CN103936982B - A kind of backbone chain type azobenzene polymer and preparation method thereof - Google Patents
A kind of backbone chain type azobenzene polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of backbone chain type azobenzene polymer and preparation method thereof.The present invention adopts the reductive coupling reaction of nitro first, prepares backbone chain type fragrance azobenzene polymer.First dissimilar monomer is synthesized by series reaction, i.e. conjugated type monomer and non-co-yoke type monomer; Secondly the photocatalyst needed for synthesized polymer system, i.e. the golden nanometer particle of load on zirconium white, characterizes catalyzer by a series of test; Last under toluene and the mixed solvent of Virahol and the existence of potassium hydroxide, carry out the nitroreduction coupling polymerization reaction of monomer, thus obtain backbone chain type fragrance azobenzene polymer.In the preparation method of the present invention's exploitation, polyreaction component is single, simple, purification process convenient, reaction conditions is gentle, has the advantage of low toxicity high effective green environmentally friendly; The backbone chain type fragrance azobenzene polymer obtained accordingly has good solubility and functional, has good optical application and is worth.
Description
Technical field
The invention belongs to synthesis of polymer material field, be specifically related to conjugation and non-conjugated polymeric thing and preparation method thereof that a kind of main chain contains azo group.
Background technology
The favor of aromatic azo compound extremely chemist always, has experienced the developing history of centuries so far, and lasting.Aromatic azo compound has a wide range of applications as in dyestuff, foodstuff additive, free radical reaction inductor etc. in traditional chemical industry, also shows good prospect in drug release and photoelectron chemical field.Mainly because aromatic azo-compound has the characteristic and excellent photochromic properties that photic cis-trans isomerization can occur under the effect of light and heat, the concern of its research in Modern High-Tech field also extremely people, 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 potentiality.
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 some in recent years and upgraded more effective synthetic method.Conversion and reduction etc. of the such as oxidizing reaction of metal catalyzed coupling reaction, arylamine, the reductive coupling reaction of nitroaromatic and fragrant azo oxide compound.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 reactions such as certain group or free radicals.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 some fabricated in situ azobenzene polymers is more and more subject to the favor of people at present.But nowadays also there is certain inferior position in fabricated in situ aromatic azo polymers, such as, need in reaction system to introduce some metal ions, reaction conditions is harsher, and not high and low conversion rate of raw material stability etc., causes 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 race azobenzene polymer.
Summary of the invention
The object of this invention is to provide a kind of novel processing step of backbone chain type azobenzene polymer, the backbone chain type azobenzene polymer of synthesis comprises conjugation and non-co-yoke type; The main chain that another kind of object of the present invention is to provide a kind of novel texture contains the polymkeric substance of azobenzene group, and 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), carries out the reductive coupling of nitro respectively and then synthesize backbone chain type conjugation or non-conjugated azobenzene polymer under xenon (Xe) lamp irradiation, nano gold catalysis condition to each monomer.
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 ultrapure water and obtains chloric acid gold solution; Then Zirconium oxide powder is mixed with chloric acid gold solution, stir and obtain mixed solution; Then add in mixing solutions by Methionin, sodium borohydride aqueous solution, hydrochloric acid soln, after 0.5 hour, add in mixed solution by stirring at room temperature 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 potassium hydroxide is prepared; Then add containing nitro monomer, toluene, Virahol, photocatalyst successively in the aqueous isopropanol of potassium hydroxide, ultrasonic disperse 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 containing 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 ~ 10mg/mL;
(3), in argon gas atmosphere, under xenon lamp radiation, above-mentioned polymerization system is carried out 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), when the ratio of toluene and Virahol is excessive, has by product zinin and generate; When 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 ~ 10mg/mL, and the concentration of promotor potassium hydroxide is 0.93mg/mL; When 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, carry out purification processes to product respectively, described purge process comprises the following steps:
The purification processes of (i) photocatalyst: after reaction terminates, suction filtration, with water, washing with alcohol filter cake, by the filter cake vacuum-drying under 60 DEG C of conditions after washing, namely obtaining purple product is photocatalyst;
(ii) purification processes of backbone chain type azobenzene polymer: after the completion of reaction, add and with the tetrahydrofuran (THF) of reaction solution equal volume amounts, reaction solution is diluted, then by the reaction solution instillation methyl alcohol after dilution or normal hexane, and add saturated aqueous common salt polymkeric substance is settled, leave standstill after 12 ~ 24 hours, suction filtration, then the filter cake tetrahydrofuran (THF) obtained is dissolved, then suction filtration; Utilize methyl alcohol sedimentation to obtain solids the filtrate obtained, through suction filtration, obtain henna product, be backbone chain type azobenzene polymer.
