CN103396428A - Zirconium metal complex of furan aldehyde (ketone) hydrazone as well as preparation method and application of zirconium metal complex - Google Patents
Zirconium metal complex of furan aldehyde (ketone) hydrazone as well as preparation method and application of zirconium metal complex Download PDFInfo
- Publication number
- CN103396428A CN103396428A CN2013102981159A CN201310298115A CN103396428A CN 103396428 A CN103396428 A CN 103396428A CN 2013102981159 A CN2013102981159 A CN 2013102981159A CN 201310298115 A CN201310298115 A CN 201310298115A CN 103396428 A CN103396428 A CN 103396428A
- Authority
- CN
- China
- Prior art keywords
- ketone
- hydrazone
- zirconium metal
- molecular weight
- furan
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a zirconium metal complex of furan aldehyde (ketone) hydrazone, a preparation method of the zirconium metal complex and an application of the complex as a catalyst to the preparation of ultra-high molecular weight polyethylene. The preparation method of the complex comprises the following steps of: subjecting the furan aldehyde (ketone) hydrazone and lithium diisopropylamide (LDA) to dehydrogenation reaction, then, subjecting the furan aldehyde (ketone) hydrazone and a tetrahydrofuran solution of ZrX4 to reaction to obtain the complex, wherein the tetrahydrofuran solution of ZrX4 is same as the furan aldehyde (ketone) hydrazone in molar weight. The complex and alkylaluminoxane are formed into a catalytic system for catalyzing vinyl polymerization. Experimental results show that the catalytic system adopted by the invention can be used for preparing ultra-high molecular weight polyethylene with the weight-average molecular weight ranging from 2.3*106g/mol to 7.3*106g/mol, and has moderate catalytic activity. The complex provided by the invention is simple and easy to prepare, easy for obtaining raw materials, high in yield, easy for purification and the like.
Description
Technical field
The present invention relates to the zirconium metal complexes, zirconium metal complexes of a kind of Furan Aldehydes (ketone) hydrazone and preparation method thereof specifically, using and as the application for preparing extra high-molecular polythene catalyst.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is a kind of molecular weight greater than 1,000,000 thermoplastics.Long molecular chain i.e. higher molecular weight, and the main advantage of giving UHMWPE is that hardness, toughness, wear resistance and anti-stress cracking are all very high.In addition, UHMWPE also has good oilness, chemical resistant properties and good electrical property.Due to the good physicals of ultrahigh molecular weight polyethylene(UHMWPE), it is widely used in the fields such as machinery, transportation, weaving, papermaking, mining industry, agricultural, chemical industry and sports movement apparatus, such as the running gear that can be used as mechanical component, loom, bearing, gear, table trencher etc., wherein being most widely used with heavy packages container and pipeline.In addition due to the physiology inertia of ultrahigh molecular weight polyethylene(UHMWPE) excellence, as heart valve, orthopedics's part, joint prosthesis etc. use clinically (M.C.Sobieraj, et al., J.Mech.Behave.Biomed.Mater., 2009,2,433-443).
At present, the catalyzer for preparing ultrahigh molecular weight polyethylene(UHMWPE) mainly contains ziegler natta catalyst, metallocene catalyst and non-metallocene catalyst.Ziegler natta catalyst is the industrializeding catalyst for preparing ultrahigh molecular weight polyethylene(UHMWPE), and people also are improved further research at aspects such as the load to such catalyzer and internal electron donors to its catalytic activity and products obtained therefrom performance etc. always.The metallocene catalyst catalytic activity is high, but its under normal temperature condition just performance high reactivity is arranged, be not suitable for the solution polymerization process under present industrial general high temperature.One of study hotspot of metallocene catalyst is by its load now, to adapt to general gas phase and slurry polymerization processes.
