorine 23.6% (23.6%).Infrared spectrum is presented at 1627.5cm
-1The characteristic peak of C=N appears in the place.
Example 3
This examples preparation pyrrole aldehyde contracts 2,6-dimethyl benzene amido titanous chloride.
With 1.9 gram (0.020mol) pyrrole aldehydes and 2.4 gram (0.020mol) 2,6-xylidine (Sweden, ACR S company) joins in 5 ml methanol, splashes into several formic acid and makes catalyzer, be heated to reflux temperature 6 hours under stirring, being cooled to room temperature promptly has a large amount of crystal to produce.Filter, solid makes the ligand compound pyrrole aldehyde and contracts 2, the 6-xylidine with 6 ml methanol washing 3 times.
0.248 gram (1.25mmol) part is dissolved with 10 milliliters of tetrahydrofuran (THF)s, make the chlorination magnesium salts of part by described method of 1 (2) step of example.Make deep yellow solid catalyst C by (3) step working method again.
Ultimate analysis shows that the content of each element among the catalyzer C is: carbon 44.1% (44.4%), hydrogen 3.9% (3.7%), nitrogen 7.9% (8.0%), titanium 12.4% (13.6%), chlorine 30.2% (30.3%).Infrared spectrum is presented at 1626.3cm
-1The characteristic peak of C=N appears in the place.
Example 4
This examples preparation pyrrole aldehyde contracts 2,6-dimethyl benzene amido tri-chlorination zirconium.
Method by example 3 prepares catalyzer, and different is to replace titanium tetrachloride with 0.29 gram (1.25mmol) zirconium tetrachloride in the reaction of (3) step, and filtrate decompression produces faint yellow solid after draining toluene, is catalyzer D.
Ultimate analysis shows that the content of each element among the catalyzer D is: carbon 39.3% (39.5%), hydrogen 3.6% (3.3%), nitrogen 7.0% (7.1%), zirconium 22.8% (23.1%), chlorine 26.7% (27.0%).Infrared spectrum is presented at 1625.2cm
-1The characteristic peak of C=N appears in the place.
Example 5
This examples preparation pyrrole aldehyde 2 base titanous chloride that contracts.
With 1.9 gram (0.020mol) pyrrole aldehydes and 2.7 gram (0.020mol) 2 (Sweden, ACR S company) joins in 5 ml methanol, splash into several formic acid and make catalyzer, be heated to reflux temperature reaction 6 hours under stirring, be cooled to room temperature, promptly have a large amount of crystal to produce.Filter, solid washs 3 times with 6 ml methanol, obtains the ligand compound pyrrole aldehyde 2 that contracts.
0.265 gram part is dissolved with 10 milliliters of tetrahydrofuran (THF)s, make the chlorination magnesium salts of part by described method of 1 (2) step of example.Make catalyzer E by (3) step working method again.
Ultimate analysis shows that the content of each element among the catalyzer E is: carbon 45.8% (46.0%), hydrogen 4.5% (4.1%), nitrogen 7.7% (7.7%), titanium 13.0% (13.1%), chlorine 29.0% (29.1%).Infrared spectrum is presented at 1627.3cm
-1The characteristic peak of C=N appears in the place.
Example 6
This examples preparation pyrrole aldehyde 2 base tri-chlorination zirconium that contracts.
Method by example 5 prepares catalyzer, different is to replace the chlorination magnesium salts of titanium tetrachloride and title complex to react with 0.29 gram (1.25mmol) zirconium tetrachloride in the reaction of (3) step, filtrate decompression produces faint yellow solid after draining toluene, is catalyzer F.
Ultimate analysis shows that the content of each element among the catalyzer F is: carbon 40.6% (41.1%), hydrogen 4.0% (3.7%), nitrogen 6.6% (6.8%), zirconium 22.5% (22.3%), chlorine 25.6% (26.0%).Infrared spectrum is presented at 1627.1cm
-1The characteristic peak of C=N appears in the place.
Example 7
This examples preparation 2-acetyl pyrrole contracts 2,6-diisopropyl benzene amido titanous chloride.
With 2.2 gram (0.020mol) 2-acetyl pyrrole (Sweden; ACR S company) and 3.5 the gram (0.020mol) 2; the 6-diisopropyl aniline joins in 5 ml methanol; splash into several formic acid and make catalyzer; be heated to reflux temperature reaction 6 hours under stirring; be cooled to room temperature, promptly have a large amount of crystal to produce.Filter, solid obtains ligand compound 2-acetyl pyrrole and contracts 2, the 6-diisopropyl aniline with 6 ml methanol washing 3 times.
