阅读说明：本技术 基于改性顺式-5-降冰片烯-2,3-二羧酸酐的偶氮苯侧链可聚合单体及其应用 (Azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride and application thereof ) 是由 封伟 刘浩 符林霞 冯奕钰 于 2018-07-18 设计创作，主要内容包括：本发明公开基于改性顺式-5-降冰片烯-2,3-二羧酸酐的偶氮苯侧链可聚合单体及其应用,将合成出偶氮苯接枝到降冰片烯酸酐上得到可聚合单体,将多羟基偶氮苯作为侧链连接到降冰片烯酸酐的主链上,通过分子间氢键作用力与偶氮苯的顺反异构实现聚合物能量的存储与释放。本发明通过开环异位聚合得到目标聚合物。得到的含偶氮苯侧链的聚合物材料较普通偶氮分子在能量密度与半衰期有很大提升,较偶氮苯-石墨烯材料有较好的可塑性,为太阳能的利用提出了新的方法,也扩宽了偶氮苯聚合物的应用范围。(The invention discloses an azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride and application thereof, wherein the synthesized azobenzene is grafted to norbornene anhydride to obtain the polymerizable monomer, polyhydroxy azobenzene is used as a side chain to be connected to a main chain of the norbornene anhydride, and the storage and release of polymer energy are realized through intermolecular hydrogen bond acting force and cis-trans isomerization of the azobenzene. The invention obtains the target polymer by ring-opening ectopic polymerization. Compared with common azo molecules, the energy density and half-life period of the obtained polymer material containing the azobenzene side chain are greatly improved, and the obtained polymer material has better plasticity than an azobenzene-graphene material, thereby providing a new method for utilizing solar energy and widening the application range of the azobenzene polymer.)

1. An azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride is characterized by having the following chemical formula.

2. The preparation method of the azobenzene side chain polymerizable monomer based on the modified cis-5-norbornene-2, 3-dicarboxylic anhydride is characterized by comprising the following steps: uniformly dispersing modified cis-5-norbornene-2, 3-dicarboxylic anhydride in dimethylformamide, adding an azobenzene monomer and anhydrous potassium carbonate, heating and refluxing in an inert protective gas atmosphere, and purifying to obtain an azobenzene side chain polymerizable monomer, wherein the modified cis-5-norbornene-2, 3-dicarboxylic anhydride has a structure shown in the following chemical formula;

the azobenzene monomer is shown in the following chemical formula.

3. The process for preparing an azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride according to claim 2, wherein the modified cis-5-norbornene-2, 3-dicarboxylic anhydride is used in an amount of 20 to 30 parts by mole per parts by mole, the molar ratio of the azobenzene monomer to the modified cis-5-norbornene-2, 3-dicarboxylic anhydride is (1-2): 1, and the molar ratio of the anhydrous potassium carbonate to the modified cis-5-norbornene-2, 3-dicarboxylic anhydride is (3-4): 1.

4. The method for preparing the modified cis-5-norbornene-2, 3-dicarboxylic anhydride based azobenzene side chain polymerizable monomer according to claim 2, wherein the inert shielding gas is nitrogen, helium or argon; heating to 100-120 ℃ to carry out reflux reaction for 5-10 hours, preferably 8-10 hours; after the reflux reaction, extracting for 1-5 times by using a mixed solution of water and dichloromethane (the volume ratio of the water to the dichloromethane solution is 1:3), combining organic phases, and then removing the organic solvent by rotary evaporation to obtain a crude product, and separating by using a chromatographic column.

5. The modified cis-5-norbornene-2, 3-dicarboxylic anhydride is characterized by having a structure represented by the following chemical formula.

6. A process for producing a modified cis-5-norbornene-2, 3-dicarboxylic anhydride, which comprises the steps of: uniformly dispersing 6-amino-hexanol in hydrobromic acid, and performing reflux reaction at 80-100 ℃ to obtain 6-amino-bromohexane; and then 6-amino-bromohexane is uniformly dispersed in toluene, cis-5-norbornene-2, 3-dicarboxylic anhydride is added, and the reaction is carried out at 80-100 ℃ to obtain the modified cis-5-norbornene-2, 3-dicarboxylic anhydride.

