CN103360431B - Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex - Google Patents
Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex Download PDFInfo
- Publication number
- CN103360431B CN103360431B CN201310298187.3A CN201310298187A CN103360431B CN 103360431 B CN103360431 B CN 103360431B CN 201310298187 A CN201310298187 A CN 201310298187A CN 103360431 B CN103360431 B CN 103360431B
- Authority
- CN
- China
- Prior art keywords
- compound
- amidoquinaldine
- quinoline
- room temperature
- dissolved
- 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 invention provides a metal complex with 8-aminoquinaldine as a matrix and a synthesis method of the metal complex. According to the method provided by the invention, a guanidine ligand with the 8-aminoquinaldine as the matrix is synthesized from the 8-aminoquinaldine as the raw material, and the guanidine ligand functioning as a transfer reagent reacts with a metal halide to synthesize a series of metal complexes. The method has the characteristics of simple steps, relatively low requirements on conditions, quite high yield and the like. The complex synthesized by using the method can be used as an olefin polymerization catalyst. As the complex can be used for reducing the molecular weight and branching degree of oligomerized ethylene and is high in catalysis activity and selectivity for ethylene oligomerization and polymerization, a polyolefin material with quite good performance can be obtained.
Description
Technical field
The present invention relates to organometallics, specifically belong to a kind of with 8-amidoquinaldine be parent dual-nuclei structure model and synthetic method thereof, this metal complexes can be used as olefin polymerization catalysis.
Background technology
Alpha-olefin refers to the linear alpha-olefin of double bond in molecule one end, is a kind of important industrial chemicals.Wherein the alpha-olefin of C6 ~ C8 is mainly used as the comonomer of linear low density polyethylene or Low Density Polyethylene, and consumption is maximum, and appreciation potential is maximum, is the domestic product be badly in need of most at present.At present, the main method of producing alpha-olefin is ethylene oligomerization method, and the alpha-olefin utilizing this method to produce accounts for 94.1% of whole alpha-olefin production.Used catalyst mainly contains aluminum alkyls system, titanium system, nickel system, iron system, chromium system, zirconium system etc.
Nickel catalyst
Nineteen ninety-five, Brookhart reported first diimine class nickel olefin polymerizing catalyst, and mention and reduce the sterically hindered of part, oligomerizing ethylene molecular weight and the degree of branching can be reduced, even can synthesize alpha-olefin, this discovery makes nickel catalyst more noticeable.This kind of catalyzer forms positively charged ion under Lewis acid is as the effect of MAO etc., has good catalytic activity and products distribution to ethylene oligomerization.2002,
etc. the research reported oligomerisation catalyst performance, by changing the substituting group on arylamine and complex compound skeleton, can modulation catalytic activity and products distribution.Sun Wenhua etc. reported the multiple N ∩ N ∩ N-type catalyzer for ethylene oligomerization in addition.The nickel catalyzator being wherein framework counterpart with 8-quinolylamine has very high activity to ethylene oligomerization, reaches 4.7 × 10
6g mol
-1(Ni) h
-1.
Iron cobalt series catalyst
In the last few years, Americanized scholar Brookhart teaches study group and Englishize scholar Gibson professor study group is achieving significant progress containing in the iron cobalt series catalyst of diimide pyridine, and these catalyzer all have high catalytic activity.Inspire by this, many chemists start the research being devoted to three tooth nitrogen ferrum-cobalt catalysts, and Sun Wenhua research group had reported a series of three tooth nitrogen complexes, and research finds that the polymerization of these catalysts towards ethylene and oligomerisation have high catalytic activity.2008, Sun Wenhua reported a series of ferrum-cobalt catalyst containing 8-aminoquinoline derivatives, and they not only have high catalytic activity to ethylene oligomerization, and have high selectivity.
Bianchini etc. have studied a class and have Cs symmetry and the symmetric pyridine diimine iron of C1, cobalt complex, be promotor with MAO, this kind of title complex can catalyzed ethylene oligomerisation effectively, 99% is reached to the selectivity of alpha-olefin, oligomerization product meets Schulz-Flory distribution, and dispersion index is 0.61 ~ 0.91.
