CN105061255A - Series of asymmetric double-Schiff base mononuclear copper complexes, and preparation method and application thereof - Google Patents
Series of asymmetric double-Schiff base mononuclear copper complexes, and preparation method and application thereof Download PDFInfo
- Publication number
- CN105061255A CN105061255A CN201510450415.3A CN201510450415A CN105061255A CN 105061255 A CN105061255 A CN 105061255A CN 201510450415 A CN201510450415 A CN 201510450415A CN 105061255 A CN105061255 A CN 105061255A
- Authority
- CN
- China
- Prior art keywords
- schiff base
- dissymmetrical
- copper compound
- butyl
- bis
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A series of asymmetric double-Schiff base mononuclear copper compounds have the structural formula shown in the description. A preparation method of the series of asymmetric double-Schiff base mononuclear copper compounds includes the following steps: 1) preparation of (E)-2-((2-amino-aniline)-methyl)-4,6-2-tert-butyl-phenol; 2) preparation of an intermediate; and 3) preparation of the asymmetric double-Schiff base mononuclear copper compounds; an application of the series of asymmetric double-Schiff base mononuclear copper compounds as catalysts in a styrene free radical polymerization reaction; the method for preparing the asymmetric double-Schiff base mononuclear copper complexes by using a copper metal ion template method is provided, the asymmetric double-Schiff base mononuclear copper complexes as the catalysts are used the olefin free radical polymerization reaction; the catalysts are higher in activity, and can effectively catalyze styrene monomer polymerization.
Description
Technical field
The invention belongs to technical field of organic chemistry, be specifically related to a series of dissymmetrical double Schiff base Cu title complex, its preparation method and application.
Background technology
Based on the metallic compound of dissymmetrical double Schiff base, especially late transition metal compound (as copper complex), as catalyzer in the application of catalytic polymerization, is subject to showing great attention to of domestic and international scientist in recent years.In olefinic polymerization, due to the character of its uniqueness, as oxytropism is little, good etc. to polar monomer tolerance, be the novel catalyzer of the class of rising after Ziegler-Natta catalyst, metallocene catalyst.Its structure is similar to metallocene compound, and can modify its structure neatly, thus in catalyzed polymerization, show good characteristic.Except having the feature of metallocene catalyst, as single active center, beyond the features such as resulting polymers narrow molecular weight distribution, also there is high reactivity and good cutting out property of molecule, by regulating microstructure or the polymerization process condition such as temperature, pressure of catalyzer, molecular designing and the assembling of olefin polymer can be realized on molecular level, realize the adjustable and controlled of polymer physics character.Therefore the application of novel double-Schiff base metal complexes in catalyzed polymerization field becomes one of the study hotspot in Polymer Synthesizing field day by day, has wide tempting prospect.
The present invention develop a series of there is Schiff base structure presoma and Cu metal ion carry out the styrene polymerization catalyzer of four tooth Asymmetry coordinations, the advantages such as its metal complex catalysts has that preparation is simple, stable performance, catalytic performance are good.Can this Schiff Cu metal complexes be catalyzer, Diisopropyl azodicarboxylate, benzoyl peroxide or persulphate be initiator, make vinylbenzene generation homopolymerization, obtain the random polystyrene of rule between being rich in.
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art, the object of the invention is to propose a series of dissymmetrical double Schiff base Cu title complex, its preparation method and application, tool has the presoma of Schiff base structure and Cu metal ion to carry out coordination and obtains intermediate, be that template can prepare the catalyzer of dissymmetrical double Schiff base monokaryon copper compound as styrene polymerization with intermediate, have that preparation is simple, stable performance, advantage that catalytic performance is good, have a extensive future.
For achieving the above object, the technical solution used in the present invention is: serial dissymmetrical double Schiff base Cu title complex, and its structure expression is as shown in (I):
The mol ratio of described O-Phenylene Diamine and 3,5-, bis--tert-butyl-salicylaldehyde is 1 ~ 3:1.
Described alcohol is anhydrous methanol or ethanol.