In recent years, the research of non-metallocene catalyst is very active, although also there is no ripe industrial applications, but this class catalyzer have manufacturing cost low, can generate the advantages such as the wider polymer materials of range of application, gained polyolefin products excellent property, for the preparation ultra-high molecular weight polyethylene a kind of new approach is provided.For example the Fujita of Mitsui company has developed highly active FI catalyzer (T.Fujita, et al., Chem.Rew., 2011,111,2363-2449), M.S.Weiser etc. have obtained polyethylene (the weight-average molecular weight M of ultra-high molecular weight by the modification to the FI catalyzer
wBe 5.5 * 10
6G/mol; M.S.Weiser, et al., J.Organomet.Chem., 2006,691,2945-2952).At first the people such as Brookhart report, the Ni De α – diimine ligand compound that has obtained again subsequently continuing research in the laboratory of E.I.Du Pont Company can high reactivity ground catalyzed ethylene polymerization (L.K.Johnson, C.M.Killian, M.Brookhart.J.Am.Chem.Soc.1995,117,6414-6415), and obtain polyethylene (the weight-average molecular weight M of high molecular
wCan reach 1.6 * 10
6G/mol).Since entering this century, non-metallocene catalyst more and more is subject to people and payes attention to widely, as patent US7951743, US6635728, WO2013020896, US6265504, US5637660, US6767975 etc. disclose and have a kind ofly adopted non-luxuriant transition-metal catalyst to prepare the method for ultrahigh molecular weight polyethylene(UHMWPE).China is more late to the research of non-metallocene catalyst, relevant also less for the preparation of applying for a patent of ultrahigh molecular weight polyethylene(UHMWPE), it is that the patent of invention of CN101654492 and CN102958955 has been reported the method that adopts such catalyzer to prepare ultrahigh molecular weight polyethylene(UHMWPE) that publication number is only arranged.
Therefore, in this area, need the non-metallocene catalyst of continual exploitation development for the synthesis of ultrahigh molecular weight polyethylene(UHMWPE), to promote such catalyzer, prepare the industrialization development of ultrahigh molecular weight polyethylene(UHMWPE).
Summary of the invention
The purpose of this invention is to provide zirconium metal complexes of a kind of Furan Aldehydes (ketone) hydrazone and preparation method thereof, and this title complex is as the application for preparing extra high-molecular polythene catalyst.
The zirconium metal complexes of a kind of Furan Aldehydes provided by the invention (ketone) hydrazone, structural formula is as follows:
Wherein: R
1For hydrogen, or be selected from alkyl, aryl, alkaryl, the alkoxyl group of 1-10 carbon atom; R
2, R
3Be respectively independently of one another hydrogen, halogen, or be selected from alkyl, aryl, alkaryl, the alkoxyl group of 1-10 carbon atom.Such as R
1, R
2, R
3Can be respectively hydrogen, methyl, ethyl, propyl group, butyl, benzyl, phenyl or methoxyl group etc.; R
2, R
3Also can be respectively chlorine atom, bromine atoms, iodine atom etc.
X is halogen or alkyl, such as chlorine atom, bromine atoms, iodine atom, methyl, ethyl, propyl group, benzyl, phenyl etc.
The preparation method of the zirconium metal complexes of a kind of Furan Aldehydes provided by the invention (ketone) hydrazone, comprise the steps:
(1) preparation of Furan Aldehydes (ketone) hydrazone part:
Furan Aldehydes or ketone are dissolved in ethanol, under 0 ° of C, drip the phenylhydrazine of the replacement of equimolar amount, reaction solution rises to room temperature gradually, continues stirring reaction overnight, removes by filter ethanol, with the solid that the ether washing obtains, is target ligand, and reaction equation is as follows:
Furan Aldehydes or ketone described in step (1) can be 2 furan carboxyaldehyde, 2-acetyl furan, 2-propionyl furans, 2-butyryl radicals furans, 2-benzoyl furans, 2-phenylacetyl furans etc.