The demand of China to material aspect is huge, especially the polymer of polyolefins.But owing to starting to walk evening, technology is lower, a lot of polyolefine material needs import, and therefore, the olefin polymerization catalysis developed becomes a very important aspect of modern chemistry research.
Summary of the invention
The object of the present invention is to provide a kind of with 8-amidoquinaldine be parent metal complexes and synthetic method thereof, this metal complexes can be used as olefin polymerization catalysis.
A kind of dual-nuclei structure model that is parent with 8-amidoquinaldine provided by the invention, its structural formula is:
Or
Synthetic route is:
Structural formula provided by the invention is a kind of with the synthetic method of the 8-amidoquinaldine dual-nuclei structure model that is parent of (1), comprises the steps:
(1) by 8-amidoquinaldine with hmds in molar ratio for 1:1 mixes, then be that 1:50 adds catalyst chlorotrimethysilane by trimethylchlorosilane and 8-amidoquinaldine mol ratio, at least 24h is reacted at 120 DEG C-130 DEG C, underpressure distillation (5mmHg), collect 126 DEG C of cuts, obtain the compound a of pale yellowish oil liquid;
(2) be dissolved in by compound a in normal hexane solvent, under 0 ° of C, the n-Butyl Lithium with compound a equimolar amount dropwise added stirring, after reacting half an hour, return to room temperature and continue reaction at least 8 hours, stop stirring, filtration, obtains compound b;
(3) be dissolved in ether solvent by compound b, under 0 ° of C, dropwise added wherein by the nitrile with compound b equimolar amount, after reacting half an hour, return to room temperature and continue reaction at least 12 hours, stop stirring, removal ether, obtains compound c;
(4) compound c is dissolved in ether solvent, under acetone bath (-78 DEG C), by compound c and M
1cl
2mol ratio is that 1:2 adds M
1cl
2, stir, recover the follow-up continuous stirring reaction of room temperature at least 24h, except desolventizing and volatile substances, add dichloromethane extraction and filter, filtrate obtains compound d through condensing crystal.
Structural formula provided by the invention is a kind of with the synthetic method of the 8-amidoquinaldine dual-nuclei structure model that is parent of (2), comprises the steps:
(1) by 8-amidoquinaldine with hmds in molar ratio for 1:1 mixes, then be that 1:50 adds catalyst chlorotrimethysilane by trimethylchlorosilane and 8-amidoquinaldine mol ratio, at least 24h is reacted at 120 DEG C-130 DEG C, underpressure distillation (5mmHg), collect 126 DEG C of cuts, obtain the compound a of pale yellowish oil liquid;
(2) be dissolved in by compound a in normal hexane solvent, under 0 ° of C, the n-Butyl Lithium with compound a equimolar amount dropwise added stirring, after reacting half an hour, return to room temperature and continue reaction at least 8 hours, stop stirring, filtration, obtains compound b;
(3) be dissolved in ether solvent by compound b, under 0 ° of C, dropwise added wherein by the nitrile with compound b equimolar amount, after reacting half an hour, return to room temperature and continue reaction at least 12 hours, stop stirring, removal ether, obtains compound c;
(4) compound c is dissolved in ether solvent, under acetone bath (-78 DEG C), by compound c and M
2cl
4mol ratio is that 1:2 adds M
2cl
4, stir, recover the follow-up continuous stirring reaction of room temperature at least 24h, except desolventizing and volatile substances, add dichloromethane extraction and filter, filtrate obtains Verbindung through condensing crystal.
Compared with prior art, advantage of the present invention:
The present invention with 8-amidoquinaldine for parent synthesis guanidine radicals lithium salts, then using guanidine radicals lithium salts as part transfering reagent, respectively with FeCl
2, CoCl
2, NiCl
2, ZrCl
4, TiCl
4, HfCl
4act in ether solvent, obtain the title complex of various metal, preparation method is simple, and conditional request is relatively low, and productive rate is relatively high, and the title complex obtained can be used as olefin polymerization catalysis.Oligomerizing ethylene molecular weight and the degree of branching can be reduced due to this title complex and have high catalytic activity and high selectivity to ethylene oligomerization and polymerization, therefore can obtain the polyolefine material of better performances.