A kind of serial dissymmetrical double Schiff base Cu title complex
preparationmethod, comprises the following steps:
1) prepare (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol as presoma (
hL)
At ambient temperature, O-Phenylene Diamine and 3,5-, bis--tert-butyl-salicylaldehyde are dissolved in alcohol, the alcoholic solution heating reflux reaction of gained 4 hours; Separation, purifying obtain (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol;
2) intermediate is prepared
(E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol are dissolved in methylene dichloride or trichloromethane, add methyl alcohol or the ethanolic soln of neutralized verdigris, reflux stirring reaction 1 hour; Separation, purifying obtain needle-like yellow-green colour intermediate;
3) preparation of dissymmetrical double Schiff base monokaryon copper compound, this step comprises again following A and B two kinds of methods,
A: two-step approach
The intermediate of above-mentioned preparation is added methyl alcohol or the ethanolic soln of salicylic aldehyde or salicylaldehyde derivatives, room temperature successive reaction is after 3 hours, collecting by filtration filtrate, volatilization, obtain dissymmetrical double Schiff base monokaryon copper compound respectively, the consumption mol ratio of described intermediate and salicylic aldehyde or salicylaldehyde derivatives is 1:1; The consumption weight ratio of methylene dichloride or trichloromethane and methyl alcohol or ethanol is: 1 ~ 3:0.5 ~ 1;
B: single stage method
(E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol is dissolved in methylene dichloride or trichloromethane, first add methyl alcohol or the ethanolic soln of neutralized verdigris, reflux stirring reaction is after 1 hour, add methyl alcohol or the ethanolic soln of salicylic aldehyde or salicylaldehyde derivatives again, further room temperature successive reaction is after 3 hours, collecting by filtration filtrate, volatilization, obtains dissymmetrical double Schiff base monokaryon copper compound; The consumption mol ratio of described (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol and neutralized verdigris and salicylic aldehyde or salicylaldehyde derivatives is 1:1:1; The consumption weight ratio of methylene dichloride or trichloromethane and methyl alcohol or ethanol is: 1 ~ 3:0.5 ~ 1.
The mol ratio of described O-Phenylene Diamine and 3,5-, bis--tert-butyl-salicylaldehyde is 1 ~ 3:1;
Described alcohol is anhydrous methanol or ethanol;
The structure expression of described intermediate is such as formula shown in (II):
The present invention proposes first and uses asymmetric Schiff presoma, Cu metal ion template is utilized to prepare the method for serial dissymmetrical double Schiff base mononuclear copper complex by single stage method or two-step approach, this catalyst activity is higher, and can effective catalyzed alkene radical polymerization.
A kind of serial dissymmetrical double Schiff base monokaryon copper compound is as the application of catalyzer in alkene radical polymerization.
Described alkene is vinylbenzene etc.
Described vinylbenzene Raolical polymerizable carries out under anhydrous and oxygen-free condition: 80 ~ 120 DEG C, under nitrogen atmosphere, in the dimethylbenzene of described dissymmetrical double Schiff base mononuclear copper complex or toluene solution, add radical initiator, then the styrene monomer of super-dry process is added, stirring reaction 2 ~ 36 hours, obtains polystyrene.
Described radical initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or persulphate.
The present invention proposes the method utilizing copper metal ion template synthesis dissymmetrical double Schiff base mononuclear copper complex first, and it can be used as catalyzer for alkene Raolical polymerizable; This catalyst activity is higher, and the effective styrene catalyzed monomer polymerization of energy; In addition, the polymkeric substance that catalytic polymerization obtains be rich between the unregulated polymer (nmr spectrum in concrete visible accompanying drawing) of rule.This provides effective means for the performance improving unregulated polymer.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure of intermediate of the present invention.
Fig. 2 is the crystalline structure figure of title complex of the present invention.
Fig. 3 is collaboration thing of the present invention carries out the polystyrene that catalytic polymerization obtains nmr spectrum as catalyzer.
Embodiment
Be described in further detail the present invention below in conjunction with specific embodiment, the present invention is not limited to following embodiment.
The present invention is with 3,5-di-tert-butyl salicylaldehyde, O-Phenylene Diamine is starting raw material, through obtained (the E)-2-((2-amino-anilide)-methyl)-4 of series reaction step, 6-bis--t-butyl-phenol presoma, the Cu (OAc) of presoma and 1 times of molar weight
2h
2the methyl alcohol of O or ethanolic soln, by copper metal ion template, and salicylic aldehyde or salicylaldehyde derivatives reaction, through filtration, the treating processess such as air volatilization, obtain the catalyzer shown in corresponding formula I.
