CN101619078A - Metal organic complex with catalytic activity and preparation method thereof - Google Patents
Metal organic complex with catalytic activity and preparation method thereof Download PDFInfo
- Publication number
- CN101619078A CN101619078A CN200910012790A CN200910012790A CN101619078A CN 101619078 A CN101619078 A CN 101619078A CN 200910012790 A CN200910012790 A CN 200910012790A CN 200910012790 A CN200910012790 A CN 200910012790A CN 101619078 A CN101619078 A CN 101619078A
- Authority
- CN
- China
- Prior art keywords
- solid
- cod
- catalytic activity
- complex
- metal organic
- 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.)
- Pending
Links
Images
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
- Catalysts (AREA)
Abstract
The invention provides a metal organic complex with catalytic activity and a preparation method thereof, relating to the chemical fields of metal organic catalyst and high molecular material. A novel metal organic catalyst Pd (SIMes) (Cl) (COD) which is used for catalyzing DCPD is synthesized by the following steps: taking N-heterocyclic carbine and COD as ligand, taking palladium ion as central atom, coordinating with the central ion palladium by changing the volume ratio of ligand and sequencing collaboration to obtain the complex. The novel complex has definite structure and catalytic activity which can catalyze PDCPD reaction; as the new structure in the invention is substantially similar to some structures of ruthenium, meanwhile, as palladium (II) and ruthenium (II) have substantially similar properties, the invention can lower cost when used in olefin polymerization compared with expensive ruthenium.
Description
Technical field
The invention belongs to chemical field (orgnometallic catalyst), particularly DPCP (dicyclopentadiene) polymerization reaction take place under this orgnometallic catalyst effect produces this resinous polymer that can widespread use of PDCPD (polydicyclopentadiene).
Background technology
Dicyclopentadiene (dicyclopentadiene is called for short DCPD) is the by product of petroleum cracking system ethene and coal coking.Owing to contain two unsaturated double-bonds simultaneously in the dicyclopentadiene molecular structure, cause its chemical property very active.It is the up-to-date focus of domestic and international researchdevelopment at polymeric material field as the application in unsaturated polyester resin, dicyclopentadiene-phenol resin, dicyclopentadiene material, Resins, epoxy, optics pmma material, the engineering plastics.At present increasing at the sales volume of the resin of the DCPD of developed country, all there is this series products in the nearly all resin processing plant of the U.S., and the resin processing plant in Japan and Taiwan is also all at production DCPD resin.Because its polymer P DCPD product has outstanding transparency, thermotolerance and high rigidity and highly purified advantage, by widely as optical lens material, shower house, bathtub, farm machinery, the application of boats and ships top shell etc.At present, the main main method of synthetic PDCPD is the orgnometallic catalyst catalyzed polymerization on the market.Along with the development of catalyzer such as Grubbs, the catalyzer of nitrogen heterocycle carbine ligand more and more is applied to this.We synthesize the Pt compound of having developed the nitrogen heterocyclic ring part, and prove that it has catalysis DCPD polymeric activity.It is compared with the ruthenium compound of widespread use on the market, and to have synthetic method simple, and compound property is more stable, and the very similar feature of catalytic activity.
Summary of the invention
The aza ring carbene complex Pd (SIMes) that the object of the present invention is to provide a kind of palladium is the preparation method and the condition of (COD) (Cl), stresses the proportioning of each component in this title complex.Because palladium (II) is extremely similar to ruthenium (II) character, its structure has the effect of the catalytic polymerization that ruthenium (II) had, thereby compares unstable and valuable ruthenium (II) class title complex, and the present invention has reduced cost, has increased the accessibility of use.
The objective of the invention is to be achieved through the following technical solutions:
A metal-organic complex with catalytic activity, the structural formula of this title complex is as follows:
Preparation method with a metal-organic complex of catalytic activity, the building-up reactions of a metal-organic complex is carried out under the anhydrous and oxygen-free condition, its described method comprises following process: take by weighing palladium tetrachloride and be dissolved in the dry toluene, 1.5 equivalent COD are mixed with it, 80 ℃ of reactions 5 hours, evaporating solvent after have solid to separate out, cooling, filter, washing, obtain PdCl2 (COD) solid; Take by weighing carbene precursor and be dissolved in the exsiccant toluene, make it with mol ratio TlOEt reaction, stir and produce Cabbeen; Take by weighing PdCl2 (COD) solid and be dissolved in the dry toluene, transfer in the carbene reaction device, stir back, evaporating solvent to there being solid to separate out; Do not separate out to there being solid again at the refrigerator internal cooling, filter, wash, obtain (Cl) (COD) solid of Pd (SIMes).
Description of drawings
Accompanying drawing of the present invention is for having catalytically-active metals organic coordination compound structure iron.