In technique scheme, monomer component is one-component, and the monomer utilization ratio avoiding multi-component reaction system is 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, in the synthesis being widely used in reaction between all kinds of chemical group and various functional materials and design, wherein the photocatalysis technology design of the green high-efficient of development in recent years and the polymer materials of complex functionality obtain certain concern.But the azobenzene polymer being prepared backbone chain type by photocatalytic process reduction nitroaromatic is 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, backbone chain type azobenzene polymer is obtained to the reductive coupling reaction carrying out nitro containing nitro monomer;
2, disclosed by the inventionly prepare in the process of backbone chain type azobenzene polymer, reaction conditions is gentle, and monomer component is single, and the waste rate of raw material is low, and the generation of side reaction is few, avoids 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, what both avoided metal ion mixes the waste that turn avoid natural resources and energy resources, embody the feature of low toxicity high effective green environmentally friendly, meet the demand for development of green industry.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that in embodiment one, preparation contains nitro monomer;
Fig. 2 is the nuclear-magnetism phenogram of compd A and compd B in embodiment one;
Fig. 3 is the Electronic Speculum figure of photocatalyst in embodiment one;
Fig. 4 is the schematic flow sheet preparing backbone chain type azobenzene polymer in embodiment one;
Fig. 5 is the GPC elution curve figure of non-conjugated polymeric thing PA and conjugated polymers PB, PC in embodiment one;
Fig. 6 is the infrared spectrum of non-conjugated polymeric thing PA and conjugated polymers PB, PC in embodiment one;
Fig. 7 is the photic cis-trans isomerism change spectrogram of non-conjugated polymeric thing PA in embodiment two;
Fig. 8 is the photic cis-trans isomerism change spectrogram of conjugated polymers PB in embodiment two;
Fig. 9 is the photic cis-trans isomerism change spectrogram of conjugated polymers PC in embodiment two.
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, 30nm, 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 order, 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: Waters of the U.S. (Waters) 1515 type GPC; Condition determination: HR1, HR3 and HR4 three columns in series uses, Composition distribution, and moving phase is tetrahydrofuran (THF) (1mL/min), and column temperature 30 DEG C, corrects with polymethylmethacrylate standard specimen;
Ultra-violet absorption spectrum: the UV-3150 ultraviolet-visual spectrometer of Japanese Shimadzu Corporation measures;
Infrared absorption spectrum: infrared spectra (FT-IR) adopts Mangna-550Nicocet determination of infrared spectroscopy, KBr pressed disc method.
The synthesis of embodiment one, backbone chain type azobenzene polymer (PA, PB, PC)
Fig. 1 is the schematic flow sheet that the present invention prepares containing nitro monomer, with reference to the accompanying drawings 1:
Containing the synthesis of nitro monomeric compound A
14.0g salt of wormwood and 200mL is added successively in reaction flask
n,N-dimethyl formamide, stirs 2 hours, then joins in above-mentioned solution by the pyrocatechol of 12.0g, stir 1 hour at 80 DEG C.Again the 1-bromo-dodecane of 20.0g is added dropwise in above-mentioned mixing solutions, and adds a small amount of potassiumiodide, stir 8 hours at 80 DEG C, afterwards, joined by reaction solution in the cryosel bath beaker of 500mL, stir, leave standstill, suction filtration, obtains crude product.The leacheate of crude product petrol ether/ethyl acetate=20/1 is carried out column chromatography for separation, obtains pure white product.Get above white product 8g, 1,12-dibromo-dodecane 3.2g and salt of wormwood 5g and 200mL
n,N-dimethyl formamide is placed in reaction flask, stirs 12 hours at 80 DEG C.Reaction terminates to be joined by reaction solution in the cryosel bath beaker of 500mL, and stir, leave standstill, suction filtration, obtains crude product.Utilize ethanol to carry out recrystallization to crude product and obtain pure intermediate 2.5g;
Taking cupric nitrate 1.5g joins in the mixing solutions of 10mL acetic acid and 10mL diacetyl oxide, and stirring at normal temperature is to even.Take above-mentioned intermediate 1.44g again, slowly add in mixing solutions, normal-temperature reaction 6 hours.Reaction terminates to be joined by reaction solution in the cryosel bath beaker of 250mL, and stir, leave standstill, suction filtration, obtains crude product.The leacheate of crude product sherwood oil/tetrahydrofuran (THF)=5/1 is carried out column chromatography for separation, obtains pure monomer (compd A) 1.1g.