Embodiment 1:
1) (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol presomas (
hL) synthesis
1g O-Phenylene Diamine is dissolved in as in 50ml round-bottomed flask in 20ml ethanol, then uses 24ml dissolve with ethanol 1.0883g3,5-di-tert-butyl salicylaldehyde, then pour in flask, reflux 4h, after having reacted, solution is concentrated into the half of original volume; Cooling, filters, and filtrate air volatilizees, and can obtain (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol parts.
2) intermediate [Cu (L) (OAc)] is prepared
2
By 8.2mg, (E)-2-((2-amino-anilide)-methyl)-4 of 0.025mmol, 6-bis--t-butyl-phenol is dissolved in 2ml methylene dichloride as presoma, add the ethanol solution 2ml containing 5.0mg, 0.025mmol neutralized verdigris, reflux stirring reaction 1 hour; Separation, purifying obtain needle-like yellow-green colour (II) formula intermediate; Intermediate is through characterized by techniques such as ultimate analysis, infrared spectra and single X-ray diffractometers, and product single crystal structure is specifically shown in Fig. 1, and concrete reaction equation is as follows:
3) preparation of dissymmetrical double Schiff base monokaryon copper compound, this step comprises again following A and B two kinds of methods,
A: two-step approach
Intermediate shown in the formula (II) of above-mentioned preparation is added methyl alcohol or the ethanolic soln of salicylic aldehyde or salicylaldehyde derivatives, further room temperature successive reaction is after 3 hours, collecting by filtration filtrate, volatilization, obtains the dissymmetrical double Schiff base monokaryon copper compound shown in formula (I).The consumption mol ratio of described intermediate and salicylic aldehyde or salicylaldehyde derivatives is 1:1; The consumption weight ratio of methylene dichloride or trichloromethane and methyl alcohol or ethanol is: 1 ~ 3:0.5 ~ 1.Concrete reaction equation is as follows:
B: single stage method
(E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol is dissolved in methylene dichloride or trichloromethane, first add methyl alcohol or the ethanolic soln of neutralized verdigris, reflux stirring reaction is after 1 hour, add methyl alcohol or the ethanolic soln of salicylic aldehyde or salicylaldehyde derivatives again, further room temperature successive reaction is after 3 hours, collecting by filtration filtrate, volatilization, obtains the dissymmetrical double Schiff base monokaryon copper compound shown in formula (I); The consumption mol ratio of described (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol and neutralized verdigris and salicylic aldehyde or salicylaldehyde derivatives is 1:1:1; The consumption weight ratio of methylene dichloride or trichloromethane and methyl alcohol or ethanol is: 1 ~ 3:0.5 ~ 1.Concrete reaction equation is as follows:
Embodiment 2
The synthesis of polystyrene
in 50 milliliters of vials through vacuum and heating drying to 110 degree Celsius, the title complex shown in 0.09mmol formula I is added successively as catalyzer under the protection of nitrogen, 10mL is through dimethylbenzene, the Diisopropyl azodicarboxylate 5.0mg (0.03mmol) of sodium Metal 99.5 backflow drying, then 20ml(220mmol is added) through the vinylbenzene of the monomer of drying treatment, stirring reaction 6 hours, adds acidic ethanol termination reaction; By polymer filtration, and by washing with alcohol 3 times, vacuum-drying 24 hours at 50 DEG C; Take tetrahydrofuran (THF) as moving phase, by normal temperature gpc measurement, obtain a component polymer; The highest number-average molecular weight M of this component polystyrene n be 1.573 × 10 4 g/mol, molecular weight distribution is 2.41.Nmr spectrum is shown in accompanying drawing 3.
