CN105199025A - Ruthenium catalyst used for norbornene polymerization and preparation method thereof - Google Patents
Ruthenium catalyst used for norbornene polymerization and preparation method thereof Download PDFInfo
- Publication number
- CN105199025A CN105199025A CN201510540853.9A CN201510540853A CN105199025A CN 105199025 A CN105199025 A CN 105199025A CN 201510540853 A CN201510540853 A CN 201510540853A CN 105199025 A CN105199025 A CN 105199025A
- Authority
- CN
- China
- Prior art keywords
- ruthenium catalyst
- preparation
- polymerization
- norbornene
- norbornene polymerization
- 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
Abstract
The invention discloses a ruthenium catalyst used for norbornene polymerization and a preparation method thereof. The novel ruthenium catalyst is formed by uthenium trichloride and phosphorus ligands through a complex reaction, and the ruthenium catalyst is purified through recrystallization. The ruthenium catalyst and the preparation method have the advantages that the preparation method of the catalyst is easy and convenient to operate, the catalysis efficiency is high, the production cost is reduced, the obtained polymers have excellent electrical performance, high thermal stability and the like, and the development of the olefin polymerization industry is promoted.
Description
Technical field
The present invention relates to the ruthenium catalyst and preparation method thereof of a class for norbornene polymerization; Norbornene polymer is a kind of polymkeric substance of unique properties, is applied to microelectronic device, liquid-crystal display supercoat, the aspects such as resistant to elevated temperatures protective material; Belong to meticulous field of chemical technology.
Background technology
Norbornene polymer is a kind of polymkeric substance of unique properties, there is excellent electrical property, extremely low water absorbability, good thermostability, higher tension fracture value and low-tension, to metal, there is good adhesive, very strong anti-ultraviolet radiation ability, excellent optical property, is therefore widely used in each department of national economy.In recent years, China starts to be studied norbornene polymerization, flourish in the whole nation so far, except norbornylene, the polymerization of some norbornene derivatives also in fast development, to meet the industrial demand to this type of material.
Metal ruthenium catalyst is the catalyzer that a class is comparatively early applied on norbornene polymerization, and as far back as eighties of last century seventies, the external ruthenium trichloride catalyst application that just used, in production norbornylene suitability for industrialized production, has defined comparatively ripe production technique.
In addition, metal ruthenium catalyst has higher catalytic activity in norbornene polymerization reaction, and polymericular weight can reach hundreds of thousands of, even millions of.Its polymerization product has good thermostability, excellent electrical property and optical property etc., so metal ruthenium catalyst still has good development and application prospect for the polymerization of norbornylene.But along with the industrial requirement to norbornene polymer performance is more and more higher, the polymkeric substance that former catalyzer obtains is difficult to the demand meeting people.Therefore, the more excellent catalyzer of performance is developed to produce norbornene polymer with regard to needing.
In order to solve the problem, design and synthesis of the present invention one class is used for the ruthenium catalyst of norbornene polymerization, and this catalyzer not yet reports at present.
Summary of the invention
The invention discloses the ruthenium catalyst and preparation method thereof of a class for norbornene polymerization.Find in our study, the polymer performance that raw catalyst obtains is better.
The invention provides the ruthenium catalyst of a class for norbornene polymerization,
A described class is used for the ruthenium catalyst of norbornene polymerization, it is characterized in that, comprises the steps: that hydrate ruthenium trichloride and phosphorus part join in reaction vessel by the first step, add ethanolic soln, uniform stirring under reflux temperature, the reaction times is 1h, is purified by gained solid ethyl alcohol recrystallization.Second step will products therefrom and phosphorus part continue to react in ethanolic soln before, add potassium hydroxide, stop after reaction 4h.Purify with ethyl alcohol recrystallization and obtain target product.
Embodiment
The ruthenium catalyst of the novel norbornene polymerization of a class as described above is for having good catalytic activity in the middle of the polymerization of norbornylene, and the polymkeric substance obtained has excellent electrical property, and good thermostability etc., facilitates the development of olefinic polymerization industry.Below, applicant is to invention has been specific experiment, and the ruthenium catalyst describing the novel norbornene polymerization of a class in detail is applied in the experimentation in the middle of norbornene polymerization.These only for elaborating the present invention, and limit scope of invention never in any form.
