CN101307133A - Poly {acetylene [-2,5-du(methoxyl)]benzene } and method for preparing same - Google Patents
Poly {acetylene [-2,5-du(methoxyl)]benzene } and method for preparing same Download PDFInfo
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- CN101307133A CN101307133A CNA2008100447804A CN200810044780A CN101307133A CN 101307133 A CN101307133 A CN 101307133A CN A2008100447804 A CNA2008100447804 A CN A2008100447804A CN 200810044780 A CN200810044780 A CN 200810044780A CN 101307133 A CN101307133 A CN 101307133A
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Abstract
The invention discloses a new material called polyacetylene-2, 5-methoxyphenyl and a method for preparing the same. The polyacetylene-2,5-methoxyphenyl has a structural formula as shown in figure 4; the preparation method comprises the following steps that: 1,4-dibromo-2,5-dioxygen methyl benzene and acetenyl tri-n-butylstannyl are utilized as main raw materials, dissolved by tetrahydrofuran, heated to a temperature of between 50 and 80 DEG C, stirred, reacted for 12 to 16 hours, then cooled to a temperature of between 10 DEG C below zero and 25 DEG C below zero, added with LDA(lithium dirsopropylamide), stirred for 15 minutes and positioned in a room temperature environment for temperature rise; after the mixture is kept stand for 24 hours, the mixture is separated by filter paper finally, thereby obtaining a polymer. The reaction is completed through only two steps; and the reaction condition is mild and easy to control. The polyacetylene-2, 5-methoxyphenyl provided by the invention has wide application prospect in mass gas-sensing materials.
Description
Technical field
The present invention relates to organic gas-sensitive material technology field, be specifically related to a kind of new synthetic poly-{ acetylene [2,5-two (methoxyl group)] benzene } and preparation method thereof.
Background technology
The organic gas-sensitive material is a kind of structure that can pass through to change macromolecular chain, change the material of its chemical physical property, can obtain selectivity thus to gas, raising is to the sensitivity of gas, and organic polymer material is cheap, and, can be by the gas sensor of organic gas-sensitive material development at working and room temperature, therefore it is low in energy consumption, is easy to the penetration and promotion of the gas sensor of this kind material preparation.Based on these characteristics, this material can be used for the development and the exploitation of gas sensor.In recent years coal mining accident takes place frequently, and the development of coal mine gas dependent sensor is subjected to extensive concern, develops very fast.
π structure covalent linkage atomic structure is arranged and is determined it can make the electronics on the polymer backbone chain leave its original seat, so making these polymer materialss have certain electronic conduction characteristic under certain electric field or magnetic field.According to document (M.Penza, G.Cassano, A.Sergi, C.Lo SAW chemical sensing usingpoly-ynes and organometallic polymer films, Sens.Actuators B81 (2001) 88-98), π structure covalent linkage is to be made of a phenyl ring and an acetylene, as Figure 1-3.
The polymkeric substance with π structure that appears in the newspapers at present has Pt-DEBP (poly-(bistributyl-phosphine)-platinum-diethynylbiphenyl), DOEB (poly-2,5-dibutoxyethynylbenzene), DBEB (poly-2,5-dioc-tyloxyethynylbenzene) etc., and be used on SAW humidity sensor, the SAW organic gas sensor.Wherein the Pt-DEBP film is to NO
2, SO
2, H
2S, NO, NH
3, CH
4Gas all has sensitivity preferably, and the DOEB film is all least responsive to all gas, above-mentioned materials exists significantly not enough aspect selectivity, can not judge it is which kind of gas effectively, therefore, it can only could judge gaseous constituent and concentration effectively by gas sensor array technology and mode identification technology.
Summary of the invention
Technical problem to be solved by this invention is how a kind of new π structure organic gas-sensitive material and preparation method thereof that has is provided, this novel material has good susceptibility to four kinds of composition gases of methane gas, and cost of manufacture is low, and its preparation method is simple, is convenient to make.