Embodiment
Below the present invention is described in detail:
The aza ring carbene complex Pd (SIMes) of palladium of the present invention is the method and the condition of (COD) (Cl).Metal-organic building-up reactions requires to carry out under the anhydrous and oxygen-free condition.Take by weighing palladium tetrachloride (0.001mol) and be dissolved in the 10ml dry toluene, 1.5 equivalent COD are mixed with it, 80 ℃ of reactions 5 hours, evaporating solvent cool off 1 hour after have solid to separate out, and filtered, and washed, and obtained PdCl2 (COD) solid.Take by weighing carbene precursor (0.0011mol) and be dissolved in the 10ml exsiccant toluene, make it with mol ratio TlOEt reaction, stirs 15-20 minute generation Cabbeen.Take by weighing PdCl2 (COD) solid (0.001mol) and be dissolved in the 10ml dry toluene, transfer in the carbene reaction device, stir after 2 hours, evaporating solvent is after have solid to separate out.Do not separate out to there being solid again at the refrigerator internal cooling, filter, washing obtains (Cl) (COD) solid of Pd (SIMes).Because some title complex of its new structure and ruthenium and similar, and palladium has extremely similar character to ruthenium, as everyone knows, ruthenium has obtained using widely in catalysed olefin polymerization, and play a good role, the new title complex that we made is tested, and proves its catalytic activity.
The present invention is because extremely similar of its some structure of new structure and ruthenium has extremely similar character owing to palladium (II) to ruthenium (II) simultaneously, and for valuable ruthenium metal, this invention is used in the olefinic polymerization and will be reduced cost.
Metal-organic building-up reactions requires to carry out under the anhydrous and oxygen-free condition in present method.With COD as first part, with N-heterocyclic carbine as second part, with Palladous chloride (II) as central ion.At first take by weighing a certain amount of Palladous chloride and be dissolved in the 10ml dry toluene, more a certain amount of COD is added in this solution, make it to react 5 hours at 80 ℃.Evaporating solvent cooled off 1 hour after have solid to separate out then, filtered, and washing obtains PdCl2 (COD) solid.Before adding the second part N-heterocyclic carbine, online preparation Cabbeen.Take by weighing a certain amount of carbene precursor and be dissolved in the 10ml exsiccant toluene, make it reaction, stir and produced Cabbeen in 15-20 minute with 1.1 mol ratio TlOEt.Front system PdCl2 (COD) solid take by weighing and the same molar weight of Cabbeen, and be dissolved in toluene solvant, be added in the Cabbeen solution stirring reaction 2 hours then.Evaporating solvent is after have solid to separate out then.Do not separate out to having solid again at the refrigerator internal cooling, filter, use dry hexane wash, obtain (Cl) (COD) solid of Pd (SIMes).And characterize with means such as NMR.
With DCPD is that substrate carries out the polyreaction test, proves the catalytic activity that it has catalysis DPCPD polyreaction.
Claims (2)
1. have a metal-organic complex of catalytic activity, it is characterized in that, the structural formula of this title complex is as follows:
2. the preparation method who has a metal-organic complex of catalytic activity, the building-up reactions of a metal-organic complex is carried out under the anhydrous and oxygen-free condition, it is characterized in that described method comprises following process: take by weighing palladium tetrachloride and be dissolved in the dry toluene, 1.5 equivalent COD are mixed with it, 80 ℃ of reactions 5 hours, evaporating solvent after have solid to separate out, cooling, filter, washing, obtain PdCl2 (COD) solid; Take by weighing carbene precursor and be dissolved in the exsiccant toluene, make it with mol ratio TlOEt reaction, stir and produce Cabbeen; Take by weighing PdCl2 (COD) solid and be dissolved in the dry toluene, transfer in the carbene reaction device, stir back, evaporating solvent to there being solid to separate out; Do not separate out to there being solid again at the refrigerator internal cooling, filter, wash, obtain (Cl) (COD) solid of Pd (SIMes).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910012790A CN101619078A (en) | 2009-07-29 | 2009-07-29 | Metal organic complex with catalytic activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910012790A CN101619078A (en) | 2009-07-29 | 2009-07-29 | Metal organic complex with catalytic activity and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101619078A true CN101619078A (en) | 2010-01-06 |
Family