The phenylhydrazine that replaces described in step (1) can be 2-chlorophenyl hydrazine, 4-chlorophenyl hydrazine, 2 bromo phenyl hydrazine, 4-bromophenyl-hydrazine, 2,4-dichloro phenyl hydrazine, 2,4-dibromo phenylhydrazine, 2-procarbazine, 4-procarbazine, 2,4-dimethyl hydrazinobenzene, 2-methoxyl group phenylhydrazine, 4-methoxyl group phenylhydrazine, 2,4-dimethoxy phenylhydrazine etc.
(2) preparation of the zirconium metal complexes of Furan Aldehydes (ketone) hydrazone:
In the diethyl ether solution of part Furan Aldehydes (ketone) hydrazone, add the LDA of equimolar amount, the gained yellow solution rises to room temperature gradually, and stirring is spent the night, and stratification removes by filter solvent ether to obtain yellow solid, adds tetrahydrofuran (THF) to dissolve this solid; Under low temperature, slowly drip equimolar amount ZrX again
4Tetrahydrofuran solution, rise to gradually room temperature, the stirring overnight of gained reaction solution; Removal of solvent under reduced pressure, then add the toluene extraction to filter, and filtrate is concentrated places, and can obtain the zirconium metal complexes of Furan Aldehydes (ketone) hydrazone, and reaction equation is:
Title complex of the present invention is as the polymerization of catalyzer for catalyzed ethylene and derivative thereof, and catalytic reaction kettle used with nitrogen, ethylene gas displacement, is in the environment of ethylene gas reaction system successively.At first add solvent toluene, then add successively toluene solution and the promoter aluminium alkyl oxygen alkane of catalyzer, under specified criteria, carry out the catalytic polymerization of ethene, react complete, add the hydrochloric acid termination reaction, the polymkeric substance sedimentation and filtration of formation is collected, use a large amount of washing with alcohol, oven dry, weigh.The molecular weight of gained polyethylene product uses the method for high temperature GPC to measure.
The characteristics such as title complex provided by the invention, have the preparation method simple, and raw materials used cheap and easy to get, productive rate is high, and purifying is easy; Title complex of the present invention forms catalyst system as Primary Catalysts and promoter aluminium alkyl oxygen alkane (as methylaluminoxane MAO etc.), and first Application is in vinyl polymerization, and (weight-average molecular weight is up to 7.3 * 10 to obtain the polyethylene of ultra-high molecular weight
6G/mol), the activity of catalyzer reaches medium, is about 10
5G PE/mol (Zr) h; Widened the field of non-luxuriant transition metal catalyst for olefin polymerization.
The accompanying drawing explanation
The crystalline structure figure of the zirconium metal complexes described in Fig. 1 embodiment 1.
Embodiment
The preparation of embodiment 1 zirconium metal complexes
The preparation of part 2 furan carboxyaldehyde phenylhydrazone:
2 furan carboxyaldehyde (1.92g, 20mmol) is dissolved in the ethanol of 20ml, under 0 ° of C, drips the phenylhydrazine (2.16g, 20mmol) of equimolar amount, reaction solution rises to room temperature gradually, separates out very soon more faint yellow solid, continues stirring reaction overnight.Suction filtration is removed ethanol, and yellow solid obtains faint yellow solid with the ether washing, is part 2 furan carboxyaldehyde phenylhydrazone (2.87g), and productive rate is 77%.
The preparation of the zirconium metal complexes of the tri-chlorination 2 furan carboxyaldehyde phenylhydrazone of tetrahydrofuran (THF) coordination:
Under 0 ° of C, in the approximately 25ml diethyl ether solution of ligand compound 2 furan carboxyaldehyde phenylhydrazone (0.47g, 2.52mmol), add LDA(0.27g, the 2.52mmol of equimolar amount), the suspension of gained yellow rises to room temperature gradually, and stirring is spent the night.Stratification, remove by filter solvent ether, and decompressing and extracting obtains the corresponding lithium salt compound of part.Add afterwards tetrahydrofuran (THF) dissolving lithium salt compound, under-78 ° of C, slowly be added dropwise to ZrCl
4The tetrahydrofuran solution of (0.582g, 2.52mmol), rise to room temperature gradually, and stirring overnight.Removal of solvent under reduced pressure, add the toluene extraction to filter, filtrate is concentrated places, and the solid that obtains is used the tetrahydrofuran (THF) recrystallization again, can obtain the zirconium metal complexes (0.69g) of the tri-chlorination 2 furan carboxyaldehyde phenylhydrazone of amber bar-shaped catalyzer tetrahydrofuran (THF) coordination, productive rate is 52%.