Accompanying drawing explanation
Fig. 1 is with the X-ray diffraction crystalline structure figure of the 8-amidoquinaldine cobalt complex that is parent.
Fig. 2 is with the X-ray diffraction crystalline structure figure of the 8-amidoquinaldine ferrous coordination compound that is parent.
Embodiment
All reactions are all carrying out under the dried high pure nitrogen of potassium post or argon shield, use the Schlenk technological operation of standard.
Embodiment 1: the preparation of cobalt complex
In 100ml round-bottomed flask, add 8-amidoquinaldine (9.843g, 62mmol), hmds (13ml, 62mmol) and then add 0.16mL(1.26mmol) trimethylchlorosilane, at N
2120 DEG C are heated to, reaction 24h under protective condition.After completion of the reaction, vacuum removing volatile matter, obtains red oil, underpressure distillation (5mmHg), collects 126 DEG C of cuts, obtain compound a (8-NHSiMe
3-2CH
3-C
9h
5n) pale yellowish oil liquid 13.39g, productive rate 93%.
1H-NMR(300MHz,CDCl
3):δ(ppm)0.379(s,Si(CH
3)
3,9H),2.697(s,CH
3,3H),6.185(s,NHSi(CH
3)
3,1H),6.882-6.907(d,CH of quinoline,1H),7.032-7.059(d,CH of quinoline,1H),7.183-7.292(m,CH of quinoline,2H),7.892-7.920(d,CH of quinoline,1H)。
13C-NMR(75MHz,CDCl
3):δ(ppm)-0.287(Si(CH
3)
3),25.053(CH
3),109.215(C of quinoline),114.506(C of quinoline),121.950(Cof quinoline),126.241(C of quinoline),126.796(C of quinoline),136.161(C of quinoline),138.361(C of quinoline),144.292(C of quinoline),155.647(C of quinoline)。
Get 1.516g (6.580mmol) a in Schlenk bottle, under agitation add 30mL normal hexane solvent, the hexane solution (6.551mmol of 1.22mL n-Butyl Lithium at 0 DEG C, 5.37mol/L) dropwise join in above-mentioned solution, solution becomes muddy immediately, recovers room temperature after half an hour, continue stirring reaction and obtain yellow turbid liquid after 8 hours, leave standstill, cross and filter filtrate, obtain compound b (8-LiN (SiMe
3)-2-CH
3-C
9h
5n) yellow powdery solid 1.208g, productive rate 78%.
1H-NMR(300MHz,C
6D
6):δ(ppm)0.245(s,Si(CH
3)
3,9H),2.131(s,CH
3,3H),6.466(d,CH of quinoline,1H),6.832(d,CH of quinoline,1H),7.188-7.247(m,CH of quinoline,2H),7.387(d,CH of quinoline,1H)。
13C-NMR(75MHz,C
6D
6):δ(ppm)6.646(Si(CH
3)
3),29.253(CH
3),118.011(C of quinoline),125.492(C of quinoline),141.637(C of quinoline),159.009(C of quinoline)。
7Li-NMR(300MHz,C
6D
6):δ(ppm)2.808。
Getting 0.874g (3.701mmol) b in Schlenk bottle, under agitation add 30mL ether solvent, is orange red color cloud liquid.At 0 DEG C, 0.30mL dimethylamino nitrile (3.681mmol) is dropwise joined in above-mentioned turbid liquid, solution is without considerable change, room temperature is recovered after half an hour, continue stirring reaction and obtain orange red clear liquid after 12 hours, vacuum drains removing ether, obtains compound c ({ [8-NC (N (Me)
2) N (SiMe
3) (2-CH
3-C
9h
5n)] Li}
2) yellow solid 1.042g, productive rate 92%.
