CN103936982A - Main chain type azobenzene polymer and preparation method thereof - Google Patents
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Abstract
The invention discloses a main chain type azobenzene polymer and a preparation method thereof. According to the preparation method, the main chain type aromatic azo polymer is prepared by adopting nitro reduction coupling reaction for the first time. The preparation method comprises the following steps: firstly synthesizing different types of monomers through a series of reactions, namely conjugate monomers and non-conjugate monomers; secondly, synthesizing a photocatalyst required by a polymerization system, namely gold nanoparticles loaded on zirconium oxide, and characterizing the photocatalyst through a series of tests; and finally carrying out nitro reduction coupling reaction of the monomers in the presence of a methylbenzene-isopropanol mixed solvent and potassium hydroxide, thus obtaining the main chain type aromatic azo polymer. The preparation method disclosed by the invention needs few polymerization reaction components, is simple, practicable, convenient in a purification process, mild in reaction conditions and has the advantages of low toxicity, high efficiency and environmental protection. The main chain type aromatic azo polymer prepared by using the method has good solubility and functionality and high optical application value.
Description
Technical field
The invention belongs to synthesis of polymer material field, be specifically related to conjugation that a kind of main chain contains azo group and non-conjugated polymeric thing and preparation method thereof.
Background technology
Aromatic azo compound is extremely chemist's favor always, has experienced so far the developing history of centuries, and lasting.Aromatic azo compound has a wide range of applications as aspects such as dyestuff, foodstuff additive, free radical reaction inductors in traditional chemical industry, also shows good prospect in drug release and photoelectron chemical field.Mainly, because aromatic azo-compound has, the characteristic of photic cis-trans isomerization and good photochromic properties to occur under the effect of light and heat, also extremely people's concern of its research aspect Modern High-Tech field, potentiality have a wide range of applications in fields such as liquid crystal material, photochemistry molecular switch, chemical sensor, biological photosensitizers and nonlinear optics information materials.
Based on the above using value of aromatic azo compound, more synthetic methods about aromatic azo compound are also developed by people.As everyone knows, the most classical synthetic method of aromatic azo compound is diazo coupling reaction, along with to new aromatic azo-compound in the urgent need to, in succession developed again in recent years some and upgraded more effective synthetic method.The conversion of for example reductive coupling reaction of the oxidizing reaction of metal catalyzed coupling reaction, arylamine, nitroaromatic and fragrant azo oxide compound and reduction etc.Wherein most synthetic method has been used to prepare aromatic azo polymers.
In the prior art, preparing aromatic azo polymers basic skills is previously prepared azo micromolecular compound, and then prepares aromatic azo polymers by certain reaction such as group or free radical.But the experimentation of these class methods is more loaded down with trivial details, and reactive component is more, cause certain wasting of resources.The method of the synthetic azobenzene polymer of some original positions is more and more subject to people's favor at present.But also there is certain inferior position in original position synthetic aroma family azobenzene polymer nowadays, for example in reaction system, need to introduce some metal ions, reaction conditions is harsher, and not high and low conversion rate of raw material stability etc., has caused certain environmental pollution and the wasting of resources.
Therefore, need to seek more preparation method with low toxicity high effective green environmentally friendly ground synthetic aroma family azobenzene polymer.
Summary of the invention
The object of this invention is to provide a kind of novel preparation method of backbone chain type azobenzene polymer, synthetic backbone chain type azobenzene polymer comprises conjugation and non-conjugated type; The polymkeric substance that the main chain that another kind of object of the present invention is to provide a kind of novel texture contains azobenzene group, this polymkeric substance has good solubility and functional.
For achieving the above object, general plotting of the present invention is by a series of monomers containing bifunctional (nitro), each monomer is carried out respectively reductive coupling and then synthetic backbone chain type conjugation or the non-conjugated azobenzene polymer of nitro under xenon (Xe) lamp irradiation, nano gold catalysis condition.
The concrete technical scheme of the present invention is: a kind of backbone chain type azobenzene polymer, and its chemical structural formula is the one in following structural formula:
Wherein x > 2; Y > 2; Z > 2.
In preferred technical scheme, the molecular weight of described backbone chain type azobenzene polymer is 2145～30000 grams/mol.