ID=41512497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910012790A Pending CN101619078A (en) | 2009-07-29 | 2009-07-29 | Metal organic complex with catalytic activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101619078A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588681A (en) * | 2013-11-14 | 2014-02-19 | 沈阳化工大学 | Pd (palladium) (II) coordination compound and preparation method thereof |
| CN105693776A (en) * | 2016-03-08 | 2016-06-22 | 沈阳化工大学 | Crystals of cage-like Ru metal-organic complexes and preparation method of crystals |
-
2009
- 2009-07-29 CN CN200910012790A patent/CN101619078A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588681A (en) * | 2013-11-14 | 2014-02-19 | 沈阳化工大学 | Pd (palladium) (II) coordination compound and preparation method thereof |
| CN103588681B (en) * | 2013-11-14 | 2015-07-29 | 沈阳化工大学 | A kind of palladium (II) coordination compound and preparation method thereof |
| CN105693776A (en) * | 2016-03-08 | 2016-06-22 | 沈阳化工大学 | Crystals of cage-like Ru metal-organic complexes and preparation method of crystals |
| CN105693776B (en) * | 2016-03-08 | 2018-03-13 | 沈阳化工大学 | Caged ruthenium Function for Organometallic Complex Crystals and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Prechtl et al. | H/D exchange at aromatic and heteroaromatic hydrocarbons using D2O as the deuterium source and ruthenium dihydrogen complexes as the catalyst | |
| Zhu et al. | Chiral metal–organic framework as a platform for cooperative catalysis in asymmetric cyanosilylation of aldehydes | |
| Cai et al. | Fine-tuning nickel phenoxyimine olefin polymerization catalysts: performance boosting by alkali cations | |
| Halbach et al. | Novel ruthenium-based metathesis catalysts containing electron-withdrawing ligands: synthesis, immobilization, and reactivity | |
| Nakano et al. | Copolymerization of epoxides with carbon dioxide catalyzed by iron–corrole complexes: synthesis of a crystalline copolymer | |
| Krause et al. | Synthesis and reactivity of homogeneous and heterogeneous ruthenium‐based metathesis catalysts containing electron‐withdrawing ligands | |
| Fan et al. | Highly effective and recyclable dendritic BINAP ligands for asymmetric hydrogenationElectronic supplementary information (ESI) available:(A) characterisation of dendritic ligands and in situ catalysts;(B) time-dependent conversion of 8 catalysed by dendritic catalysts. See http://www. rsc. org/suppdata/cc/b0/b001503m | |
| Durand et al. | The role of nitrogen-donor ligands in the palladium-catalyzed polyketones synthesis | |
| Polborn et al. | Molecular imprinting with an organometallic transition state analogue | |
| Suarez et al. | Rh-mediated C1-polymerization: copolymers from diazoesters and sulfoxonium ylides | |
| CN102432640A (en) | Half-sandwiched iridium (Ir) and rhodium (Rh) compound having carborane-amidine-containing structure, and preparation method and application of half-sandwiched Ir and Rh compound | |
| Madhavan et al. | Highly Active Polymer‐Supported (Salen) Al Catalysts for the Enantioselective Addition of Cyanide to α, β‐Unsaturated Imides | |
| Dulai et al. | C-substituted bis (diphenylphosphino) methane-type ligands for chromium-catalyzed selective ethylene oligomerization reactions | |
| CN102190583A (en) | Method for synthesizing low carbon alcohol ester of acrylic acid by catalyzing acetylene carbonyl through palladium-phosphine complex | |
| CN105764611A (en) | Catalyst systems for use in continuous flow reactors and methods of manufacture and use thereof | |
| Gerber et al. | Synthesis of Methylidene Complexes that Contain a 2, 6-Dimesitylphenylimido Ligand and Ethenolysis of 2, 3-Dicarbomethoxynorbornadiene | |
| Kim et al. | Halide-free and bifunctional one-component catalysts for the coupling of carbon dioxide and epoxides | |
| CN101619078A (en) | Metal organic complex with catalytic activity and preparation method thereof | |
| Liang et al. | Generation of self‐supported Noyori‐type catalysts using achiral bridged‐BIPHEP for heterogeneous asymmetric hydrogenation of ketones | |
| Ullah Khan et al. | Recent Advances in Transition Metal‐Based Catalysts for Ethylene Copolymerization with Polar Comonomer | |
| Lv et al. | Progress of Azametallacyclopentadienes in the New Century | |
| Campos-Carrasco et al. | Cationic palladium (II) complexes for CO/vinyl arene copolymerization in the presence of carbon dioxide | |
| Gámez‐Rivera et al. | Mononuclear Ruthenium and Osmium Complexes with a Bicyclic Guanidinate Ligand: Synthesis and Catalytic Behavior in Olefin Isomerization Processes | |
| Wang et al. | Revealing the role of hydrogen bond, mechanism and kinetic for hydroesterification of ethylene to methyl propionate | |
| Bie et al. | Studies on Alternating Copolymerization of Ethylene and Carbon Monoxide Using Nickel‐Based Catalyst: Cocatalyst and the Polarity of Solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100106 |