Embodiment one: one class is used for ruthenium catalyst of norbornene polymerization and preparation method thereof, comprises following processing step:
Hydrate ruthenium trichloride (0.100g) and thricyclohexyl phosphorus (15mmol) are joined in reaction vessel, add 30mL dehydrated alcohol, uniform stirring under reflux temperature, filters after stopped reaction after reaction 1h, is purified by gained solid ethyl alcohol recrystallization.Continuation previous step gained three thricyclohexyl phosphorus ruthenous chloride and triphenyl phosphorus react in ethanol, add potassium hydroxide, stop after reaction 4h, and purifying with ethyl alcohol recrystallization obtains target product.
Productive rate: 69%.
Gained sterling is applied in the middle of norbornene polymerization, add the norbornylene solution (1.5mmol) for preparing in advance in reactor, add q. s. toluene solvent, add ruthenium catalyst (1.5umol), be warming up to 70 DEG C, stop after polymerase 10 .5h, joined by reaction solution in the middle of ethanol, adularescent jelly generates, by washing with alcohol three times, obtain norbornene polymer, transformation efficiency is 84%.Through GPC, to record polymkeric substance Mn be 240526, Mn/Mw is 1.14.
Embodiment two: one class is used for ruthenium catalyst of norbornene polymerization and preparation method thereof, comprises following processing step:
Hydrate ruthenium trichloride (0.100g) and diphenylcyclo base phosphorus (15mmol) are joined in reaction vessel, add 30mL dehydrated alcohol, uniform stirring under reflux temperature, filters after stopped reaction after reaction 1h, is purified by gained solid ethyl alcohol recrystallization.Continuation previous step product and diphenylcyclo base phosphorus react in ethanol, add potassium hydroxide, stop after reaction 3h, and purifying with ethyl alcohol recrystallization obtains target product.
Productive rate: 74%.
Gained sterling is applied in the middle of norbornene polymerization, add the norbornylene solution (1.5mmol) for preparing in advance in reactor, add q. s. toluene solvent, add ruthenium catalyst (1.5umol), be warming up to 70 DEG C, stop after polymerization 1h, joined by reaction solution in the middle of ethanol, adularescent jelly generates, by washing with alcohol three times, obtain norbornene polymer, transformation efficiency is 76%.Through GPC, to record polymkeric substance Mn be 264524, Mn/Mw is 1.60.
Claims (2)
1. the invention provides the ruthenium catalyst and preparation method thereof of a class for norbornene polymerization.
2. a class described in is used for the ruthenium catalyst of norbornene polymerization, it is characterized in that, comprises the steps: that hydrate ruthenium trichloride and phosphorus part join in reaction vessel by the first step, add ethanolic soln, uniform stirring under reflux temperature, the reaction times is 1h, is purified by gained solid ethyl alcohol recrystallization.Second step will products therefrom and phosphorus part continue to react in ethanolic soln before, add potassium hydroxide, stop after reaction 4h.Purify with ethyl alcohol recrystallization and obtain target product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510540853.9A CN105199025A (en) | 2015-08-28 | 2015-08-28 | Ruthenium catalyst used for norbornene polymerization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510540853.9A CN105199025A (en) | 2015-08-28 | 2015-08-28 | Ruthenium catalyst used for norbornene polymerization and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105199025A true CN105199025A (en) | 2015-12-30 |
Family
ID=54947007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510540853.9A Pending CN105199025A (en) | 2015-08-28 | 2015-08-28 | Ruthenium catalyst used for norbornene polymerization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105199025A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189784A (en) * | 1996-04-30 | 1998-08-05 | 阿莫科公司 | Ruthenium-based catalyst system for olefin metathesis |
| CN1244199A (en) * | 1996-11-15 | 2000-02-09 | 加州理工学院 | Synthesis of ruthenium or osmium metathesis catalysts |