The preparation method of above-mentioned backbone chain type azobenzene polymer, comprises the following steps:
(1) chloric acid gold is dissolved in to ultrapure water and obtains chloric acid Jinsui River solution; Then by Zirconium oxide powder and chloric acid gold aqueous solution, stir and obtain mixed solution; Then Methionin is added in mixing solutions, stirring at room temperature, after 0.5 hour, adds sodium borohydride aqueous solution, hydrochloric acid soln in mixed solution successively, stirring at room temperature 24 hours; Obtaining product is photocatalyst;
Wherein, the mol ratio of zirconium white and chloric acid gold, Methionin, sodium borohydride, hydrochloric acid is 20.3: (0.3～0.6): 10.6: (3.0～5.0): 3.0;
(2) aqueous isopropanol of preparation potassium hydroxide; Then will add successively in the aqueous isopropanol of potassium hydroxide containing nitro monomer, toluene, Virahol, photocatalyst, ultrasonic dispersion obtains polymerization system;
Described is compd A, compd B or Compound C containing nitro monomer;
The structural formula of described compd A is
;
The structural formula of described compd B is
;
The structural formula of described Compound C is
;
In described polymerization system, the mass ratio that contains nitro monomer and photocatalyst, potassium hydroxide is (70～120): (30～60): 5.6; The volume ratio of Virahol and toluene is 1: (1～2); The concentration of photocatalyst is 3～10 mg/mL;
(3), in argon gas atmosphere, under xenon lamp radiation, above-mentioned polymerization system is carried out to photochemical catalysis polymerization and obtain backbone chain type azobenzene polymer; Described polymerization temperature is 40～50 DEG C, and polymerization time is 6～24 hours.
In technique scheme, the Virahol of step (2) and the ratio of toluene are 1: (0.5～2), in the time that the ratio of toluene and Virahol is excessive, has by product zinin and generate; In the time that the ratio of toluene and Virahol is too small, the decreased solubility of monomer in mixed solvent, affects carrying out smoothly of light-catalyzed reaction.
In technique scheme, the concentration of catalyzer is 3～10 mg/mL, and the concentration of promotor potassium hydroxide is 0.93 mg/mL; In the time that the concentration of catalyzer and promotor is less than normal, catalytic efficiency declines, and the transformation efficiency of monomer is not high and have certain intermediate and can not change into product completely.
In technique scheme, the particle diameter 20～100nm of Zirconium oxide powder in step (1).
In preferred technical scheme, after step (1), step (3) complete, respectively product is carried out to purification processes, described purge process comprises the following steps:
(i) purification processes of photocatalyst: after reaction finishes, suction filtration, water, washing with alcohol filter cake, by the filter cake vacuum-drying under 60 DEG C of conditions after washing, obtaining purple product is photocatalyst;
(ii) purification processes of backbone chain type azobenzene polymer: after reaction finishes, add with the tetrahydrofuran (THF) of reaction solution equal volume amounts reaction solution is diluted, then the reaction solution after dilution is splashed in methyl alcohol or normal hexane, and add saturated aqueous common salt that polymkeric substance is settled, leave standstill after 12～24 hours, suction filtration, then the filter cake obtaining is dissolved with tetrahydrofuran (THF), then suction filtration; Utilize methyl alcohol sedimentation to obtain solids the filtrate obtaining, through suction filtration, obtain henna product, be backbone chain type azobenzene polymer.
In technique scheme, monomer component is one-component, has avoided the monomer utilization ratio of multi-component reaction system not high, the shortcoming that by product is many.
Photocatalysis technology has adapted to the requirement of modern chemistry low toxicity high effective green environmentally friendly, synthetic and the design that has been widely used in reaction between all kinds of chemical groups and various functional materialss is upper, and wherein the polymer materials of the design of the photocatalysis technology of the green high-efficient of development in recent years and complex functionality has obtained certain concern.But, reduce by photocatalytic process the azobenzene polymer that nitroaromatic prepares backbone chain type and be not also in the news so far.
Due to the enforcement of such scheme, the present invention compared with prior art, has the following advantages:
1, first passage of the present invention be applicable to photochemical catalysis polymer main chain type azobenzene polymer containing nitro monomer, and the nanometer gold of working load on zirconium white is as catalyzer, under Xe (xenon) lamp irradiation, the reductive coupling reaction that carries out nitro containing nitro monomer is obtained to backbone chain type azobenzene polymer;
2, in the process of preparing backbone chain type azobenzene polymer disclosed by the invention, reaction conditions gentleness, monomer component is single, and the waste rate of raw material is low, and the generation of side reaction is few, has avoided loaded down with trivial details purification operations;
3, the present invention utilizes light to carry out the reductive coupling reaction of catalysis nitro, compared with existing metal ion catalysis, electrocatalysis and other reductive agent catalysis, not only avoided the waste of having mixed but also avoided natural resources and energy resources of metal ion, embody the feature of low toxicity high effective green environmentally friendly, met the demand for development of green industry.