1H-NMR(300MHz,C
6D
6):δ(ppm)0.568(s,Si(CH
3)
3,9H),2.525(s,CH
3of quinoline,3H),2.736(s,N(CH
3)
2,6H),6.314-6.341(d,CH of quinoline,1H),6.743-6.769(d,CH of quinoline,1H),6.841-6.865(d,CH of quinoline,1H),7.176-7.203(m,CH of quinoline,1H),7.360-7.386(m,CH of quinoline,1H)。
13C-NMR(75MHz,C
6D
6):δ(ppm)8.462(Si(CH
3)
3),29.656(CH
3ofquinoline),44.270(N(CH
3)
2),117.216(C of quinoline),118.432(C of quinoline),119.617(Cof quinoline),125.791(C of quinoline),141.954(C of quinoline),157.569(C of quinoline),159.604(C of quinoline),171.755(NCN)。
Getting 0.580g (0.943mmol) compound c in Schlenk bottle, under agitation add 30mL ether solvent, is orange red color cloud liquid.At-78 DEG C, add the anhydrous CoCl of 0.245g
2(1.887mmol), after returning to room temperature, continuing stirring reaction 24 hours, is blackish green color cloud liquid.Vacuum removing ether solvent and volatile matter, residuum methylene dichloride dissolves, and blackish green filtrate is filtered to obtain in extraction, is concentrated, and places 2 days to obtain green bulk crystals d ({ [8-NC (N (Me) under normal temperature
2) N (SiMe
3) (2-CH
3-C
9h
5n)] CoCl}
2(CH
2cl
2)) 0.371g, productive rate 45%.Ultimate analysis: measured value C, 45.37; H, 5.57; N, 12.84%.Theoretical value C, 45.42; H, 5.54; N, 12.84%.Molecular structure is shown in Fig. 1.
The part bond distance of title complex d
with bond angle (°) data
The X-ray single crystal diffraction data of title complex d
Embodiment 2: the preparation of ferrous metals title complex
Getting 0.569g (0.926mmol) compound c in Schlenk bottle, under agitation add 30mL ether solvent, is orange red color cloud liquid.At-78 DEG C, add the anhydrous FeCl of 0.235g
2(1.854mmol), after returning to room temperature, continuing stirring reaction 24 hours, is pale brown color cloud liquid.Vacuum removing ether solvent and volatile matter, residuum methylene dichloride dissolves, red-brown filtrate is filtered to obtain in extraction, after being drained, add after a small amount of ether washes away viscous material and obtain yellow-brown solid, be dissolved in methylene dichloride concentrated, under normal temperature, placed 1 day to obtain red bulk crystals d ({ [8-NC (N (Me)
2) N (SiMe
3) (2-CH
3-C
9h
5n)] FeCl}
2(CH
2cl
2)) 0.315g, productive rate 39%, decomposition temperature, 172-173 DEG C.Ultimate analysis: measured value C, 45.68; H, 5.64; N, 12.99%.Theoretical value C, 45.74; H, 5.58; N, 12.93%.The molecular structure of title complex is shown in Fig. 2.
The part bond distance of title complex d
with bond angle (°) data
The X-ray single crystal diffraction data of title complex d
Embodiment 3: the preparation of zirconium metal complexes and ethylene catalyst
Getting (0.53g, 0.86mmol) compound c is dissolved in diethyl ether solution, is orange red color cloud liquid.Under acetone bath (-78 DEG C), add the anhydrous ZrCl of 0.4g
4(1.72mmol), after recovering room temperature, stirring reaction 24 hours is dark red color cloud liquid.Vacuum removing ether and volatile matter, remaining viscous solid dichloromethane solvent extracts, and leaves standstill, and filters, obtains dark red filtrate, concentrated.Red bulk crystals e0.190g is placed 2 days to obtain, productive rate 28.5% under normal temperature.
