CN103319709A - Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof - Google Patents
Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof Download PDFInfo
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- CN103319709A CN103319709A CN2013102792091A CN201310279209A CN103319709A CN 103319709 A CN103319709 A CN 103319709A CN 2013102792091 A CN2013102792091 A CN 2013102792091A CN 201310279209 A CN201310279209 A CN 201310279209A CN 103319709 A CN103319709 A CN 103319709A
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Abstract
The invention discloses a terpolymer of carbene-diazo compound-acraldehyde and a preparation method thereof, wherein the product is obtained by reprecipitating, centrifugalizing and vacuum-drying a precipitate after reaction by taking diazo compound and acraldehyde as a polymerization monomer. The polymer is obtained by copolymerization of C1/C2N2/C2. The main chain consists of carbine, a diazo compound and acraldehyde. The polymerization reaction of C1/C2N2/C2 disclosed by the invention and the polymer obtained have the following remarkable characteristics of easiness in obtaining reaction monomer, simple preparation method of the polymer, no catalysts and solvents, no heating, convenience in post-treatment and convenience in large-scale application and quick polymerization speed. Meanwhile, the polymer has luminescent property and can be used in the optical and optical detection field.
Description
Technical field
The present invention relates to terpolymer of a kind of Cabbeen-diazonium compound-propenal and preparation method thereof, belong to field of polymer technology.
Background technology
The concept of Cabbeen (carbene) is to be proposed when studying the cyclopropanization reaction of ethyl diazoacetate (EDA) in 1903 by Eduard Buchner.In organic synthesis, Cabbeen is widely used as a kind of important intermediate.2002, Liu etc. utilized copper catalysis diazoacetic acid allyl ester to obtain the carbalkoxy polymkeric substance, and this is the Cabbeen polyreaction (being also referred to as the C1 polymerization) of first case diazoacetic acid ester derivative.Henceforth, the C1 polyreaction begins to be paid close attention to gradually, and Bas de Bruin and Eiji Ihara study group have made very important contribution for the development that promotes this field.
Diazonium compound has the preparation characteristics such as simple, relatively stable, safe, is usually used in the precursor of Cabbeen.Usually the reaction of diazonium compound and alkene is divided into two kinds: a kind of is that denitrogenation forms Cabbeen and alkene generation cyclopropanization reaction; Another kind is that 1,3-Dipolar Cycloaddition occurs, and generates pyrazoline.
The copolyreaction of diazonium compound and alkene is the rare C1/C1N2/C2 copolyreaction of an example, only has the Ihara seminar of Japan once to report diazonium compound and cinnamic copolymerization.
Summary of the invention
The invention provides terpolymer of a kind of Cabbeen-ethyl diazoacetate-propenal and preparation method thereof
Technical scheme provided by the invention is: the terpolymer of a kind of Cabbeen-ethyl diazoacetate-propenal, and concrete general formula is as follows:
Wherein, x, y, z are the arbitrary integers greater than zero, and R is hydrogen atom, alkyl, aryl, alkoxyl group or aryloxy.
The preparation method of the terpolymer of above-mentioned Cabbeen-diazonium compound-propenal is specially:
With diazonium compound RCOCHN
2Mix with the propenal of fresh distillation, R is hydrogen atom, alkyl, aryl, alkoxyl group or aryloxy; In-70～150 ℃ of lower polyreactions, reaction is cooled to room temperature after finishing, and process reprecipitation and vacuum-drying obtain the terpolymer of Cabbeen-diazonium compound-propenal.
Polyreaction can be mass polymerization, also can be solution polymerization.
During solution polymerization, suitable solvent comprises acetonitrile, tetrahydrofuran (THF), chloroform, 1, and 2-ethylene dichloride, methylene dichloride, tetracol phenixin, toluene, benzene, pyridine etc. in order to prevent solvent evaporates, can add the backflow device.
Used diazonium compound RCOCHN
2, R is hydrogen atom, alkyl, aryl, alkoxyl group or aryloxy, can obtain by prior art is synthetic.As by glycine ethyl ester hydrochloride and Sodium Nitrite cheap and easy to get, can prepare more easily ethyl diazoacetate; By two (p-methylphenyl alkylsulfonyl) hydrazines of 1,2-, bromoacetyl bromide and corresponding alcohol can prepare α-diazoacetate, such as diazoacetic acid benzyl ester etc.; By the diazo transfer method, can prepare the compounds such as the diazoacetic acid tert-butyl ester; By acyl chlorides and diazomethane, can prepare the compounds such as diazonium ethanoyl benzene.