Brief description of the drawings
Fig. 1 is the schematic flow sheet that in embodiment mono-, preparation contains nitro monomer;
Fig. 2 is the nuclear-magnetism phenogram of compd A and compd B in embodiment mono-;
Fig. 3 is the Electronic Speculum figure of photocatalyst in embodiment mono-;
Fig. 4 is the schematic flow sheet of preparing backbone chain type azobenzene polymer in embodiment mono-;
Fig. 5 is the GPC elution curve figure of non-conjugated polymeric thing PA and conjugated polymers PB, PC in embodiment mono-;
Fig. 6 is the infrared spectrum of non-conjugated polymeric thing PA and conjugated polymers PB, PC in embodiment mono-;
Fig. 7 is that the photic cis-trans isomerism of non-conjugated polymeric thing PA in embodiment bis-changes spectrogram;
Fig. 8 is that the photic cis-trans isomerism of conjugated polymers PB in embodiment bis-changes spectrogram;
Fig. 9 is that the photic cis-trans isomerism of conjugated polymers PC in embodiment bis-changes spectrogram.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described:
Chemical reagent used in the present embodiment: cupric nitrate, 99%, Aldrich; Trimethylamine hydrochloride, 98%, Aldrich; Ethyl formate, 99%, Aldrich; Dodecyl bromination magnesium, 1M, Aldrich; 1,12-dibromo-dodecane, 98%, Acros; 1-bromo-dodecane, 98%, Acros; Adjacent stupid biphenol, Acros; Methyl-sulphoxide, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Carbazole, 97%, China Medicine (Group) Shanghai Chemical Reagent Co.; Zirconium white, 30 nm, Lang Ge bio tech ltd, Suzhou; 2,7-dinitrobenzene-9,9-di-n-octyl-9-fluorenes (Compound C), 98%, Lang Ge bio tech ltd, Suzhou; Tosyl chloride, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Neutral alumina 100～200 orders, column chromatography FCP, China Medicine (Group) Shanghai Chemical Reagent Co.; Anhydrous sodium sulphate, sodium hydroxide, acetic acid, diacetyl oxide, hydrochloric acid, hydrochloro-auric acid, Methionin, sodium borohydride, sodium bicarbonate and potassiumiodide, analytical pure, China Medicine (Group) Shanghai Chemical Reagent Co.; Tetrahydrofuran (THF) (THF), methylene dichloride, methyl alcohol, ethanol, normal hexane and ethyl acetate, analytical pure, Chinasun Specialty Products Co., Ltd.
Testing tool and condition: gel permeation chromatograph: the 1515 type GPC of Waters of the U.S. (Waters); Condition determination: HR1, HR3 and HR4 tri-posts series connection are used, differential detector, moving phase is tetrahydrofuran (THF) (1mL/min), 30 DEG C of column temperatures are proofreaied and correct with polymethylmethacrylate standard specimen;
Ultra-violet absorption spectrum: the UV-3150 ultraviolet-visual spectrometer of Japanese Shimadzu company is measured;
Infrared absorption spectrum: infrared spectra (FT-IR) adopts Mangna-550 Nicocet determination of infrared spectroscopy, KBr pressed disc method.