1H-NMR(300MHz,C
6D
6):2.713(s,CH
3of quinoline,3H),δ(ppm):3.015(s,N(CH
3)
2,6H),7.393(d,CH of quinoline,1H),7.43(d,CH of quinoline,1H),7.531(m,CH of quinoline,1H),8.018-8.17(m,CH of quinoline,1H),8.24(d,CH of quinoline,1H)。
Title complex e is to the research of vinyl polymerization: dry at 120 DEG C to baking oven after reactor is clean with alcohol flushing, takes out, vacuumize make temperature in the kettle reach desired temperature after fast sealing with oil pump after about 2h.After substituting three nitrogen, twice ethene, the ethene in still is a pressure.Now, accurately take 3 μm of ol catalyzer in Schlenk bottle, after adding 30mL toluene after substituting three nitrogen, ultrasonic wave is dissolved, and injects in still by solution syringe, use 50mL toluene wash bottle and syringe again, in same injection still, then add promotor, finally add 20mL toluene again, passing into rapidly ethylene gas to pressure is 10atm, setting speed is 400 revs/min, and start timing, in reaction process, continuous make-up ethylene gas maintains pressure at 10atm.Stop after being reacted to required time stirring and ventilating.Add a large amount of industrial alcohol to stop polymerization, promotor is reacted into aluminium salt by the dilute hydrochloric acid of 10% appropriate concentration, and the sample that takes a morsel carries out the content of its low-molecular-weight oligomer of gas chromatographic analysis.Stirred at ambient temperature half an hour, filter, collect solid.
When title complex e is using MMAO as promotor, the impact of different catalytic temperature and Al/Zr comparison catalyzed ethylene polymerization
Note: MAO concentration 1.46mol/L, MMAO concentration 1.93mol/L, Et2AlCl concentration 0.5mol/L test proves that this title complex is 750 at Al/Zr ratio, and when temperature is 70 DEG C, its activity is the highest.
Claims (2)
1. with the dual-nuclei structure model that 8-amidoquinaldine is parent, it is characterized in that, structural formula is:
2. a kind of with the synthetic method of the 8-amidoquinaldine dual-nuclei structure model that is parent as claimed in claim 1, it is characterized in that, comprise the steps:
(1) by 8-amidoquinaldine with hmds in molar ratio for 1:1 mixes, then be that 1:50 adds catalyst chlorotrimethysilane by trimethylchlorosilane and 8-amidoquinaldine mol ratio, at least 24h is reacted at 120 DEG C-130 DEG C, underpressure distillation under 5mmHg, collect 126 DEG C of cuts, obtain the compound a of pale yellowish oil liquid;
(2) be dissolved in by compound a in normal hexane solvent, at 0 DEG C, the n-Butyl Lithium with compound a equimolar amount dropwise added stirring, after reacting half an hour, return to room temperature and continue reaction at least 8 hours, stop stirring, filtration, obtains compound b;
(3) be dissolved in ether solvent by compound b, at 0 DEG C, dropwise added wherein by the nitrile with compound b equimolar amount, after reacting half an hour, return to room temperature and continue reaction at least 12 hours, stop stirring, removal ether, obtains compound c;
(4) compound c is dissolved in ether solvent, under acetone bath, by compound c and M
2cl
4mol ratio is that 1:2 adds M
2cl
4, stir, recover the follow-up continuous stirring reaction of room temperature at least 24h, except desolventizing and volatile substances, add dichloromethane extraction and filter, filtrate obtains dual-nuclei structure model through condensing crystal.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310298187.3A CN103360431B (en) | 2013-07-16 | 2013-07-16 | Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310298187.3A CN103360431B (en) | 2013-07-16 | 2013-07-16 | Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103360431A CN103360431A (en) | 2013-10-23 |
CN103360431B true CN103360431B (en) | 2015-07-01 |
Family
ID=49362775
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310298187.3A Expired - Fee Related CN103360431B (en) | 2013-07-16 | 2013-07-16 | Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103360431B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114891035B (en) * | 2022-06-07 | 2023-12-26 | 山西大学 | Difunctional tetranuclear metal lithium complex and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2456348A1 (en) * | 2001-08-23 | 2003-03-06 | Yechezkel Barenholz | Platinum complexes and their uses in therapy |
CN1809596A (en) * | 2003-06-20 | 2006-07-26 | 伊奎斯塔化学有限公司 | Multi-catalyst system for olefin polymerization |