7. The process for producing a modified cis-5-norbornene-2, 3-dicarboxylic anhydride according to claim 6, wherein the 6-amino-hexanol is used in an amount of 20 to 30 parts by mole, 1mmol per parts by mole, and the 6-amino-hexanol is uniformly dispersed in hydrobromic acid and refluxed at 80 to 100 ℃ for 1 to 5 hours, preferably 3 to 5 hours, and the 6-amino-bromohexane is used in an amount of 10 to 30 parts by mole, 1mmol per parts by mole, and the molar ratio of the 6-amino-bromohexane to the cis-5-norbornene-2, 3-dicarboxylic anhydride is 1 (1-2), and the mixture is heated to 80 to 100 ℃ and refluxed for 10 to 20 hours, preferably 10 to 16 hours.

8. The process according to claim 6, wherein triethylamine is added as an acid-binding agent to uniformly disperse 6-amino-bromohexane in toluene, and the volume ratio of toluene to triethylamine is (5-20): 1, preferably (5-15): 1.

9. the preparation method of the azobenzene side chain polymerizable monomer based on the modified cis-5-norbornene-2, 3-dicarboxylic anhydride is characterized in that the azobenzene monomer is prepared by uniformly dispersing tricarboxyaniline and sodium hydroxide in water to form a solution A, uniformly dispersing sodium nitrite in water to form a solution B, dropwise adding the solution B into the solution A at 0-5 ℃ under stirring, adding hydrochloric acid after the solution B is completely added into the solution A, continuously stirring, adding 3, 5-dimethoxyaniline into the mixed solution of the solution A and the solution B under an inert protective gas atmosphere, keeping the temperature of 0-5 ℃ and reacting under stirring to obtain the azobenzene monomer, wherein the molar ratio of tricarboxyaniline is 20-30 mol parts, 1mmol per mol parts, the molar ratio of tricarboxyaniline and sodium hydroxide is 1 (2-5), the molar ratio of tricarboxyaniline and sodium nitrite is equal, the molar ratio of tricarboxyaniline and 3, 5-dimethoxyaniline is 1 (1-2), the molar ratio of tricarboxyaniline and sodium hydroxide is 1 (2-5), stirring is preferably performed after adding hydrogen chloride to react under stirring at 100-5 h, and stirring to obtain an inert protective gas solution.

10. Use of the modified cis-5-norbornene-2, 3-dicarboxylic anhydride based azobenzene side chain polymerizable monomer according to claim 1 or the modified cis-5-norbornene-2, 3-dicarboxylic anhydride according to claim 5 for the preparation of energy storage materials or for enhancing the energy storage properties of polymers.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to an azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride, application thereof, an azobenzene polymer energy storage material with plasticity and a preparation method thereof, which have an application prospect of in the field of solar energy storage.

Background

Nowadays, the economy in the world is rapidly developed, science and technology are rapidly improved, and the demand for the existing energy sources is more and more increased, for example, stone resources such as coal, oil, natural gas and the like are increasingly deficient, however, the resources are increasingly deficient, and human beings have many environmental problems such as greenhouse effect, haze and the like while exploiting and utilizing the resources, and the problems all pose serious threats to the fine life of the human beings and the sustainable development of the society. Therefore, the development and utilization of new green energy is imminent.

The solar energy is clean natural renewable energy sources, which are inexhaustible, the development and the utilization of the solar energy are favored by researchers due to the advantages of no air pollution and no influence on the ecological balance of the nature as long as the sunlight reaches the place, the solar energy can be utilized, the solar energy has important achievements in the aspects of organic photoelectricity, photocatalysis, photo-thermal storage and the like due to the advantages of permanence, reproducibility, no pollution and the like, the azobenzene molecules are organic molecules with cis-trans isomerism, cis-trans isomerism can occur under the external stimulation of illumination, heating, pressure and the like, the trans-structure is converted into a metastable cis-structure after absorbing ultraviolet energy, and the cis-structure returns to the trans-structure to release stored energy under the illumination of visible light or the heating condition.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides azobenzene side chain polymer energy storage materials and a preparation method thereof, and the azobenzene side chain polymer energy storage materials have plasticity and can be practically used.

The technical purpose of the invention is realized by the following technical scheme:

an azobenzene side chain polymerizable monomer (i.e., an azobenzene side chain polymerizable monomer based on a modified cis-5-norbornene-2, 3-dicarboxylic anhydride) having the structure of the formula:

azobenzene side chain polymers, i.e. (azobenzene side chain) polymeric energy storage materials, have the structure of the following formula:

the preparation method and process of the polymerizable monomer and polymer are as follows:

specifically, the method comprises the following steps:

the azobenzene monomer is shown in the chemical formula and prepared according to the following steps: uniformly dispersing tricarboxylaniline and sodium hydroxide in water to form a solution A, uniformly dispersing sodium nitrite in water to form a solution B, dropwise adding the solution B into the solution A at 0-5 ℃ under stirring, adding hydrochloric acid after the solution B is completely added into the solution A, continuously stirring, adding 3, 5-dimethoxyaniline into a mixed solution of the solution A and the solution B under the atmosphere of inert protective gas, and reacting at 0-5 ℃ under stirring to obtain an azobenzene monomer.