Technical problem proposed by the invention is to solve like this: a kind of poly-{ acetylene [2,5-two (methoxyl group)] benzene } is provided, and is a kind of yellow oily liquid, it is characterized in that its general structure is as follows:
The preparation method of a kind of poly-{ acetylene [2,5-two (methoxyl group)] benzene } is characterized in that, may further comprise the steps:
1. dispose mixing solutions: with 1,4-two bromo-2,5-dioxy methyl and ethynyl tri-n-butyl tin are dissolved among the organic solvent THF, and add catalyzer;
2. reacting by heating: with the step 1. mixture heating up to 50 ℃ of gained～80 ℃ and under this temperature stirring reaction 12-16 hour;
3. cold filtration: with step 2. the reaction solution of gained be cooled to-10 ℃～-25 ℃ add an amount of LDA after, take out mixture, be put in the room temperature environment and heat up naturally, then filtration;
4. washing and filtering is drained: with step 3. the polymkeric substance of gained repeatedly wash and filter the gained yellow oil with methyl alcohol and be poly-{ acetylene [2,5-two (methoxyl group)] benzene }.
Preparation method according to poly-{ acetylene [2,5-two (methoxyl group)] benzene } provided by the present invention is characterized in that, step 1. described in catalyzer be metal Pb.
Preparation method according to poly-{ acetylene [2,5-two (methoxyl group)] benzene } provided by the present invention is characterized in that, step 1. in 1,4-two bromo-2, the mol of 5-dioxy methyl and ethynyl tri-n-butyl tin is than greater than 1.
Preparation method according to poly-{ acetylene [2,5-two (methoxyl group)] benzene } provided by the present invention is characterized in that, the 3. middle LDA of step is 1ml～1.2ml.
Preparation method according to poly-{ acetylene [2,5-two (methoxyl group)] benzene } provided by the present invention is characterized in that, step is 4. middle uses the methanol wash number of times greater than 5 times.
Preparation method according to poly-{ acetylene [2,5-two (methoxyl group)] benzene } provided by the present invention is characterized in that, the 2. middle mixture heating up of step is the waters even heating.
The principle that the present invention prepares poly-{ acetylene [2,5-two (methoxyl group)] benzene } can be expressed as:
Wherein Ar is,
Should gather { acetylene [2,5-two (methoxyl group)] benzene } novel material, to four kinds of composition gas CH of methane gas as π structure covalent linkage organic polymer
4, CO, H
2And NH
3All has susceptibility.Compared to now leading semi-conductor coal mine gas dependent sensor, not only working temperature is low for the transmitter that adopts the present invention to make, the susceptibility height, gas-selectively is good, in addition cost can control very low, this has a significant impact extensively popularizing gas sensor.
Description of drawings
Fig. 1 is the Pt-DEBP (structural formula of poly-(bistributyl-phosphine)-platinum-diethynylbiphenyl);
Fig. 2 is DOEB (poly-2, structural formula 5-dibutoxyethynylbenzene);
Fig. 3 is DBEB (poly-2, structural formula 5-dioctyloxyethynylbenzene);
Fig. 4 is the structural formula of poly-{ acetylene [2,5-two (methoxyl group)] benzene } provided by the present invention (poly{ethynyl[-2,5-di (methoxy)] benzene}).
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and embodiment.
Poly-{ acetylene [2,5-two (methoxyl group)] benzene } provided by the present invention as shown in Figure 4.Preparation method's embodiment is as follows:
Embodiment 1
The THF that gets 40ml is as in the beaker, and is first with 1 of 0.023ml, 4-two bromo-2, and the 5-benzylene chloride adds, and adds 4.417mg metal Pd (catalyzer) then, stirs with glass rod; With after solvent THF melts fully mutually, the ethynyl tri-n-butyl tin of getting 58.6mg is added in the mixing solutions at bromide; 85-2 type constant temperature magnetic force heat agitated machine with Shanghai Si Le instrument company stirs mixing solutions then, and heating, and temperature should be made as 70 ℃, and churning time is 12 hours; Then take out beaker, beaker is put in the ESL-D2KA type high-low temperature test chamber of Guangzhou Ace peck company, be cooled to-20 ℃, required time 20 minutes approximately; Take out the good solution of cooling, the LDA solvent that takes out 1.16ml with transfer pipet adds, and stirs 15 minutes; Standing mixt 24 hours separates it with filter paper at last, obtains than pure polymer.Polymkeric substance is yellow oil at normal temperatures.By its Infrared spectroscopy is found 2055cm
-1There is a little absorption peak at the place; Wavelength＞3300cm
-1Have strong absorption peak; 1270cm
-1～1210cm
-1And 1050cm
-1～1000cm
-1Strong absorption peak can appear in these two scopes.The novel material of this invention is yellow oily liquid at ambient temperature, and is water insoluble, is soluble in the part organic solvent, as alcohol, and tetrahydrofuran (THF), but be insoluble to organic solvent methane.Its fusing point is in 30 ℃～34 ℃ scopes.