0.335 gram part is dissolved with 10 milliliters of tetrahydrofuran (THF)s, make the chlorination magnesium salts of part by described method of 1 (2) step of example.Make deep yellow solid catalyst G by (3) step working method again.
Ultimate analysis shows that the content of each element among the catalyzer G is: carbon 51.0% (51.3%), hydrogen 5.5% (5.4%), nitrogen 6.6% (6.6%), titanium 11.2% (11.4%), chlorine 25.2% (25.3%).Infrared spectrum is presented at 1627.6cm
-1The characteristic peak of C=N appears in the place.
Example 8
This examples preparation 2-acetyl pyrrole contracts 2,6-diisopropyl benzene amido tri-chlorination zirconium.
Method by example 7 prepares catalyzer, and different is to replace the chlorination magnesium salts of titanium tetrachloride and title complex to react with 0.29 gram (1.25mmol) zirconium tetrachloride in the reaction of (3) step, and filtrate decompression produces pale yellow colored solid body catalyst H after draining toluene.
Ultimate analysis shows that the content of each element among the catalyzer H is: carbon 46.5% (46.5%), hydrogen 5.0% (4.9%), nitrogen 6.0% (6.0%), zirconium 19.6% (20.0%), chlorine 22.1% (22.9%).Infrared spectrum is presented at 1626.8cm
-1The characteristic peak of C=N appears in the place.
Example 9
This examples preparation 3-indolecarboxaldehyde contracts 2,6-diisopropyl benzene amido titanous chloride.
With 3.65 gram (0.025mol) 3-indolecarboxaldehyde (Sweden, ACR S company) and 4.32 (0.024mol) gram 2, the 6-diisopropyl aniline joins in 5 milliliters of ethanol, splash into several formic acid and make catalyzer, be heated to reflux temperature reaction 6 hours under stirring, be cooled to room temperature, promptly have a large amount of crystal to produce.Filter, solid obtains ligand compound 3-indolecarboxaldehyde and contracts 2, the 6-diisopropyl aniline with 6 ml methanol washing 3 times.
0.38 gram (1.25mmol) part is dissolved with 10 milliliters of tetrahydrofuran (THF)s, make the chlorination magnesium salts of part by described method of 1 (2) step of example.Make the yellow solid catalyst I by (3) step working method again.
Ultimate analysis shows that the content of each element in the catalyst I is: carbon 55.4% (55.1%), hydrogen 5.3% (5.0%), nitrogen 5.9% (6.1%), titanium 10.4% (10.5%), chlorine 22.9% (23.3%).Infrared spectrum is presented at 1622.8cm
-1The characteristic peak of C=N appears in the place.
Example 10
This examples preparation 3-indolecarboxaldehyde contracts 2,6-diisopropyl benzene amido tri-chlorination zirconium.
Method by example 9 prepares catalyzer, and different is to replace the chlorination magnesium salts of titanium tetrachloride and title complex to react with 0.29 gram (1.25mmol) zirconium tetrachloride in the reaction of (3) step, and filtrate decompression produces yellow solid catalyzer J after draining toluene.
Ultimate analysis shows that the content of each element among the catalyzer J is: carbon 51.0% (50.3%), hydrogen 4.9% (4.6%), nitrogen 5.8% (5.6%), zirconium 18.1% (18.2%), chlorine 21.2% (21.3%).Infrared spectrum is presented at 1627.3cm
-1The characteristic peak of C=N appears in the place.
Example 11～20
Following example is that Primary Catalysts carries out polyreaction with catalyzer provided by the invention, the preparation polyethylene.
With 100 milliliters of reaction flasks that agitator is housed with nitrogen replacement after, feed purified ethylene gas, pressure is 0.1MPa.Add 50 milliliters of exsiccant toluene, stirred 5 minutes, add the catalyst A～J of example 1～10 preparation respectively, the catalyzer dosage is about 1.0 * 10
-5Mole, and be mixed with toluene solution.The concentration that adds the production of an amount of U.S. Albemarle company again is the toluene solution of the methylaluminoxane (MAO) of 10 heavy %, the mol ratio that makes aluminium and transition metal is 2000: 1,80 ℃ of isothermal reactions 0.5 hour add 10 milliliters of acidifying ethanol that contain 30%HCl and stop polyreactions.Reactant was continued to stir in excess ethyl alcohol 1 hour, filter, use washing with alcohol, 70 ℃, decompression dry 4 hours down get polymkeric substance.Each example polyreaction catalyst system therefor and polymer property see Table 1.Polymkeric substance weight-average molecular weight (Mw), molecular weight distribution (Mw/Mn) all use gel chromatography (GPC) to measure.