Synthesizing of embodiment mono-, backbone chain type azobenzene polymer (PA, PB, PC)
Fig. 1 is that the present invention prepares the schematic flow sheet containing nitro monomer, with reference to the accompanying drawings 1:
Containing synthesizing of nitro monomeric compound A
In reaction flask, add successively 14.0g salt of wormwood and 200 mL
n, N-dimethyl formamide stirs 2 hours at 80 DEG C, then the pyrocatechol of 12.0 g is joined in above-mentioned solution, stirs 1 hour.Again the 1-bromo-dodecane of 20.0g is added dropwise in above-mentioned mixing solutions, and adds a small amount of potassiumiodide,, at 80 DEG C, stir 8 hours, afterwards, the cryosel that reaction solution is joined to 500 mL is bathed in beaker, stirs, and leaves standstill, and suction filtration, obtains crude product.The leacheate of petrol ether/ethyl acetate=20/1 for crude product is carried out to column chromatography for separation, obtain pure white product.Get above white product 8 g, 1,12-dibromo-dodecane 3.2g and salt of wormwood 5g and 200 mL's
n, N-dimethyl formamide is placed in reaction flask, stirs 12 hours at 80 DEG C.Reaction finishes reaction solution to join in the cryosel bath beaker of 500 mL, stirs, and leaves standstill, and suction filtration, obtains crude product.Utilize ethanol to carry out recrystallization to crude product and obtain pure intermediate 2.5 g;
Take in the mixing solutions that cupric nitrate 1.5g joins 10mL acetic acid and 10 mL diacetyl oxides, stirring at normal temperature is to evenly.Take again above-mentioned intermediate 1.44 g, slowly add in mixing solutions, normal-temperature reaction 6 hours.Reaction finishes reaction solution to join in the cryosel bath beaker of 250 mL, stirs, and leaves standstill, and suction filtration, obtains crude product.The leacheate of sherwood oil/tetrahydrofuran (THF)=5/1 for crude product is carried out to column chromatography for separation, obtain pure monomer (compd A) 1.1 g.
Containing synthesizing of nitro monomeric compound B
Add 155 mL ether and 7.4 g ethyl formates at dry three-necked bottle.Control temperature at-78 degree, under argon shield condition, dropwise add the diethyl ether solution of the octane magnesium bromide of 300mL (1 M).After dropwising, under room temperature condition, stir and spend the night.After reaction finishes, drip after the methyl alcohol cancellation reaction of 100 mL, then add the saturated ammonium chloride solution reaction of 50 mL.Then utilize saturated nacl aqueous solution to repeat to wash 3 times, by organic layer anhydrous sodium sulfate drying, revolve steaming, obtain white clean product (B1) 22.5 g;
In reaction flask, add successively the dichloromethane solution of 9.0 g B1,13.5 mL triethylamines, 3.7 g trimethylamine hydrochlorides and 50 mL, at 0 DEG C, stir, again 50 mL dichloromethane solutions of the Tosyl chloride of 11.3g are dropwise joined in above-mentioned solution to stirring at room temperature 12 hours.After reaction finishes, add saturated aqueous common salt extraction 5 times, use anhydrous sodium sulfate drying organic layer, revolve steaming, obtain thick product.The leacheate of petrol ether/ethyl acetate=10/1 for crude product is carried out to column chromatography for separation, obtain pure white product (B2) 7.6 g;
The potassium hydroxide and the 50 mL methyl-sulphoxides that in the reaction flask of 250 mL, add 1.67 g carbazoles, 2.8g, stir under room temperature.5.0 g B2 are dissolved in the methyl-sulphoxide of 50 mL, dropwise join in above-mentioned mixing solutions, stirring at room temperature 12 hours.After reaction finishes, add the water of 50 mL, and be extracted with ethyl acetate three times, organic layer anhydrous sodium sulfate drying, revolves steaming, obtains thick product.Under 80 degree, carry out recrystallization by ethyl acetate, obtain clean product B3 2.1 g;
Take in the mixing solutions that cupric nitrate 0.7g joins 10mL acetic acid and 10 mL diacetyl oxides, stirring at normal temperature is to evenly.Take again above-mentioned product B 3 0.5 g, slowly add in mixing solutions, normal-temperature reaction 6 hours.Reaction finishes reaction solution to join in the cryosel bath beaker of 250 mL, stirs, and leaves standstill, and suction filtration, obtains crude product.The leacheate of petrol ether/ethyl acetate=20/1 for crude product is carried out to column chromatography for separation, obtain pure monomer (compd B) 0.6 g.
Accompanying drawing 2 is the nuclear magnetic spectrum of above-claimed cpd A and compd B, can find in monomer the ownership of corresponding hydrogen from figure, and the integration of each hydrogen-like and ratio is all consistent with theory, has illustrated and has successfully synthesized above-mentioned monomer.