Containing the synthesis of nitro monomeric compound B
155mL ether and 7.4g ethyl formate is added at the three-necked bottle of drying.Control temperature, at-78 degree, under argon shield condition, dropwise adds the diethyl ether solution of the octane magnesium bromide of 300mL (1M).After dropwising, stir under room temperature condition and spend the night.After reaction terminates, after dripping the methyl alcohol cancellation reaction of 100mL, then add the saturated ammonium chloride solution reaction of 50mL.Then utilize saturated nacl aqueous solution to repeat to wash 3 times, by organic over anhydrous dried over sodium sulfate, revolve steaming, obtain white clean product (B1) 22.5g;
The dichloromethane solution of 9.0gB1,13.5mL triethylamine, 3.7g trimethylamine hydrochloride and 50mL is added successively in reaction flask, stir at 0 DEG C, again the 50mL dichloromethane solution of the Tosyl chloride of 11.3g is dropwise joined in above-mentioned solution, stirring at room temperature 12 hours.Add saturated aqueous common salt after reaction terminates and extract 5 times, use anhydrous sodium sulfate drying organic layer, revolve steaming, obtain thick product.The leacheate of crude product petrol ether/ethyl acetate=10/1 is carried out column chromatography for separation, obtains pure white product (B2) 7.6g;
In the reaction flask of 250mL, add 1.67g carbazole, the potassium hydroxide of 2.8g and 50mL methyl-sulphoxide, stirred at ambient temperature is even.5.0gB2 is dissolved in the methyl-sulphoxide of 50mL, dropwise joins in above-mentioned mixing solutions, stirring at room temperature 12 hours.Add the water of 50mL after reaction terminates, and be extracted with ethyl acetate three times, organic over anhydrous dried over sodium sulfate, revolves steaming, obtains thick product.Under 80 degree, carry out recrystallization by ethyl acetate, obtain clean product B32.1g;
Taking cupric nitrate 0.7g joins in the mixing solutions of 10mL acetic acid and 10mL diacetyl oxide, and stirring at normal temperature is to even.Take above-mentioned product B 30.5g again, slowly add in mixing solutions, normal-temperature reaction 6 hours.Reaction terminates to be joined by reaction solution in the cryosel bath beaker of 250mL, and stir, leave standstill, suction filtration, obtains crude product.The leacheate of crude product petrol ether/ethyl acetate=20/1 is carried out column chromatography for separation, obtains pure monomer (compd B) 0.6g.
Accompanying drawing 2 is the nuclear magnetic spectrum of above-claimed cpd A and compd B, can find the ownership of hydrogen corresponding in monomer, and the integration of each hydrogen-like and ratio is all consistent, and describe and successfully synthesize above-mentioned monomer from figure with theory.
The synthesis of photocatalyst
The chloric acid of 1g gold is dissolved in the ultrapure water of 99mL, the Zirconium oxide powder of the 30nm of 2.5g and above-mentioned chloric acid gold solution 20mL is joined in the three-necked bottle of 500mL, stirs.Take 1.55g Methionin adds in above-mentioned homogeneous mixture solotion simultaneously, stirring at room temperature is after 0.5 hour, the sodium borohydride aqueous solution of the 10mL (0.35M) of preparation is slowly added in above-mentioned mixed solution, and then at the hydrochloric acid soln adding the 10mL (0.3M) prepared in mixing solutions, stirring at room temperature 24 hours.After reaction terminates, suction filtration, with large water gaging, washing with alcohol filter cake, vacuum-drying under 60 degree of conditions, namely obtains purple product 2.4g.Accompanying drawing 3 is the Electronic Speculum figure of above-mentioned photocatalyst; As shown in Figure 3, nanometer gold success load is on zirconic surface.
Accompanying drawing 4 prepares the schematic flow sheet of backbone chain type azobenzene polymer for the present invention, and with reference to the accompanying drawings 4, be polymerized by non-conjugative monomer compd A and obtain non-conjugated polymeric thing PA, be polymerized obtaining conjugated polymers PB, PC by conjugative monomer compd B, Compound C.