The method comprises the following steps of preparing tricarboxyaniline, sodium nitrite, hydrochloric acid, 100-300 revolutions per minute, stirring at a reaction temperature of preferably 0-2 ℃, continuously stirring for reacting for 1-5 hours after adding the hydrochloric acid, adding the 3, 5-dimethoxyaniline, and continuously stirring for reacting for 1-5 hours after adding the 3, 5-dimethoxyaniline, wherein the using amount of the tricarboxyaniline is 20-30 mol parts, each mol parts is 1mmol, the molar ratio of the tricarboxyaniline to the sodium hydroxide is 1 (2-5), the molar ratio of the tricarboxyaniline to the sodium nitrite is equal, the molar ratio of the tricarboxyaniline to the 3, 5-dimethoxyaniline is 1 (1-2), the molar ratio of the tricarboxyaniline to the hydrogen chloride is 1 (3-5), the stirring condition is 100-300 revolutions per minute, the reaction temperature is preferably 0-2 ℃, and.

The modified cis-5-norbornene-2, 3-dicarboxylic anhydride (i.e., monomer 1) has the following structure and is prepared according to the following procedure: uniformly dispersing 6-amino-hexanol in hydrobromic acid, and performing reflux reaction at 80-100 ℃ to obtain 6-amino-bromohexane; and then 6-amino-bromohexane is uniformly dispersed in toluene, cis-5-norbornene-2, 3-dicarboxylic anhydride is added, and the reaction is carried out at 80-100 ℃ to obtain the modified cis-5-norbornene-2, 3-dicarboxylic anhydride.

Wherein the dosage of 6-amino-hexanol is 20-30 mol parts, 1mmol per mol parts, 6-amino-hexanol is uniformly dispersed in hydrobromic acid to carry out reflux reaction for 1-5 hours, preferably 3-5 hours, at 80-100 ℃, the dosage of 6-amino-bromohexane is 10-30 mol parts, the molar ratio of 1mmol per mol parts, 6-amino-bromohexane and cis-5-norbornene-2, 3-dicarboxylic anhydride is 1 (1-2), the mixture is heated to 80-100 ℃ to carry out reflux reaction for 10-20 hours, preferably 10-16 hours, preferably, triethylamine is added as an acid binding agent when 6-amino-bromohexane is uniformly dispersed in toluene, and the volume ratio of toluene and triethylamine is (5-20): 1, preferably (5-15): 1.

The azobenzene side chain polymerizable monomer (i.e., an azobenzene side chain polymerizable monomer based on a modified cis-5-norbornene-2, 3-dicarboxylic anhydride) was prepared according to the following procedure: uniformly dispersing modified cis-5-norbornene-2, 3-dicarboxylic anhydride in dimethylformamide, adding an azobenzene monomer and anhydrous potassium carbonate, heating and refluxing in an inert protective gas atmosphere for reaction, and purifying to obtain the azobenzene side chain polymerizable monomer.

The method comprises the steps of preparing a modified cis-5-norbornene-2, 3-dicarboxylic anhydride, an azobenzene monomer, a modified cis-5-norbornene-2, 3-dicarboxylic anhydride, an inert protective gas, nitrogen, helium or argon, heating to 100-120 ℃, carrying out reflux reaction for 5-10 hours, preferably 8-10 hours, extracting for 1-5 times by using a mixed solution of water and dichloromethane (the volume ratio of the water to the dichloromethane solution is 1:3) after reflux reaction, combining organic phases, carrying out rotary evaporation to remove an organic solvent to obtain a crude product, and separating by using a chromatographic column to obtain the side chain azobenzene polymerizable monomer.

The preparation method of the azobenzene side chain polymer energy storage material is characterized in that under the catalysis of Grubbs' third generation reagent, azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride is used as polymerization monomer, and the azobenzene side chain polymerizable monomer is prepared by an active ring-opening metathesis polymerization method, wherein:

the molar ratio of the Grubbs' third generation reagent to the modified cis-5-norbornene-2, 3-dicarboxylic anhydride based azobenzene side chain polymerizable monomer is 1: (30-60), preferably 1: (50-60).