US7094723B2 (en) * | 2002-04-18 | 2006-08-22 | Equistar Chemicals Lp | Catalysts containing at least one heterocyclic ligand for improving the catalysts' performance of olefin polymerization |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120016092A1 (en) * | 2010-07-14 | 2012-01-19 | Sandor Nagy | Catalysts based on quinoline precursors |
-
2013
- 2013-07-16 CN CN201310298187.3A patent/CN103360431B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2456348A1 (en) * | 2001-08-23 | 2003-03-06 | Yechezkel Barenholz | Platinum complexes and their uses in therapy |
US7094723B2 (en) * | 2002-04-18 | 2006-08-22 | Equistar Chemicals Lp | Catalysts containing at least one heterocyclic ligand for improving the catalysts' performance of olefin polymerization |
CN1809596A (en) * | 2003-06-20 | 2006-07-26 | 伊奎斯塔化学有限公司 | Multi-catalyst system for olefin polymerization |
Also Published As
Publication number | Publication date |
---|---|
CN103360431A (en) | 2013-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102060944B (en) | Alpha-diimine nickel (II) olefin polymerization catalyst as well as preparation method and application thereof | |
JP6832123B2 (en) | Ligand-based chromium catalysts and applications that catalyze ethylene oligomerization | |
CN109906229A (en) | Chromium compound, the catalyst system using the chromium compound and the method for preparing ethylene low polymer | |
CN101348501B (en) | 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof | |
US10875818B2 (en) | Chromium compound, catalyst system including the same, and method for trimerizing ethylene using the catalyst system | |
CN105646598B (en) | Asymmetric Branched polyethylene containing naphthyl substituted and the preparation method and application thereof | |
CN101085788A (en) | Metal complex using pyridine as matrix and synthetic method thereof | |
CN101391979B (en) | Unsymmetrical bis(imino)pyridines iron and cobalt complexes containing halogen, preparation method and use | |
RU2571829C2 (en) | Catalyst composition for ethylene oligomerisation and oligomerisation method | |
Chandran et al. | Ni (II) complexes with ligands derived from phenylpyridine, active for selective dimerization and trimerization of ethylene | |
CN101274290B (en) | Late transition metal catalyst and preparation method and application thereof | |
Nelkenbaum et al. | Synthesis, molecular structure and catalytic activity of chiral benzamidinate nickel complexes | |
CN104892681A (en) | Alpha-diimine nickel metal organic compound and preparation method thereof | |
CN103360431B (en) | Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex | |
CN111995516B (en) | Synthesis method of difluoro acetyl fluoride | |
JP7332700B2 (en) | Halogen-Containing Compounds and Uses, and Catalyst Compositions and Ethylene Oligomerization, Ethylene Trimerization, and Ethylene Tetramerization Processes | |
Liu et al. | Chromium-based complexes bearing N-substituted diphosphinoamine ligands for ethylene oligomerization | |
CN101357931A (en) | Imino-1,10-phenanthroline chromium dichloride complex, preparation method and application thereof | |
CN111434668B (en) | Halogen-containing compound, application thereof, catalyst composition, ethylene oligomerization method, ethylene trimerization method and ethylene tetramerization method | |
CN101376663A (en) | 6-benzimidazole-pyridine-2- formiate amide metal complexe, preparation and use | |
US11826743B2 (en) | Halogen-containing compound and use thereof as catalyst ligand in ethylene oligomerization | |
CN111434667B (en) | Fluorine-containing compound and application thereof, ethylene oligomerization catalyst composition, ethylene oligomerization method, ethylene trimerization method and ethylene tetramerization method | |
CN102260284B (en) | Novel ethylene-bridged indenyl fluorene zirconium compound, as well as preparation method and application of compound in high-selectivity catalysis of propylene dimerization | |
CN105884819B (en) | A kind of pentacoordinate imines titanium compound and its preparation method and application | |
RU2802019C2 (en) | Halogen-containing compound and its use, catalyst composition and methods for oligomerization, trimerization and tetramerization of ethylene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150701 Termination date: 20180716 |
|
CF01 | Termination of patent right due to non-payment of annual fee |