1H?NMR(300MHz,CDCl
3,ppm):δ7.95(s,1H,CH=N),7.51-7.12(m,7H,furanyl-H?and?Ph-H),6.50(s,1H,furanyl-H),4.38(br?s,8H,OCH
2CH
2,THF),1.99(s,8H,OCH
2CH
2,THF),.
13C?NMR(75MHz,CDCl
3,ppm):δ150.6,143.8,113.4,112.1(furanyl-C),145.4,130.3,127.4,124.5(Ph-C),121.5(CH=N),75.2(OCH
2CH
2,THF),26.5(OCH
2CH
2,THF).
The application in catalyzed ethylene polymerization as catalyzer of embodiment 2 title complexs
Polymerizing condition is selected:
Under 10atm, at MAO: the molar weight of catalyzer than for 1000:1 the time, changes temperature, tests respectively 30 ° of C, 50 ° of C, and 70 ° of C, the activity during 90 ° of C, be respectively 0.96 * 10
5, 1.52 * 10
5, 1.96 * 10
5, 0.44 * 10
5GPE/mol (Zr) h.When temperature is 70 ° of C, test respectively MAO: the molar weight ratio of catalyzer is 500:1,1500:1, and the activity during 2000:1, be respectively 0.52 * 10
5, 1.64 * 10
5, 1.52 * 10
5GPE/mol (Zr) h.
1: being aggregated in the stainless steel pressure still that volume is 250ml of ethene carried out, and this autoclave pressure is connected with the ethene steel cylinder of buffering, can pass through the continuous make-up ethylene of spiral shell shape steel pipe, thereby make in polymerization process to keep constant pressure (under 10atm pressure).Polymeric kettle is after abundant drying, and vacuum nitrogen filling gas is replaced three times, and ethene displacement three times, make in reaction flask to be in ethene atmosphere.First inject 50ml toluene, then add successively 20ml to dissolve the toluene solution of zirconium complex (2.6mg, 5 μ mol) and promotor MAO(2ml, 2.4M) make Al/Zr=1000, finally add 28ml toluene, the cumulative volume that makes reaction system is 100ml.Under 30 ° of C, react, after reaction 30min, use the hydrochloric acid termination reaction, the polymkeric substance precipitation that obtains, filter, and uses a large amount of washing with alcohol, and oven dry, obtain product 0.24g, and activity is 0.96 * 10
5GPE/mol (Zr) h.The weight-average molecular weight of resulting polymers is 5.5 * 10
6G/mol, molecular weight distribution is 126.
2: device and concrete operation step are with 1, after making in polymeric kettle to be full of ethene atmosphere, first inject 50ml toluene, add successively again 20ml to dissolve zirconium complex (2.6mg, 5 μ mol) toluene solution, promotor MAO(2ml, 2.4M) make Al/Zr=1000, finally add 28ml toluene, the cumulative volume that makes reaction system is 100ml.Under 50 ° of C, react, after reaction 30min, use the hydrochloric acid termination reaction, the polymkeric substance precipitation that obtains, filter, and uses a large amount of washing with alcohol, and oven dry, obtain product 0.38g, and activity is 1.52 * 10
5GPE/mol (Zr) h.The weight-average molecular weight of resulting polymers is 7.3 * 10
6G/mol, molecular weight distribution is 630.