Dichloromethane is used as a reaction solvent, and a Grubbs third-generation reagent and an azobenzene side chain polymerizable monomer based on modified cis-5-norbornene-2, 3-dicarboxylic anhydride are uniformly dispersed.

The polymerization temperature is from room temperature to 20 to 25 ℃ and the reaction time is from 10 to 20 hours, preferably from 10 to 16 hours.

Stirring is used during the polymerization process to make the system participate in the reaction uniformly, such as 100-300 rpm, while an inert protective gas is used to provide an atmosphere for the polymerization, such as nitrogen, argon or helium.

Adding a terminating agent to terminate the living ring-opening metathesis polymerization reaction, such as vinyl ethyl ether; in the process of terminating the polymerization reaction by adding the terminator, stirring is used to uniformly stop the reaction of the system, and in consideration of influence factors such as the degree of the reaction, the stirring is carried out for at least 30min, preferably 0.5 to 1 hour after the addition of the terminator to terminate the polymerization reaction.

The Grubbs third-generation reagent is used for catalyzing and carrying out active ring-opening metathesis polymerization, the molecular structure, the molecular weight and the molecular weight distribution of the magnetic polymer are controllable in the whole active polymerization process, the dispersion coefficient of the molecular weight of the prepared polymer is less than 1.3, the polymerization degree n of the prepared polymer is 30-80, and n is preferably 45-60.

In the process of preparing the polymer of the present invention, the catalyst used is a Grubbs third generation reagent (i.e., a Grubbs third generation catalyst) having a structure according to the following general chemical structure:

the polymerization of cis-norbornene monomer catalyzed by The compound is active polymerization which has The advantages of mild reaction condition, high reaction efficiency and high speed, etc. The Polymer obtained by The polymerization has The characteristics of controllable molecular weight and narrow dispersity ( is The dispersion coefficient less than 1.3). The method of ring-opening metathesis polymerization catalyzed by Grubbs 'third generation reagent can realize The control and adjustment of molecular weight and molecular weight distribution of The magnetic Polymer, wherein The benzene ring Ph of The end group of The Polymer is from The benzene ring Ph in The Grubbs' third generation reagent, The other end group of The Polymer is from The terminator added at The end of The polymerization reaction, The terminator used is vinyl ethyl ether, so The other end group of The Polymer is in The structure of ethyl ether (refer to The structure of arita Leitgeb, Julian Wappel, Chrisan Slugovc, The ROMP toolbox graded 2010, Polymer 51 (2927-2946)).

The reaction mixture obtained by polymerization is dropped into vigorously stirred n-hexane to precipitate the reaction solution, and then the polymer containing the azo side chain is obtained after vacuum drying for 24 hours under the condition of 40 ℃ to 50 ℃.

The polymer disclosed by the invention has plasticity, namely, can form a film, overcomes the defect of poor film forming property of an azobenzene-graphene composite material, is uniformly dispersed in tetrahydrofuran and is spin-coated into a mold, and the film can be formed after forming, wherein the film thickness is between 0.5mm and 1mm, wherein: the amount of the polymer is 0.2-0.5 parts by mass (1 g per part by mass), and the amount of tetrahydrofuran is 1-5 parts by volume (1 ml per part by volume); selecting ultra-dry tetrahydrofuran as tetrahydrofuran; and uniformly dispersing the polymer in tetrahydrofuran, spin-coating the polymer on a mold, and heating the mold on a hot table at 40-50 ℃ for 4-6 hours to form a film.

Compared with the prior art, in the technical scheme of the invention, polycarboxyazobenzene is used as a side chain to be grafted to an alkyl chain to prepare a polymerizable monomer with storage and release functions, then a polymer with a controllable structure is prepared by an active ring-opening metathesis polymerization method under the catalysis of Grubbs three-generation reagent, and the storage and release of polymer energy under illumination are realized by utilizing intermolecular acting force and cis-trans isomerization of azobenzene.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of an azobenzene AZO monomer in the invention.

FIG. 2 is a UV absorption spectrum of the polymer composite of the present invention.

FIG. 3 is a DSC (differential scanning calorimetry) chart of the polymer composite of the present invention.

Detailed Description

The exothermic peak test of the prepared material is carried out by DSC scanning (differential scanning calorimetry), and then the exothermic peak is integrated by software to obtain the released energy and then divided by the mass to obtain the heat storage density of the material.