Claims (7)
1. a serial dissymmetrical double Schiff base mononuclear copper complex, is characterized in that, structure expression is such as formula shown in (I):
。
2. the preparation method of a kind of serial dissymmetrical double Schiff base monokaryon copper compound according to claim 1, is characterized in that, comprise the steps:
1) prepare (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol as presoma (
hL)
At ambient temperature, O-Phenylene Diamine and 3,5-, bis--tert-butyl-salicylaldehyde are dissolved in alcohol, the alcoholic solution heating reflux reaction of gained 4 hours; Separation, purifying obtain (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol;
2) intermediate is prepared
(E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol are dissolved in methylene dichloride or trichloromethane, add the methyl alcohol containing neutralized verdigris or ethanolic soln, reflux stirring reaction 1 hour; Separation, purifying obtain needle-like yellow-green colour intermediate;
3) preparation of dissymmetrical double Schiff base monokaryon copper compound, this step comprises again following A and B two kinds of methods,
A: two-step approach
The intermediate of above-mentioned preparation is added methyl alcohol or the ethanolic soln of salicylic aldehyde or salicylaldehyde derivatives, room temperature successive reaction is after 3 hours, collecting by filtration filtrate, volatilization, obtain dissymmetrical double Schiff base monokaryon copper compound respectively, the consumption mol ratio of described intermediate and salicylic aldehyde or salicylaldehyde derivatives is 1:1; The consumption weight ratio of methylene dichloride or trichloromethane and methyl alcohol or ethanol is: 1 ~ 3:0.5 ~ 1;
B: single stage method
(E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol is dissolved in methylene dichloride or trichloromethane, first add methyl alcohol or the ethanolic soln of neutralized verdigris, reflux stirring reaction is after 1 hour, add methyl alcohol or the ethanolic soln of salicylic aldehyde or salicylaldehyde derivatives again, further room temperature successive reaction is after 3 hours, collecting by filtration filtrate, volatilization, obtains dissymmetrical double Schiff base monokaryon copper compound; The consumption mol ratio of described (E)-2-((2-amino-anilide)-methyl)-4,6-bis--t-butyl-phenol and neutralized verdigris and salicylic aldehyde or salicylaldehyde derivatives is 1:1:1; The consumption weight ratio of methylene dichloride or trichloromethane and methyl alcohol or ethanol is: 1 ~ 3:0.5 ~ 1;
The mol ratio of described O-Phenylene Diamine and 3,5-, bis--tert-butyl-salicylaldehyde is 1 ~ 3:1;
Described alcohol is anhydrous methanol or ethanol.
3. a kind of serial dissymmetrical double Schiff base monokaryon copper compound according to claim 1 is as the application of catalyzer in alkene radical polymerization.
4. the application of serial dissymmetrical double Schiff base monokaryon copper compound according to claim 3, it is characterized in that, described alkene is vinylbenzene.
5. the application of serial dissymmetrical double Schiff base monokaryon copper compound according to claim 4, it is characterized in that, described vinylbenzene Raolical polymerizable carries out under anhydrous and oxygen-free condition: 80 ~ 120 DEG C, under nitrogen atmosphere, in the dimethylbenzene or toluene solution of a series of dissymmetrical double Schiff base monokaryon copper compound according to claim 1, add radical initiator, then add the styrene monomer of super-dry process, stirring reaction 2 ~ 36 hours, obtains polystyrene.
6. the application of serial dissymmetrical double Schiff base monokaryon copper compound according to claim 5, it is characterized in that, described radical initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or persulphate.
7. the application of serial dissymmetrical double Schiff base monokaryon copper compound according to claim 4, it is characterized in that, in 50 milliliters of vials through vacuum and heating drying to 110 degree Celsius, the title complex of 0.09mmol claim 1 is added successively as catalyzer under the protection of nitrogen, 10mL is through dimethylbenzene, the Diisopropyl azodicarboxylate 5.0mg of sodium Metal 99.5 backflow drying, then add the vinylbenzene of 20ml through the monomer of drying treatment, stirring reaction 6 hours, adds acidic ethanol termination reaction; By polymer filtration, and by washing with alcohol 3 times, vacuum-drying 24 hours at 50 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510450415.3A CN105061255A (en) | 2015-07-29 | 2015-07-29 | Series of asymmetric double-Schiff base mononuclear copper complexes, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510450415.3A CN105061255A (en) | 2015-07-29 | 2015-07-29 | Series of asymmetric double-Schiff base mononuclear copper complexes, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105061255A true CN105061255A (en) | 2015-11-18 |