3: device and concrete operation step are with 1, after making in polymeric kettle to be full of ethene atmosphere, first inject 50ml toluene, add successively again 20ml to dissolve zirconium complex (2.6mg, 5 μ mol) toluene solution, promotor MAO(2ml, 2.4M) make Al/Zr=1000, finally add 28ml toluene, the cumulative volume that makes reaction system is 100ml.Under 70 ° of C, react, after reaction 30min, use the hydrochloric acid termination reaction, the polymkeric substance precipitation that obtains, filter, and uses a large amount of washing with alcohol, and oven dry, obtain product 0.49g, and activity is 1.96 * 10
5GPE/mol (Zr) h.The weight-average molecular weight of resulting polymers is 2.3 * 10
6G/mol, molecular weight distribution is 430.
4: device and concrete operation step are with 1, after making in polymeric kettle to be full of ethene atmosphere, first inject 50ml toluene, add successively again 20ml to dissolve zirconium complex (2.6mg, 5 μ mol) toluene solution, promotor MAO(2ml, 2.4M) make Al/Zr=1000, finally add 28ml toluene, the cumulative volume that makes reaction system is 100ml.Under 90 ° of C, react, after reaction 30min, use the hydrochloric acid termination reaction, the polymkeric substance precipitation that obtains, filter, and uses a large amount of washing with alcohol, and oven dry, obtain product 0.11g, and activity is 0.4 * 10
5GPE/mol (Zr) h.
5: device and concrete operation step are with 1, after making in polymeric kettle to be full of ethene atmosphere, first inject 50ml toluene, add successively again 20ml to dissolve zirconium complex (2.6mg, 5 μ mol) toluene solution, promotor MAO(1ml, 2.4M) make Al/Zr=500, finally add 29ml toluene, the cumulative volume that makes reaction system is 100ml.Under 70 ° of C, react, after reaction 30min, use the hydrochloric acid termination reaction, the polymkeric substance precipitation that obtains, filter, and uses a large amount of washing with alcohol, and oven dry, obtain product 0.13g, and activity is 0.5 * 10
5GPE/mol (Zr) h.
6: device and concrete operation step are with 1, after making in polymeric kettle to be full of ethene atmosphere, first inject 50ml toluene, add successively again 20ml to dissolve zirconium complex (2.6mg, 5 μ mol) toluene solution, promotor MAO(3ml, 2.4M) make Al/Zr=1500, finally add 27ml toluene, the cumulative volume that makes reaction system is 100ml.Under 70 ° of C, react, after reaction 30min, use the hydrochloric acid termination reaction, the polymkeric substance precipitation that obtains, filter, and uses a large amount of washing with alcohol, and oven dry, obtain product 0.41g, and activity is 1.6 * 10
5GPE/mol (Zr) h.The weight-average molecular weight of resulting polymers is 2.57 * 10
6G/mol, molecular weight distribution is 396.
7: device and concrete operation step are with 1, after making in polymeric kettle to be full of ethene atmosphere, first inject 50ml toluene, add successively again 20ml to dissolve zirconium complex (2.6mg, 5 μ mol) toluene solution, promotor MAO(4ml, 2.4M) make Al/Zr=2000, finally add 26ml toluene, the cumulative volume that makes reaction system is 100ml.Under 70 ° of C, react, after reaction 30min, use the hydrochloric acid termination reaction, the polymkeric substance precipitation that obtains, filter, and uses a large amount of washing with alcohol, and oven dry, obtain product 0.38g, and activity is 1.52 * 10
5GPE/mol (Zr) h.The weight-average molecular weight of resulting polymers is 2.4 * 10
6G/mol, molecular weight distribution is 744.
Claims (3)
1. the zirconium metal complexes of a Furan Aldehydes (ketone) hydrazone, is characterized in that, structural formula is as follows:
Wherein: R
1For hydrogen, or be selected from alkyl, aryl, alkaryl, the alkoxyl group of 1-10 carbon atom; R
2, R
3Be respectively independently of one another hydrogen, halogen, or be selected from alkyl, aryl, alkaryl, the alkoxyl group of 1-10 carbon atom; X is halogen or alkyl.