Synthesizing of photocatalyst
The chloric acid gold of 1g is dissolved in the ultrapure water of 99 mL, the Zirconium oxide powder of 30 nm of 2.5 g and above-mentioned chloric acid Jinsui River solution 20mL are joined in the three-necked bottle of 500 mL, stir.Take 1.55 g Methionins adds in above-mentioned homogeneous mixture solotion simultaneously, after stirring at room temperature 0.5 hour, the sodium borohydride aqueous solution of the 10mL (0.35 M) of preparation is slowly added in above-mentioned mixed solution, and then in the hydrochloric acid soln that adds 10 mL (0.3 M) that prepare in mixing solutions, stirring at room temperature 24 hours.After reaction finishes, suction filtration, with large water gaging, washing with alcohol filter cake, vacuum-drying under 60 degree conditions, obtains purple product 2.4 g.The Electronic Speculum figure that accompanying drawing 3 is above-mentioned photocatalyst; As shown in Figure 3, nanometer gold successfully loads on zirconic surface.
Accompanying drawing 4 is prepared the schematic flow sheet of backbone chain type azobenzene polymer for the present invention, and with reference to the accompanying drawings 4, obtain non-conjugated polymeric thing PA by the polymerization of non-conjugative monomer compd A, obtain conjugated polymers PB, PC by conjugative monomer compd B, Compound C polymerization.
Synthesizing of backbone chain type azobenzene polymer
In 10 clean mL ampoules, add successively the potassium hydroxide of 5.6 mg, the monomeric compound A of 80mg, the catalyzer of 33mg, the Virahol of 1mL, the toluene of 3mL, the ultrasonic monomer that makes dissolves completely, and then toward the aqueous isopropanol that adds 2 mL in ampoule.To passing into tube sealing after argon gas deoxygenation in 10 minutes in ampoule, the ampoule after tube sealing is placed in to Xe lamp, temperature is to react 6 hours under 42 degree conditions; After reaction finishes, each ampoule reaction solution is followed the tracks of according to thin-layer chromatography, finds total overall reaction of monomer.After reaction finishes, add the tetrahydrofuran (THF) of equivalent that reaction solution is diluted, then the reaction solution after dilution is splashed in methyl alcohol, and add several saturated aqueous common salts that polymkeric substance is settled smoothly, leave standstill after 12 hours, suction filtration, then the filter cake obtaining is dissolved with tetrahydrofuran (THF), suction filtration, removes the catalyzer in solution.Utilize methyl alcohol sedimentation to obtain polymkeric substance the filtrate obtaining, suction filtration, obtaining henna polymkeric substance is backbone chain type azobenzene polymer PA, its chemical structural formula is (x ≈ 9):
In 10 clean mL ampoules, add successively the potassium hydroxide of 5.6 mg, the monomeric compound B of 80mg, the catalyzer of 33mg, the Virahol of 1mL, the toluene of 3mL, the ultrasonic monomer that makes dissolves completely, and then toward the aqueous isopropanol that adds 2 mL in ampoule.To passing into tube sealing after argon gas deoxygenation in 10 minutes in ampoule, the ampoule after tube sealing is placed in to Xe lamp, temperature is to react 16 hours under 45 degree conditions; After reaction finishes, each ampoule reaction solution is followed the tracks of according to thin-layer chromatography, finds total overall reaction of monomer.After reaction finishes, add the tetrahydrofuran (THF) of equivalent that reaction solution is diluted, then the reaction solution after dilution is splashed in methyl alcohol, and add several saturated aqueous common salts that polymkeric substance is settled smoothly, leave standstill after 20 hours, suction filtration, then the filter cake obtaining is dissolved with tetrahydrofuran (THF), suction filtration, removes the catalyzer in solution.Utilize methyl alcohol sedimentation to obtain polymkeric substance the filtrate obtaining, suction filtration, obtaining henna polymkeric substance is backbone chain type azobenzene polymer PB, its chemical structural formula is (y ≈ 8):
In 10 clean mL ampoules, add successively the potassium hydroxide of 5.6 mg, the monomeric compound C of 70mg, the catalyzer of 35mg, the Virahol of 1mL, the toluene of 3mL, the ultrasonic monomer that makes dissolves completely, and then toward the aqueous isopropanol that adds 2 mL in ampoule.To passing into tube sealing after argon gas deoxygenation in 10 minutes in ampoule, the ampoule after tube sealing is placed in to Xe lamp, temperature is to react 14 hours under 50 degree conditions; After reaction finishes, each ampoule reaction solution is followed the tracks of according to thin-layer chromatography, finds total overall reaction of monomer.After reaction finishes, add the tetrahydrofuran (THF) of equivalent that reaction solution is diluted, then the reaction solution after dilution is splashed in normal hexane, and add several saturated aqueous common salts that polymkeric substance is settled smoothly, leave standstill after 24 hours, suction filtration, then the filter cake obtaining is dissolved with tetrahydrofuran (THF), suction filtration, removes the catalyzer in solution.Utilize methyl alcohol sedimentation to obtain polymkeric substance the filtrate obtaining, suction filtration, obtaining henna polymkeric substance is backbone chain type azobenzene polymer PC, its chemical structural formula is (z ≈ 68):
Accompanying drawing 5 is the GPC elution curve of above-mentioned non-conjugated polymeric thing PA and conjugated polymers PB, PC; As shown in Figure 5, the molecular weight of non-conjugated polymeric thing PA is 6500 grams/mol, and the molecular weight of conjugated polymers PB is 4100 grams/mol, and the molecular weight of conjugated polymers PC is 28000 grams/mol.
