CN102977364A - Diazoacetate-ethoxycarbonyl carbene copolymer and preparation method thereof - Google Patents
Diazoacetate-ethoxycarbonyl carbene copolymer and preparation method thereof Download PDFInfo
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- CN102977364A CN102977364A CN2012105075611A CN201210507561A CN102977364A CN 102977364 A CN102977364 A CN 102977364A CN 2012105075611 A CN2012105075611 A CN 2012105075611A CN 201210507561 A CN201210507561 A CN 201210507561A CN 102977364 A CN102977364 A CN 102977364A
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Abstract
The invention discloses a diazoacetate-ethoxycarbonyl carbene copolymer and a synthesis method of the copolymer. The main chain of the polymer comprises carbon atoms and nitrogen atoms, wherein the carbon atoms are prepared by carbene polymerization reaction, and the nitrogen atoms are added into the main chain of the polymer by double-free-radical polymerization. The invention also provides a preparation method of the copolymer, which takes diazoacetate as raw material, and comprises the following steps: putting the diazoacetate into a microwave oven, and carrying out microwave irradiation on the diazoacetate for a period of time under the protection of argon; and finally, carrying out reprecipitation and vacuum drying to obtain the product. The method does not use catalyst and solvent, and is simple and convenient in steps as well as simple in reaction and aftertreatment; and the prepared polyester with the novel structure can be applied to the wide fields such as optical study and the like.
Description
Technical field
The present invention relates to multipolymer of a kind of diazonium acetate and carbethoxy carbene and preparation method thereof, belong to chemical field.
Background technology
Carbon chain polymer is obtained by olefinic polyreaction by ethene or its derivative usually.Although olefinic polyreaction is used widely in fields such as plastics, synthon and synthetic rubber, and formed huge industry, but also have some limitation, each carbon atom has the polymkeric substance of polar group, polyolefinic stereochemistry to be difficult to control on the carbochain such as obtaining.The Cabbeen polyreaction has then broken through these conventional limitation, for the carbon chain polymer of development structure uniqueness provides new way.
At present, the Cabbeen polymerization mainly relies under the help of metal species catalyzer reacts, such as, organoaluminum, organic palladium, organic copper etc.Although these researchs have obtained some challenging progress, and shown important application prospect, the structure and the performance that have conventional polyolefine not have with substituent Cabbeen polymkeric substance, but the use of catalyzer has inevitably caused the waste of resource and the destruction of environment.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and the multipolymer of a kind of diazonium acetate and carbethoxy carbene is provided.
The present invention also provides the preparation method of the multipolymer of above-mentioned diazonium acetate and carbethoxy carbene.
The present invention for the technical scheme that provides is provided is: the multipolymer of a kind of diazonium acetate and carbethoxy carbene, and concrete general formula is as follows:
Wherein, R refers to any group, comprises that a kind of in straight-chain paraffin, branched paraffin, halogen or the aromatic group, x, y refer to arbitrarily the integer greater than 0.
The preparation method of the multipolymer of a kind of above-mentioned diazonium acetate and carbethoxy carbene; under the protection of rare gas element; diazonium acetate is joined in the reaction flask; under microwave exposure, react for some time; obtain brown throw out through reprecipitation after the cooling; throw out is through centrifugal, and vacuum-drying obtains the multipolymer of diazonium acetate and carbethoxy carbene.
The microwave power of described microwave exposure 200 watts and more than, the microwave time is 2min ~ 12h.
Preparation method of the present invention carries out under the condition of microwave exposure (Microwaves), and its reaction equation is as follows:
Wherein, m, n are any one integers greater than 0, and R refers to any group, comprises long chain alkane, aromatic hydrocarbons, halogen etc.
The preparation method of the monomer diazonium acetate among the present invention is: under 0 ~ 10 ℃ environment, 0.1mol glycine ester hydrochloride, 20ml distilled water, 0.0015mol sulfuric acid and 30ml1, the 2-ethylene dichloride joins in the there-necked flask, after the cooling, the aqueous solution (15ml) that slowly adds the 0.12mol Sodium Nitrite, maintain the temperature at below 10 ℃, stirred 2 hours, reaction system is transferred in the separating funnel.Tell organic phase, water is used respectively 1 of 8ml, and the extraction of 2-ethylene dichloride merges organic phase, with saturated sodium bicarbonate solution 10ml washed twice, uses anhydrous sodium sulfate drying.Obtain diazonium acetate through underpressure distillation.