2. the preparation method of the zirconium metal complexes of a kind of Furan Aldehydes as claimed in claim 1 (ketone) hydrazone, is characterized in that, comprises the steps:
(1) Furan Aldehydes or ketone are dissolved in ethanol, under 0 ° of C, drip the phenylhydrazine of the replacement of equimolar amount, reaction solution rises to room temperature gradually, continues stirring reaction overnight, removes by filter ethanol, with the solid that the ether washing obtains, is part Furan Aldehydes (ketone) hydrazone;
(2) in the diethyl ether solution of part Furan Aldehydes (ketone) hydrazone, add the LDA of equimolar amount, the gained yellow solution rises to room temperature gradually, and stirring is spent the night, and stratification removes by filter solvent ether to obtain yellow solid, adds tetrahydrofuran (THF) to dissolve this solid; Under low temperature, slowly drip equimolar amount ZrX again
4Tetrahydrofuran solution, rise to gradually room temperature, the stirring overnight of gained reaction solution; Removal of solvent under reduced pressure, then add the toluene extraction to filter, and filtrate is concentrated places, and can obtain the zirconium metal complexes of Furan Aldehydes (ketone) hydrazone.
3. zirconium metal complexes application in preparing ultrahigh molecular weight polyethylene(UHMWPE) as catalyzer of Furan Aldehydes as claimed in claim 1 (ketone) hydrazone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310298115.9A CN103396428B (en) | 2013-07-16 | 2013-07-16 | Zirconium metal complex of furan aldehyde (ketone) hydrazone as well as preparation method and application of zirconium metal complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310298115.9A CN103396428B (en) | 2013-07-16 | 2013-07-16 | Zirconium metal complex of furan aldehyde (ketone) hydrazone as well as preparation method and application of zirconium metal complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103396428A true CN103396428A (en) | 2013-11-20 |
| CN103396428B CN103396428B (en) | 2015-04-15 |
Family
ID=49560195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310298115.9A Expired - Fee Related CN103396428B (en) | 2013-07-16 | 2013-07-16 | Zirconium metal complex of furan aldehyde (ketone) hydrazone as well as preparation method and application of zirconium metal complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103396428B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503939A (en) * | 2016-01-08 | 2016-04-20 | 山西大学 | O-methoxy phenylhydrazone dicaryon metal complex and preparation method and application thereof |
| CN106633093A (en) * | 2016-12-06 | 2017-05-10 | 商洛学院 | N-(2-isopropyl) para hydroxybenzene carbonylhydrazone lead complex, and preparation method and application thereof |
| CN113816980A (en) * | 2021-08-04 | 2021-12-21 | 青岛科技大学 | Synthesis method of zirconium and hafnium metal catalyst and application of zirconium and hafnium metal catalyst in preparation of ultrahigh molecular weight polyethylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635728B2 (en) * | 2002-01-10 | 2003-10-21 | Equistar Chemicals, Lp | Preparation of ultra-high-molecular-weight polyethylene |
| CN101274939A (en) * | 2008-05-16 | 2008-10-01 | 华东理工大学 | Novel beta-diketiminato zirconium compound, preparation thereof and application thereof |
| CN101274940A (en) * | 2008-05-16 | 2008-10-01 | 华东理工大学 | Novel bridged beta-diketiminato zirconium compound, preparation thereof and application thereof |
-
2013
- 2013-07-16 CN CN201310298115.9A patent/CN103396428B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635728B2 (en) * | 2002-01-10 | 2003-10-21 | Equistar Chemicals, Lp | Preparation of ultra-high-molecular-weight polyethylene |
| CN101274939A (en) * | 2008-05-16 | 2008-10-01 | 华东理工大学 | Novel beta-diketiminato zirconium compound, preparation thereof and application thereof |
| CN101274940A (en) * | 2008-05-16 | 2008-10-01 | 华东理工大学 | Novel bridged beta-diketiminato zirconium compound, preparation thereof and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503939A (en) * | 2016-01-08 | 2016-04-20 | 山西大学 | O-methoxy phenylhydrazone dicaryon metal complex and preparation method and application thereof |