Table 1
The active Mw instance number of catalyst agent Mw/Mn
Numbering (gram PE/ mole M hour) (* 10
4)
11 A 1.3×10
5 5.9 3.2
12 B 9.2×10
4 6.3 3.5
13 C 1.2×10
5 7.0 3.3
14 D 1.0×10
5 6.5 4.0
15 E 1.1×10
5 - -
16 F 8.7×10
4 - -
17 G 9.8×10
4 5.4 3.3
18 H 1.0×10
5 5.7 3.0
19 I 2.6×10
5 9.6 3.1
20 J 2.5×10
5 8.9 3.5
M is a transition metal in the table
Claims (9)
1, a kind of olefin polymerization catalysis, the general expression that has is: L
nMX
4-n
In the formula: M is the transition metal that is selected from IVB family, and X is a halogen, and L is a part, and n is 1 or 2, and described ligand L has the general expression of formula (I):
In the formula (I), p is
Or
Wherein R is selected from hydrogen or C
1～C
3Alkyl, R ' is selected from hydrogen or C in the formula (I)
1～C
3Alkyl, R
1～R
3Can be identical or different, independently be selected from hydrogen or C separately
1～C
6Alkyl.
2, according to the described catalyzer of claim 1, it is characterized in that the M in the catalyzer general formula is titanium or zirconium, X is a chlorine.
3, according to the described catalyzer of claim 1, it is characterized in that the R in described formula (I) part is a hydrogen, R ' is hydrogen or methyl, R
1And R
2Be selected from methyl or sec.-propyl, R
3Be hydrogen.
4, the described Preparation of catalysts method of a kind of claim 1 may further comprise the steps:
(1) with the amino benzenes compounds of formula (II) and the carbonyl compound of formula (III)
The amount of mol ratio such as pressing adds in the methyl alcohol dissolves, and in the presence of the formic acid catalyzer, being heated to reflux temperature reacts then, reduce to room temperature then,, use the methanol wash solid the solid filtering of separating out, remove and desolvate, get the described ligand compound of formula (I), the R of described formula (II) compound
1～R
3Can be identical or different, independently be selected from hydrogen or C separately
1～C
6Alkyl, the p of formula (III) compound is
Or
R ' is selected from hydrogen or C
1～C
3Alkyl, R is selected from hydrogen or C
1～C
3Alkyl,
(2) with the ligand compound that makes in the presence of ether solvents, with alkyl halide magnesium, lithium alkylide, sodium hydride or sodium Metal 99.5 reaction, generate the basic metal or the alkaline earth salt of title complex,
(3) in ether solvents, be MX with the basic metal of gained title complex or alkaline earth salt with general formula
4Transition metal halide reaction, form slurries, remove ether solvents after, resistates with the toluene extraction, filter, the solvent of filtrate is removed, promptly get catalyzer, wherein MX
4M in the formula is an IVB family metal, and X is a halogen.
5, in accordance with the method for claim 4, it is characterized in that the ether solvents in (2) and (3) is ether or tetrahydrofuran (THF), the MX in (3) step
4Be titanium tetrachloride or zirconium tetrachloride.
6, in accordance with the method for claim 4, it is characterized in that the alkyl halide magnesium described in (2) is methylmagnesium-chloride, lithium alkylide is a butyllithium.
7, in accordance with the method for claim 4, it is characterized in that the reaction times described in (1) step is 0.5～6.0 hour.
8, a kind of olefine polymerizing process, it is characterized in that with the described catalyzer of claim 1 be Primary Catalysts, with alkylaluminoxane or aluminum alkyls is promotor, make alpha-olefin at 10～110 ℃, 0.1 polymerization under the～1.0MPa, aluminium during polymerization in the promotor and the transition metal mol ratio in the Primary Catalysts are 100～10000: 1.