Compared with prior art, the raw materials used greenization of the present invention, commercialization, monomer is synthetic convenient, simple to operate; Avoid the use organo-metallic catalyst, reacted nontoxic, saved the energy; What the present invention obtained is a kind of brand-new material, and contains the polymericular weight height of azo group on the resulting main chain, can be used in widely field.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic spectrogram of gained polyester after the ethyl diazoacetate polymerization, and a ~ f among the figure is the position of hydrogen atom in the nuclear magnetic spectrogram.
Fig. 2 is the infrared spectrum of gained polyester after the ethyl diazoacetate polymerization.
Embodiment
The present invention will be further described below in conjunction with example and accompanying drawing.
Embodiment 1
Under the protection of argon gas, the 0.01mol ethyl diazoacetate places reaction flask, uses 200W microwave exposure 30 minutes, adds the tetrahydrofuran (THF) dissolving after the cooling, then splashes into a large amount of sherwood oils and carries out reprecipitation, the centrifugal thing that is precipitated of process, vacuum-drying.Productive rate is 61.9%, and the polymkeric substance carbon content that obtains is 60.66%, and hydrogen richness is 4.72%, and nitrogen content is 7.95%, and molecular weight is 6300g/mol.
Embodiment 2
Under the protection of argon gas, the 0.01mol ethyl diazoacetate places reaction flask, uses 200W microwave exposure 60 minutes, adds the tetrahydrofuran (THF) dissolving after the cooling, then splashes into a large amount of sherwood oils and carries out reprecipitation, the centrifugal thing that is precipitated of process, vacuum-drying.Productive rate is 63.8%, and the polymkeric substance carbon content that obtains is 60.31%, and hydrogen richness is 5.07%, and nitrogen content is 8.04%, and molecular weight is 35400g/mol.
Embodiment 3
Under the protection of argon gas, the 0.01mol ethyl diazoacetate places reaction flask, uses 200W microwave exposure 90 minutes, adds the tetrahydrofuran (THF) dissolving after the cooling, then splashes into a large amount of sherwood oils and carries out reprecipitation, the centrifugal thing that is precipitated of process, vacuum-drying.Productive rate is 68.1%, and the polymkeric substance carbon content that obtains is 59.08%, and hydrogen richness is 5.08%, and nitrogen content is 8.18%, and molecular weight is 22300g/mol.
Embodiment 4
Under the protection of argon gas, the 0.01mol diazoacetic acid tert-butyl ester places reaction flask, uses 200W microwave exposure 90 minutes, adds the tetrahydrofuran (THF) dissolving after the cooling, then splashes into a large amount of sherwood oils and carries out reprecipitation, the centrifugal thing that is precipitated of process, vacuum-drying.Productive rate is 69.1%, and the polymkeric substance carbon content that obtains is 65.08%, and hydrogen richness is 7.08%, and nitrogen content is 5.67%, and molecular weight is 21500g/mol.
Embodiment 5
Under the protection of argon gas, 0.01mol monomer (R=Ph) places reaction flask, uses 200W microwave exposure 720 minutes, adds the tetrahydrofuran (THF) dissolving after the cooling, then splashes into a large amount of sherwood oils and carries out reprecipitation, the centrifugal thing that is precipitated of process, vacuum-drying.Productive rate is 58.1%, and the polymkeric substance carbon content that obtains is 70.08%, and hydrogen richness is 5.08%, and nitrogen content is 4.18%, and molecular weight is 6800g/mol.
Embodiment 6
Under the protection of argon gas, 0.01mol monomer (R=(CH
2)
5CH
3) place reaction flask, use 400W microwave exposure 20 minutes, add the tetrahydrofuran (THF) dissolving after the cooling, then splash into a large amount of sherwood oils and carry out reprecipitation, the centrifugal thing that is precipitated of process, vacuum-drying.Productive rate is 59.1%, and the polymkeric substance carbon content that obtains is 71.25%, and hydrogen richness is 6.72%, and nitrogen content is 2.18%, and molecular weight is 3800g/mol.