Family
ID=54490828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510450415.3A Pending CN105061255A (en) | 2015-07-29 | 2015-07-29 | Series of asymmetric double-Schiff base mononuclear copper complexes, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061255A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732503A (en) * | 2016-02-06 | 2016-07-06 | 西安石油大学 | Novel beta-diketone Ni organic complex and preparation method and application thereof |
| CN113501912A (en) * | 2021-07-28 | 2021-10-15 | 西北师范大学 | Preparation method of high-molecular antibacterial microspheres |
-
2015
- 2015-07-29 CN CN201510450415.3A patent/CN105061255A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 丁丽芹: "新型不对称双Schiff碱类后过渡金属催化剂的开发及催化烯烃聚合研究", 《中国博士学位论文全文数据库 工程科技I辑（月刊），2012年》 * |
| 李爱科: "N^N^O型后过渡金属铁、钴、镍、钯系列配合物的合成、表征及催化烯烃聚合反应的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑（月刊）》2011年》 * |
| 闫小宁等: "不对称席夫碱过渡金属配合物的合成和催化性能", 《化学研究与应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732503A (en) * | 2016-02-06 | 2016-07-06 | 西安石油大学 | Novel beta-diketone Ni organic complex and preparation method and application thereof |
| CN105732503B (en) * | 2016-02-06 | 2018-02-09 | 西安石油大学 | A kind of new beta diketone class Ni organic coordination compounds, preparation method and applications |
| CN113501912A (en) * | 2021-07-28 | 2021-10-15 | 西北师范大学 | Preparation method of high-molecular antibacterial microspheres |
| CN113501912B (en) * | 2021-07-28 | 2022-06-14 | 西北师范大学 | Preparation method of high-molecular antibacterial microspheres |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Photo-cleavage of the cobalt–carbon bond: visible light-induced living radical polymerization mediated by organo-cobalt porphyrins | |
| Miao et al. | Preparation of a nitrate-coordinated copper (II) complex of 2-(pyrazol-3-yl)-6-(pyrazolate) pyridine as an efficient catalyst for methyl methacrylate polymerization | |
| JP2010513612A5 (en) | ||
| Li et al. | Controlled iso-specific polymerization of 2-vinylpyridine catalyzed by arylamide-ligated rare-earth metal aminobenzyl complexes | |
| CN108912009A (en) | Asymmetric diimine nickel catalyst and its ligand, preparation method and purposes | |
| CN105061255A (en) | Series of asymmetric double-Schiff base mononuclear copper complexes, and preparation method and application thereof | |
| Ebrahimipour et al. | A mixed-ligand ternary complex of nickel (II): synthesis, characterization and catalytic investigation for the synthesis of pyranopyrazoles | |
| Mariott et al. | Mechanism and scope of stereospecific, coordinative-anionic polymerization of acrylamides by chiral zirconocenium ester and amide enolates | |
| He et al. | Study on the curing kinetics of phthalonitrile promoted by bio-tyrosine cyclic peptide | |
| CN103087114A (en) | Salalen-type rare-earth metal amide as well as preparation method and application thereof | |
| CN101402694B (en) | Three-tooth salicylaldehyde imine vanadium olefin polymerizing catalyst, preparation and uses thereof | |
| CN107298763B (en) | Double-tower type polyhedral oligomeric silsesquioxane containing IVB group metal and preparation method thereof | |
| CN106883181A (en) | Novel series beta diketone class Ni/Cu complexs, preparation method and applications | |
| CN103965449A (en) | Iridium-containing optical-function polymer and preparation method thereof | |
| CN104530136B (en) | A kind of chiral platinum complex and preparation method thereof | |
| CN107286187B (en) | Alkyl aluminum complex containing N, N, N, N-tetradentate chelating penta-coordination, preparation method thereof and method for catalyzing ring-opening polymerization of lactide | |
| CN106117422B (en) | Ligand-Thermo-sensitive ionic liquid copolymer and its preparation method and application | |
| CN100465195C (en) | Beta-hydroxy propyleneimine vanadium olefinic polymerization catalyst and its preparation method and uses | |
| CN114149571A (en) | Imidazole ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method | |
| US9309332B2 (en) | Polymerization catalysts, methods and products | |
| Inokuma | Aliphatic Polyketones as Shapable Molecular Chains | |
| CN104725614B (en) | A kind of method being polymerize with catalyzed by rare-earth complex lactide | |
| Shiono et al. | A highly active catalyst composed of ansa-fluorenylamidodimethyltitanium derivative for propene polymerization | |
| CN101851307B (en) | Method for synthesizing star-shaped polystyrene polymer ruthenium complex | |
| CN105732503B (en) | A kind of new beta diketone class Ni organic coordination compounds, preparation method and applications |
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: 20151118 |
|
| WD01 | Invention patent application deemed withdrawn after publication |