The preparation method of the terpolymer of a kind of Cabbeen-ethyl diazoacetate provided by the invention-propenal, reaction was finished substantially at 2-200 minute usually.
The synthetic route of the terpolymer of Cabbeen-diazonium compound of the present invention-propenal is as follows:
This polyreaction is a kind of C1/C1N2/C2 copolymerization.Reaction monomers is diazonium compound and propenal, Cabbeen RCOCH: slough nitrogen by diazonium compound and form, reaction obtains product by Cabbeen, diazonium compound and propenal terpolymer.
The main polymer chain that synthetic method provided by the invention obtains is comprised of Cabbeen, diazonium compound and propenal.Propenal in the reaction monomers need to be removed stopper, fresh distillation and use.The used diazonium compound of the present invention adopts the preparation method in the existing reference to prepare.
Beneficial effect of the present invention is:
1, reaction monomers is easy to get, and the preparation method is simple, can need not catalysts and solvents, even can need not heating, convenient post-treatment.
2, polymerization rate is fast, the fastest can substantially finishing within 2 minutes.
3, ter-polymers of the present invention has photoluminescent property, can be applied to the fields such as optics and optical detection.
Description of drawings
Fig. 1 is the online fourier transformation-infrared spectrogram of the polymkeric substance of preparation among the embodiment 1.
Fig. 2 is the proton nmr spectra of the polymkeric substance of preparation among the embodiment 1.
Fig. 3 is the carbon-13 nmr spectra of the polymkeric substance of preparation among the embodiment 1.
Fig. 4 is the dsc spectrogram of the polymkeric substance of preparation among the embodiment 1, T among the figure
gSecond-order transition temperature for polymkeric substance.
Fig. 5 is the X-ray diffraction spectrum of the polymkeric substance of preparation among the embodiment 1.
Fig. 6 is the fluorescence spectrum of the polymkeric substance of preparation among the embodiment 5, and excitation wavelength is 459nm, and slit width is 5/5nm.1,2,4,5 polymkeric substance that are respectively among the embodiment 1,2,4,5 wherein.
Embodiment
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
Propenal (0.84g, 0.015mol) and ethyl diazoacetate (EDA) (1.14g, 0.01mol) are added the 10ml round-bottomed flask, and flask links to each other with the safety flack that mineral oil is housed.Room temperature reaction is cooled to room temperature after the end, with chloroform/ether reprecipitation, vacuum-drying obtains polymkeric substance, and recording number-average molecular weight is 25000.
Utilize online FT-IR that the course of embodiment 1 polyreaction is followed the tracks of, the result as shown in Figure 1.The characteristic peak of propenal in infrared spectra shows 1619cm
-1The stretching vibration of place-C=C-and=C-H is at 915cm
-1And 972cm
-1The out-of-plane deformation vibration at two places, along with the carrying out of reaction, San Chufeng fades away, and shows that polyreaction is opened and participated in to carbon-carbon double bond in the propenal.The characteristic peak of EDA is at 740cm
-1The place, this peak disappears substantially during 103.1s, illustrates that reactant consumes substantially.1545cm
-1Being-stretching vibration of N=N-, is 14.38% in conjunction with nitrogen content in the results of elemental analyses, the generation along with reaction can be described ,-N=N-insertion polymerization owner chain.Above result can reach a conclusion, and within less than 2 minutes time, reaction is finished substantially.
Fig. 2 and Fig. 3 are respectively embodiment 1 resulting polymers
1H NMR and
13C NMR composes (CDCl
3Be solvent).
1On the H NMR spectrum displacement of 9.4-9.8ppm place and
13The displacement at 186ppm place has proved-existence of CHO group EDA and Cabbeen CH in the C NMR spectrum
3CH
2OCOCH: in-OCH
2Vibration be reflected in
1On the H NMR spectrum 4.0-4.4ppm place and
13The 61ppm place of C NMR spectrum ,-OCH
2CH
3Methyl on the group can from
1In the H NMR spectrum 1.0-1.4ppm and
13The peak of 14ppm proves in the C NMR spectrum,
13The displacement at 170-172ppm place comes from EDA and Cabbeen CH in the C NMR spectrum
3CH
2OCOCH: the vibration of middle carbonyl.Characterize by the thermal properties of differential scanning calorimeter (DSC) to polymkeric substance, as shown in Figure 4, can find out its second-order transition temperature (T
g) be 72.1 ℃.X-ray diffraction (XRD) (Fig. 5) the analysis showed that, this polymkeric substance is random copolymers.