Embodiment 7
Under the protection of nitrogen, 0.01mol monomer (R=(CH
2)
2CH
3) place reaction flask, use 400W microwave exposure 2 minutes, add the tetrahydrofuran (THF) dissolving after the cooling, then splash into a large amount of sherwood oils and carry out reprecipitation, the centrifugal thing that is precipitated of process, vacuum-drying.Productive rate is 50.2%, and the polymkeric substance carbon content that obtains is 62.25%, and hydrogen richness is 6.52%, and nitrogen content is 2.38%, and molecular weight is 800g/mol.
Claims (4)
1. the multipolymer of a diazonium acetate and carbethoxy carbene, concrete general formula is as follows:
Wherein, R is any group, and x, y refer to arbitrarily the integer greater than 0.
2. the multipolymer of a kind of diazonium acetate according to claim 1 and carbethoxy carbene is characterized in that: described any group comprises a kind of in straight-chain paraffin, branched paraffin, halogen or the aromatic group.
3. the preparation method of the multipolymer of a diazonium acetate as claimed in claim 1 and carbethoxy carbene; it is characterized in that: under the protection of rare gas element; diazonium acetate is joined in the reaction flask; under microwave exposure, react for some time; obtain brown throw out through reprecipitation after the cooling; throw out is through centrifugal, and vacuum-drying obtains the multipolymer of diazonium acetate and carbethoxy carbene.
4. the preparation method of the multipolymer of diazonium acetate according to claim 3 and carbethoxy carbene is characterized in that: the microwave power of described microwave exposure 200 watts and more than, the microwave time is 2min ~ 12h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319709A (en) * | 2013-07-04 | 2013-09-25 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN104262621A (en) * | 2014-09-22 | 2015-01-07 | 武汉大学 | Poly(alpha-carbonyl diazo alkane) as well as preparation method and application thereof |
| CN104311822A (en) * | 2014-10-31 | 2015-01-28 | 武汉大学 | Carbene-diazo compound-olefine aldehyde terpolymer and application of carbene-diazo compound-olefine aldehyde terpolymer as bidirectional conversion fluorescent material and anti-cancer drug |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339512A (en) * | 2001-09-13 | 2002-03-13 | 武汉大学 | Polyhydrocarbon oxygen carbonyl carbene and its preparing method and use |
| US20070270593A1 (en) * | 2006-05-18 | 2007-11-22 | R.P. Scherer Technologies, Inc. | Ruthenium(II) catalysts for use in stereoselective cyclopropanations |
-
2012
- 2012-11-30 CN CN2012105075611A patent/CN102977364A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339512A (en) * | 2001-09-13 | 2002-03-13 | 武汉大学 | Polyhydrocarbon oxygen carbonyl carbene and its preparing method and use |
| US20070270593A1 (en) * | 2006-05-18 | 2007-11-22 | R.P. Scherer Technologies, Inc. | Ruthenium(II) catalysts for use in stereoselective cyclopropanations |
Non-Patent Citations (3)
| Title |
|---|
| EIJI IHARA,ET AL.: "Palladium-Mediated polymerization of alkyl diazoacetates to afford poly(alkoxycarbonylmethylene)s. First synthesis of polymethylenes bearing polar substituents", 《MACROMOLECULES》, vol. 36, no. 1, 31 December 2003 (2003-12-31), pages 36 - 41 * |
| LIJIAN LIU,ET AL.: "Carbene polymerization:characterization of poly(carballyloxycarbene)", 《POLYMER INTERNATIONAL》, vol. 51, 31 December 2002 (2002-12-31) * |
| 肖龙强等: "微波条件下的卡宾聚合", 《2011年全国高分子学术论文报告会》, 28 September 2011 (2011-09-28), pages 86 - 104 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319709A (en) * | 2013-07-04 | 2013-09-25 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN103319709B (en) * | 2013-07-04 | 2015-06-10 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN104262621A (en) * | 2014-09-22 | 2015-01-07 | 武汉大学 | Poly(alpha-carbonyl diazo alkane) as well as preparation method and application thereof |
| CN104311822A (en) * | 2014-10-31 | 2015-01-28 | 武汉大学 | Carbene-diazo compound-olefine aldehyde terpolymer and application of carbene-diazo compound-olefine aldehyde terpolymer as bidirectional conversion fluorescent material and anti-cancer drug |
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Application publication date: 20130320 |