| CN106633093A (en) * | 2016-12-06 | 2017-05-10 | 商洛学院 | N-(2-isopropyl) para hydroxybenzene carbonylhydrazone lead complex, and preparation method and application thereof |
| CN106633093B (en) * | 2016-12-06 | 2019-12-17 | 商洛学院 | n- (2-isopropyl acid) p-hydroxybenzoyl hydrazone lead complex as well as preparation method and application thereof |
| CN113816980A (en) * | 2021-08-04 | 2021-12-21 | 青岛科技大学 | Synthesis method of zirconium and hafnium metal catalyst and application of zirconium and hafnium metal catalyst in preparation of ultrahigh molecular weight polyethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103396428B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Appukuttan et al. | Stereospecific polymerizations of 1, 3-butadiene catalyzed by Co (II) complexes ligated by 2, 6-bis (benzimidazolyl) pyridines | |
| CN103842394B (en) | For preparing the catalyst of ultra-high molecular weight polyethylene (UHMWPE) | |
| CN108250252B (en) | Bridged metallocene compound containing heterocyclic structure and preparation method and application thereof | |
| Wang et al. | Chain-walking polymerization of linear internal octenes catalyzed by α-diimine nickel complexes | |
| CN107641138A (en) | For ethene and the asymmetric α diimine nickels containing the substitution of ortho position benzhydryl of 1 hexene oligomerization（Ⅱ）Complex | |
| Damavandi et al. | Novel Ni-based FI catalyst for ethylene polymerization | |
| CN105482000A (en) | Olefin polymerization catalyst as well as preparation method and application method thereof | |
| CN105481998A (en) | Olefin polymerization catalyst as well as preparation method and application method thereof | |
| CN103396428B (en) | Zirconium metal complex of furan aldehyde (ketone) hydrazone as well as preparation method and application of zirconium metal complex | |
| CN109957049B (en) | Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof | |
| CN113321679B (en) | [ NNNN ] tetradentate ligand fourth subgroup metal complex and application thereof | |
| CN109956980B (en) | Ethylidene acenaphthene asymmetric alpha-diimine nickel catalyst and preparation method and application thereof | |
| CN109956979B (en) | Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof | |
| JP6664375B2 (en) | Olefin polymerization catalyst and method for producing olefin oligomer | |
| CN102887969B (en) | Non-metallocene bimetal catalysis system for synthesizing branched polyethylene and application thereof | |
| KR101262333B1 (en) | Post-metallocene complexes based on bis(naphtoxy)pyridine and bis(naphtoxy)thiophene ligands for the polymerisation of ethylene and alpha-olefins | |
| CN106317126B (en) | Benzene oxygen 2- imine imidazole alkane metal complex and its preparation method and application | |
| CA2365954A1 (en) | Polymerization of ethylene | |
| CN108530492B (en) | Bridged dinuclear metallocene compound and preparation method and application thereof | |
| JP5186559B2 (en) | Novel tridentate ligand compound having an iminofuran unit, a process for the preparation of this compound and its use in the preparation of catalysts for the homopolymerization of ethylene and copolymerization with α-olefins | |
| Khoshsefat et al. | Practical and theoretical study on the α-substituent effect on α-diimine Nickel (II) and Cobalt (II)-based catalysts for polymerization of ethylene | |
| Liu et al. | Neutral nickel complexes chelating monoamidinate ligands: Syntheses, characterizations and catalytic properties toward ethylene oligomerization and norbornene polymerization | |
| CN101880338B (en) | Beta-hydroxy imine titanium metal catalyst and method for polymerizing ethylene | |
| CN108822237A (en) | A kind of pyridine imine palladium（Ⅱ）The method that catalyst preparation and catalysis ethylene prepare oily phase oligomer | |
| CN105503939A (en) | O-methoxy phenylhydrazone dicaryon metal complex and preparation method and application thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150415 Termination date: 20170716 |