Embodiment 2 experimental procedure 2. in, if waters Heating temperature＜50 ℃, chemical bond between the monomer does not have sufficiently high temperature to destroy, lead to the failure, no oily polymer produces, Heating temperature the best is 13 hours, 14 hours or 15 hours at 60 ℃, 65 ℃ or 70 ℃ at this temperature optimum reacting time.
Embodiment 4 experimental procedure 3. in, if cooling temperature＜-30 ℃, polymer pole is prone to crystalline polamer and stops effectively carrying out of subsequent reactions.Optimum temperature value is in the cooling scope :-10 ℃ ,-20 ℃ or-25 ℃.
Claims (7)
1, a kind of poly-{ acetylene [2,5-two (methoxyl group)] benzene } is a kind of yellow oily liquid, it is characterized in that its general structure is as follows:
2, the preparation method of a kind of poly-{ acetylene [2,5-two (methoxyl group)] benzene } is characterized in that, may further comprise the steps:
1. dispose mixing solutions: with 1,4-two bromo-2,5-dioxy methyl and ethynyl tri-n-butyl tin are dissolved among the organic solvent THF, and add catalyzer;
2. reacting by heating: with the 1. mixture heating up to 50 ℃ of gained～80 ℃ of step, and under this temperature stirring reaction 12-16 hour;
3. cold filtration: with step 2. the reaction solution of gained be cooled to-10 ℃～-25 ℃, add an amount of LDA after, take out mixture, be put in the room temperature environment and heat up naturally, then filtration;
4. washing and filtering is drained: with step 3. the polymkeric substance of gained repeatedly wash and filter the gained yellow oil with methyl alcohol and be poly-{ acetylene [2,5-two (methoxyl group)] benzene }.
3, the preparation method of poly-{ acetylene [2,5-two (methoxyl group)] benzene } according to claim 2 is characterized in that, step 1. described in catalyzer be metal Pb.
4, the preparation method of poly-{ acetylene [2,5-two (methoxyl group)] benzene } according to claim 2 is characterized in that, step 1. in 1,4-two bromo-2, the mol of 5-dioxy methyl and ethynyl tri-n-butyl tin is than greater than 1.
5, the preparation method of poly-{ acetylene [2,5-two (methoxyl group)] benzene } according to claim 2 is characterized in that, the 3. middle LDA of step is 1ml～1.2ml.
6, the preparation method of poly-{ acetylene [2,5-two (methoxyl group)] benzene } according to claim 2 is characterized in that, step is 4. middle uses the methanol wash number of times greater than 5 times.
7, the preparation method of poly-{ acetylene [2,5-two (methoxyl group)] benzene } according to claim 2 is characterized in that, the 2. middle mixture heating up of step is the waters even heating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030789A (en) * | 2012-12-17 | 2013-04-10 | 北京科技大学 | Five-membered ring polymer applied to OFET and synthetic process |
-
2008
- 2008-06-24 CN CN2008100447804A patent/CN101307133B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030789A (en) * | 2012-12-17 | 2013-04-10 | 北京科技大学 | Five-membered ring polymer applied to OFET and synthetic process |
| CN103030789B (en) * | 2012-12-17 | 2014-10-15 | 北京科技大学 | Five-membered ring polymer applied to OFET and synthetic process |
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