Propenal (0.84g, 0.015mol) and the diazoacetic acid tert-butyl ester (0.71g, 0.005mol) are added the 10ml round-bottomed flask, and flask links to each other with the safety flack that mineral oil is housed.Be heated to 150 ℃ of reaction 60min, reaction is cooled to room temperature after finishing, and with chloroform/ether reprecipitation, vacuum-drying obtains polymkeric substance, and recording number-average molecular weight is 18000.
Propenal (0.84g, 0.015mol) and diazonium ethanoyl benzene (2.92g, 0.02mol) are dissolved in the 20ml methylene dichloride, add the 50ml round-bottomed flask, flask links to each other with the safety flack that mineral oil is housed.Be heated to 50 ℃ of reaction 120min, reaction is cooled to room temperature after finishing, and with chloroform/ether reprecipitation, vacuum-drying obtains polymkeric substance, and recording number-average molecular weight is 8500.
Embodiment 4
Propenal (0.84g, 0.015mol) and diazoacetic acid Bian ester (5.28g, 0.03mol) are dissolved in 20ml toluene, add the 50ml round-bottomed flask, flask links to each other with the safety flack that mineral oil is housed.Be cooled to-70 ℃ of reaction 200min, reaction is cooled to room temperature after finishing, and with chloroform/ether reprecipitation, vacuum-drying obtains polymkeric substance, and recording number-average molecular weight is 15000.
Embodiment 5
With propenal (0.84g, 0.015mol) and EDA(0.57g, 0.005mol) add the 10ml round-bottomed flask, flask links to each other with the safety flack that mineral oil is housed.100 ℃ of heating 10min are cooled to room temperature after the end, with chloroform/ether reprecipitation, vacuum-drying obtains polymkeric substance, and recording number-average molecular weight is 11000.
Fig. 6 is the fluorescence spectrum of the polymkeric substance of preparation among the embodiment 1,2,4,5, and excitation wavelength is 459nm, and slit width is 5/5nm, and from spectrogram, the polymkeric substance of gained all has fluorescent characteristic, can be applied to the fields such as optics and optical detection.
Claims (5)
1. the terpolymer of Cabbeen-diazonium compound-propenal is characterized in that, concrete general formula is as follows:
Wherein, x, y, z are the arbitrary integers greater than zero, and R is hydrogen atom, alkyl, aryl, alkoxyl group or aryloxy.
2. the preparation method of the terpolymer of Cabbeen-diazonium compound claimed in claim 1-propenal is characterized in that:
With diazonium compound RCOCHN
2Mix with the propenal of fresh distillation, R is hydrogen atom, alkyl, aryl, alkoxyl group or aryloxy; In-70～150 ℃ of lower polyreactions, reaction is cooled to room temperature after finishing, and process reprecipitation and vacuum-drying obtain the terpolymer of Cabbeen-diazonium compound-propenal.
3. preparation method according to claim 2 is characterized in that, polyreaction is mass polymerization or solution polymerization.
4. preparation method according to claim 3 is characterized in that, during solution polymerization, solvent is acetonitrile, tetrahydrofuran (THF), chloroform, 1,2-ethylene dichloride, methylene dichloride, tetracol phenixin, toluene, benzene or pyridine.
5. preparation method according to claim 2 is characterized in that, the reaction times was at 2-200 minute.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| 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 |
| CN102977364A (en) * | 2012-11-30 | 2013-03-20 | 武汉大学 | Diazoacetate-ethoxycarbonyl carbene copolymer and preparation method thereof |
| CN102977365A (en) * | 2012-12-03 | 2013-03-20 | 武汉大学 | Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof |
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Patent Citations (3)
| 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 |
| CN102977364A (en) * | 2012-11-30 | 2013-03-20 | 武汉大学 | Diazoacetate-ethoxycarbonyl carbene copolymer and preparation method thereof |
| CN102977365A (en) * | 2012-12-03 | 2013-03-20 | 武汉大学 | Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| EIJI IHARA等: ""Thermally induced polymerization and copolymerization with styrene of diazoketones in the presence of benzoquinone"", 《POLYMERS》, vol. 66, no. 1, 5 February 2010 (2010-02-05), pages 3 - 15 * |
| 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》, 30 September 2011 (2011-09-30), pages 86 - 104 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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