9, in accordance with the method for claim 8, it is characterized in that described aikyiaiurnirsoxan beta is a methylaluminoxane, aluminium during polymerization in the promotor and the transition metal mol ratio in the Primary Catalysts are 200～3000: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00105805 CN1128820C (en) | 2000-04-07 | 2000-04-07 | Polyolefine catalyst containing pyrrole loop in its ligand and its preparing process and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00105805 CN1128820C (en) | 2000-04-07 | 2000-04-07 | Polyolefine catalyst containing pyrrole loop in its ligand and its preparing process and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1317500A CN1317500A (en) | 2001-10-17 |
| CN1128820C true CN1128820C (en) | 2003-11-26 |
Family
ID=4577954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00105805 Expired - Fee Related CN1128820C (en) | 2000-04-07 | 2000-04-07 | Polyolefine catalyst containing pyrrole loop in its ligand and its preparing process and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1128820C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2125845A1 (en) * | 2006-12-22 | 2009-12-02 | Shell Internationale Research Maatschappij B.V. | Ligands and catalyst systems thereof for the catalytic oligomerization of olefinic monomers |
| CN114853798A (en) * | 2022-06-07 | 2022-08-05 | 山东京博石油化工有限公司 | Pyrrole ring tridentate metal complex and application thereof |
-
2000
- 2000-04-07 CN CN 00105805 patent/CN1128820C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1317500A (en) | 2001-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1631910A (en) | Processes for the preparation of polyolefin resins using supported ionic catalysts and uses of said resins | |
| CN1107859A (en) | Polymerization of olefin | |
| CN1239526C (en) | Catalyst composition for olefinic polymerization | |
| CN1160381C (en) | Olefine polymerization catalyst containing double schiff base ligand and preparing method and use | |
| CN1292007C (en) | Bi active component polyolefin catalyst, and its preparing method and use | |
| CN1136239C (en) | Magnesium halide/silicon dioxide loaded semi-metallocene catalyst and its preparation and use | |
| CN1278265A (en) | Method for preparing fluvene metal complexes | |
| CN1178949C (en) | Cyclopentadienyl transition metal compounds, as polymerization catalysts | |
| CN1125088C (en) | Transition metal catalyst containing acacyclopentadiene in its ligand and its preparing process and application | |
| CN1128820C (en) | Polyolefine catalyst containing pyrrole loop in its ligand and its preparing process and application | |
| CN1132856C (en) | Catalyst for polymerizing semi-metallocene with olefin and its preparing process and application | |
| CN1103869A (en) | New halogenated complexes of lanthanides and their use in the polymerization of unsaturated monomers | |
| CN1166697C (en) | Binuclear metallocene compound and its preparation and application in olefinic polymerization | |
| CN1527841A (en) | Polymerization catalyst system, polymerization process and polymer therefrom | |
| CN1115348C (en) | Polyolefin catalyst containing azabenzene in ligand and its preparing process and application | |
| CN1129226A (en) | Metallocene compound | |
| CN1480471A (en) | Ligand of catalyzer for olefinic polymerization and transition metal complex | |
| CN1176118C (en) | Loading type olefine polymerization catalyst using xifu alkali as ligand its preparation method | |
| CN1128825C (en) | Semi-metallocene supported polyvinyl catalyst and preparation method thereof | |
| CN1132855C (en) | Olefine polymerizing semi-metallocene catalyst and its prepn. and application | |
| CN1850871A (en) | Composite catalytic system for preparing wide/dual-peak distributed high density polyethylene | |
| CN1168744C (en) | Catalyst containing mono schiff base ligand and its preparation and usage for olefine polymerization | |
| CN1208339C (en) | Single metallocene catalyst with naphthalene ring ligand and its prepn | |
| CN1887920A (en) | Vanadium non-metallocene polyolefin catalyst and its prepn and application | |
| CN1156496C (en) | Polythene catalyst loaded by double-carrier of magnesium chloride/kaolin and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Applicant after: China Petrochemical Group Corp. Applicant after: Sinopec Research Institute of Petroleum Processing Applicant before: China Petrochemical Group Corp. Applicant before: Chinese petrochemical industry Research Institute of Petro-Chemical Engineering of group company |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM + CHEMICAL CORPORATION, PETROLEUM CHEMICAL ENGINEERING INSTITUTE TO: CHINA PETROCHEMICAL CORPORATION; CHINA PETROCHEMICAL GROUP PETROCHEMICAL SINCE INSTITUTE |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20031126 Termination date: 20110407 |