| CN104371044A (en) * | 2013-12-19 | 2015-02-25 | 上海克琴化工科技有限公司 | Preparation of ruthenium metal catalyst and application of ruthenium metal catalyst in ring-opening metathesis polymerization |
-
2015
- 2015-08-28 CN CN201510540853.9A patent/CN105199025A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189784A (en) * | 1996-04-30 | 1998-08-05 | 阿莫科公司 | Ruthenium-based catalyst system for olefin metathesis |
| CN1244199A (en) * | 1996-11-15 | 2000-02-09 | 加州理工学院 | Synthesis of ruthenium or osmium metathesis catalysts |
| CN104371044A (en) * | 2013-12-19 | 2015-02-25 | 上海克琴化工科技有限公司 | Preparation of ruthenium metal catalyst and application of ruthenium metal catalyst in ring-opening metathesis polymerization |
Non-Patent Citations (2)
| Title |
|---|
| 乐传俊: "钌氢配合物合成及其催化氢转移反应研究", 《中国博士学位论文全文数据库（电子期刊） 工程科技I辑》 * |
| 顾珊珊等: "钌金属配合物催化的丁香酚双键异构反应", 《香料香精化妆品》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ryken et al. | N, O-chelating four-membered metallacyclic titanium (IV) complexes for atom-economic catalytic reactions | |
| CN102827312B (en) | Ethylidene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof | |
| CN104211726B (en) | The tooth double-core titanium complex of non-luxuriant class three, Preparation method and use | |
| CN102827311B (en) | Binuclear acenaphthene (alpha-diimine) nickel/palladium catalysts for olefins, and preparation method and application thereof | |
| CN104511311A (en) | High-selectivity catalyst system used in trimerization and tetramerization of ethylene and use method thereof | |
| CN103087223B (en) | O/p-phenethyl substituted acenaphthene alpha-diimine nickel (II) olefin polymerization catalyst and preparation and application thereof | |
| CN106488923A (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising this compound | |
| CN109364993B (en) | For catalytic conversion of CO at normal pressure2Polyion liquid catalyst and preparation method thereof | |
| CN104923299A (en) | Ruthenium catalysts used for catalyzing acetophenone for producing alpha-phenylethanol, and preparation method thereof | |
| Klosin et al. | Preparation of New Olefin Polymerization Precatalysts by Facile Derivatization of Imino–Enamido ZrMe3 and HfMe3 Complexes | |
| CN109956979B (en) | Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof | |
| CN101348502B (en) | 2-benzimidazole-1,10-phenanthroline transient metal complex, and preparation and use thereof | |
| CN105037588A (en) | Isoindole rare earth metal catalyst, preparation method and application | |
| CN104628596A (en) | Symmetrical alpha-diimine nickel complex catalyst as well as preparation method and application thereof | |
| CN105199025A (en) | Ruthenium catalyst used for norbornene polymerization and preparation method thereof | |
| Liu et al. | Chromium-based complexes bearing N-substituted diphosphinoamine ligands for ethylene oligomerization | |
| CN108864327A (en) | 5,6- dimethyl acenaphthene（Alpha-diimine）Nickel alkene catalyst and its preparation and application | |
| CN104231003B (en) | Bridging indenes fluorenes zirconium, hafnium compound and preparation method and the application in oligomerization of propene | |
| CN103333277B (en) | Two amidino groups methoxyl group bridged binuclear Zr catalyst and its preparation method and application | |
| CN105968238B (en) | A kind of combination catalyst for norbornene polymerization and preparation method thereof | |
| CN101245117B (en) | Method for producing verelite with [O,N] type catalyst of bidentate ligand coordinated with post-transition metal | |
| CN100465195C (en) | Beta-hydroxy propyleneimine vanadium olefinic polymerization catalyst and its preparation method and uses | |
| CN102631946B (en) | IVB group (N, N, O, O) complex olefin polymerization catalyst, preparation method thereof and application | |
| CN102603935B (en) | Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof | |
| KR20120092977A (en) | New transition metal compound, new organic ligand compound, catalysts composition comprising the transition metal compound and preparation method of poly-olefin using the catalysts composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151230 |
|
| WD01 | Invention patent application deemed withdrawn after publication |