Accompanying drawing 6 is the infrared spectrum of above-mentioned non-conjugated polymeric thing PA and conjugated polymers PB, PC; As shown in the figure, three kinds of polymkeric substance are at 1594 cm
-1there is obvious azo absorption peak at place.Illustrate and successfully prepared backbone chain type fragrance azobenzene polymer.
The photic cis-trans isomerism of embodiment bis-, backbone chain type azobenzene polymer (PA, PB, PC) changes
Above-mentioned non-conjugated polymeric thing PA and conjugated polymers PB, PC are dissolved in to the polymkeric substance tetrahydrofuran solution that tetrahydrofuran (THF) configuration concentration is 0.033mg/mL, use UV-irradiation solution, the photic cis-trans isomerism of studying each polymkeric substance changes.
The photic cis-trans isomerism that accompanying drawing 7, accompanying drawing 8, accompanying drawing 9 are respectively above-mentioned non-conjugated polymeric thing PA and conjugated polymers PB, PC changes collection of illustrative plates.
As shown in Figure 7, there is cis-trans isomerization in the tetrahydrofuran solution of non-conjugated polymeric thing PA (concentration is 0.033mg/mL) under the UV-irradiation of 365 nm, and irradiation is after 35 seconds, and the azo cis-trans isomerism of polymkeric substance reaches balance substantially.And then utilize the UV-light of 435 nm to carry out irradiation, make nitrogen benzide become trans and irradiation from cis and within 180 seconds, can make the cis-trans configurations of nitrogen benzide reach balance.In addition, the changing conditions of the uv atlas under different wave length irradiation has also well proved to successfully synthesize backbone chain type fragrance azobenzene polymer.
As shown in Figure 8, there is cis-trans isomerization in the tetrahydrofuran solution of conjugated polymers PB (concentration is 0.033mg/mL) under the UV-irradiation of 404 nm, and irradiation is after 70 seconds, and the azo cis-trans isomerism of polymkeric substance reaches balance substantially.And then utilize the UV-light of 546 nm to carry out irradiation, making nitrogen benzide become trans and irradiation from cis can make the cis-trans configurations of nitrogen benzide reach balance for 180 seconds, compare with the photoisomerization of the nitrogen benzide of non-conjugated polymeric thing PA as can be seen from Fig., the photoisomerization phenomenon of conjugated polymers PB is not clearly, major cause is that PB main polymer chain is rigid state, and the transformation of the cis-trans isomerism of nitrogen benzide is pind down.
As shown in Figure 9, there is cis-trans isomerization in the tetrahydrofuran solution of conjugated polymers PC (concentration is 0.033mg/mL) under the UV-irradiation of 435 nm, and irradiation is after 150 seconds, and the azo cis-trans isomerism of polymkeric substance reaches balance substantially.And then utilize the UV-light of 546 nm to carry out irradiation, making nitrogen benzide become trans and irradiation from cis can make the cis-trans configurations of nitrogen benzide reach balance for 900 seconds, the same with the photoisomerization phenomenon of conjugated polymers PB as can be seen from Fig., the photoisomerization of azo is not clearly, be also mainly because PC main polymer chain is rigid state, the transformation of the cis-trans isomerism of nitrogen benzide is pind down.
Claims (5)
1. a backbone chain type azobenzene polymer, is characterized in that: its chemical structural formula is in following structural formula
A kind of:
Wherein x > 2; Y > 2, z > 2.
2. backbone chain type azobenzene polymer according to claim 1, is characterized in that: the molecular weight of described backbone chain type azobenzene polymer is 2145～30000 grams/mol.
3. the preparation method of backbone chain type azobenzene polymer described in claim 1, is characterized in that comprising the following steps:
(1) chloric acid gold is dissolved in to ultrapure water and obtains chloric acid Jinsui River solution; Then by Zirconium oxide powder and chloric acid gold aqueous solution, stir and obtain mixed solution; Methionin is added in mixing solutions, stirring at room temperature, after 0.5 hour, adds sodium borohydride aqueous solution, hydrochloric acid soln in mixed solution successively, stirring at room temperature 24 hours again; Obtaining product is photocatalyst;
Wherein, the mol ratio of zirconium white and chloric acid gold, Methionin, sodium borohydride, hydrochloric acid is 20.3: (0.3～0.6): 10.6: (3.0～5.0): 3.0;
(2) aqueous isopropanol of preparation potassium hydroxide; Then will add successively in the aqueous isopropanol of potassium hydroxide containing nitro monomer, toluene, Virahol, photocatalyst, ultrasonic dispersion obtains polymerization system;
Described is compd A, compd B or Compound C containing nitro monomer;
The structural formula of described compd A is
;
The structural formula of described compd B is
;
The structural formula of described Compound C is
;
In described polymerization system, the mass ratio that contains nitro monomer and photocatalyst, potassium hydroxide is (70～120): (30～60): 5.6; The volume ratio of Virahol and toluene is 1: (1～2); The concentration of photocatalyst is 3～10 mg/mL;
(3), in argon gas atmosphere, under xenon lamp radiation, above-mentioned polymerization system is carried out to photochemical catalysis polymerization and obtain backbone chain type azobenzene polymer; Described polymerization temperature is 40～50 DEG C, and polymerization time is 6～24 hours.
4. preparation method according to claim 3, is characterized in that: in step (1), the particle diameter of Zirconium oxide powder is 20～100 nm.
5. preparation method according to claim 3, is characterized in that: after step (1), step (3) complete, respectively product is carried out to purification processes, described purge process comprises the following steps:
(i) purification processes of photocatalyst: after reaction finishes, suction filtration, water, washing with alcohol filter cake, by the filter cake vacuum-drying under 60 DEG C of conditions after washing, obtaining purple product is photocatalyst;
(ii) purification processes of backbone chain type azobenzene polymer: after reaction finishes, add with the tetrahydrofuran (THF) of reaction solution equal volume amounts reaction solution is diluted, then the reaction solution after dilution is splashed in methyl alcohol or normal hexane, and add saturated aqueous common salt that polymkeric substance is settled, leave standstill after 12～24 hours, suction filtration, then the filter cake obtaining is dissolved with tetrahydrofuran (THF), then suction filtration; Utilize methyl alcohol sedimentation to obtain solids the filtrate obtaining, through suction filtration, obtain henna product, be backbone chain type azobenzene polymer.
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Cited By (3)
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| CN108395527A (en) * | 2018-04-04 | 2018-08-14 | 苏州大学 | A kind of azobenzene polyether ester segmented copolymer elastomer and preparation method thereof with photo-deformable performance |
| CN112341652A (en) * | 2020-11-23 | 2021-02-09 | 苏州大学 | Chiral azobenzene polymer film and preparation method and application thereof |
| CN114805762A (en) * | 2022-05-30 | 2022-07-29 | 吉林建筑大学 | Porous organic polymer containing azobenzene, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108395527A (en) * | 2018-04-04 | 2018-08-14 | 苏州大学 | A kind of azobenzene polyether ester segmented copolymer elastomer and preparation method thereof with photo-deformable performance |
| CN112341652A (en) * | 2020-11-23 | 2021-02-09 | 苏州大学 | Chiral azobenzene polymer film and preparation method and application thereof |
| CN112341652B (en) * | 2020-11-23 | 2022-06-07 | 苏州大学 | Chiral azobenzene polymer film and preparation method and application thereof |
| CN114805762A (en) * | 2022-05-30 | 2022-07-29 | 吉林建筑大学 | Porous organic polymer containing azobenzene, and preparation method and application thereof |
| CN114805762B (en) * | 2022-05-30 | 2023-06-27 | 吉林建筑大学 | Porous organic polymer containing azobenzene and preparation method and application thereof |
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| CN103936982B (en) | 2016-01-27 |
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