The synthesis of backbone chain type azobenzene polymer
In clean 10mL ampoule, add the potassium hydroxide of 5.6mg successively, 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 adds the aqueous isopropanol of 2mL in ampoule.In ampoule, pass into tube sealing after argon gas deoxygenation in 10 minutes, the ampoule after tube sealing is placed in Xe lamp, temperature is react 6 hours under 42 degree of conditions; After reaction terminates, each ampoule reaction solution is followed the tracks of according to thin-layer chromatography, finds monomer total overall reaction.After the completion of reaction, reaction solution dilutes by the tetrahydrofuran (THF) adding equivalent, then by the reaction solution instillation methyl alcohol after dilution, and add several saturated aqueous common salts polymkeric substance is settled smoothly, leave standstill after 12 hours, suction filtration, then the filter cake tetrahydrofuran (THF) obtained is dissolved, suction filtration, the catalyzer in removing solution.Utilize methyl alcohol sedimentation to obtain polymkeric substance, suction filtration the filtrate obtained, obtaining henna polymkeric substance is backbone chain type azobenzene polymer PA, and its chemical structural formula is (x ≈ 9):
In clean 10mL ampoule, add the potassium hydroxide of 5.6mg successively, 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 adds the aqueous isopropanol of 2mL in ampoule.In ampoule, pass into tube sealing after argon gas deoxygenation in 10 minutes, the ampoule after tube sealing is placed in Xe lamp, temperature is react 16 hours under 45 degree of conditions; After reaction terminates, each ampoule reaction solution is followed the tracks of according to thin-layer chromatography, finds monomer total overall reaction.After the completion of reaction, reaction solution dilutes by the tetrahydrofuran (THF) adding equivalent, then by the reaction solution instillation methyl alcohol after dilution, and add several saturated aqueous common salts polymkeric substance is settled smoothly, leave standstill after 20 hours, suction filtration, then the filter cake tetrahydrofuran (THF) obtained is dissolved, suction filtration, the catalyzer in removing solution.Utilize methyl alcohol sedimentation to obtain polymkeric substance, suction filtration the filtrate obtained, obtaining henna polymkeric substance is backbone chain type azobenzene polymer PB, and its chemical structural formula is (y ≈ 8):
In clean 10mL ampoule, add the potassium hydroxide of 5.6mg successively, 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 adds the aqueous isopropanol of 2mL in ampoule.In ampoule, pass into tube sealing after argon gas deoxygenation in 10 minutes, the ampoule after tube sealing is placed in Xe lamp, temperature is react 14 hours under 50 degree of conditions; After reaction terminates, each ampoule reaction solution is followed the tracks of according to thin-layer chromatography, finds monomer total overall reaction.After the completion of reaction, reaction solution dilutes by the tetrahydrofuran (THF) adding equivalent, then by the reaction solution instillation normal hexane after dilution, and add several saturated aqueous common salts polymkeric substance is settled smoothly, leave standstill after 24 hours, suction filtration, then the filter cake tetrahydrofuran (THF) obtained is dissolved, suction filtration, the catalyzer in removing solution.Utilize methyl alcohol sedimentation to obtain polymkeric substance, suction filtration the filtrate obtained, obtaining henna polymkeric substance is backbone chain type azobenzene polymer PC, and 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 1594cm
-1there is obvious azo absorption peak at place.Illustrate and successfully prepared backbone chain type fragrance azobenzene polymer.
The photic cis-trans isomerism change of embodiment two, backbone chain type azobenzene polymer (PA, PB, PC)
Above-mentioned non-conjugated polymeric thing PA and conjugated polymers PB, PC are dissolved in the polymkeric substance tetrahydrofuran solution that tetrahydrofuran (THF) configuration concentration is 0.033mg/mL, use UV-irradiation solution, study the photic cis-trans isomerism change of each polymkeric substance.
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, the tetrahydrofuran solution (concentration is 0.033mg/mL) of non-conjugated polymeric thing PA there occurs cis-trans isomerization under the UV-irradiation of 365nm, 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 435nm to carry out irradiation, make nitrogen benzide become trans and irradiation can make the cis-trans configurations of nitrogen benzide reach balance for 180 seconds from cis.In addition, the changing conditions of the uv atlas under different wave length irradiation also well demonstrates and successfully synthesizes backbone chain type fragrance azobenzene polymer.
As shown in Figure 8, the tetrahydrofuran solution (concentration is 0.033mg/mL) of conjugated polymers PB there occurs cis-trans isomerization under the UV-irradiation of 404nm, 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 546nm to carry out irradiation, nitrogen benzide is made to become trans and irradiation can make the cis-trans configurations of nitrogen benzide reach balance for 180 seconds from cis, photoisomerization as can be seen from Fig. with the nitrogen benzide of non-conjugated polymeric thing PA is compared, the photoisomerization phenomenon of conjugated polymers PB is not clearly, major cause is 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, the tetrahydrofuran solution (concentration is 0.033mg/mL) of conjugated polymers PC there occurs cis-trans isomerization under the UV-irradiation of 435nm, 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 546nm to carry out irradiation, nitrogen benzide is made to become trans and irradiation can make the cis-trans configurations of nitrogen benzide reach balance for 900 seconds from cis, photoisomerization phenomenon as can be seen from Fig. with conjugated polymers PB is the same, the photoisomerization of azo is not clearly, main is also because PC main polymer chain is rigid state, and 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 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. a preparation method for backbone chain type azobenzene polymer, is characterized in that comprising the following steps:
(1) chloric acid gold is dissolved in ultrapure water and obtains chloric acid gold solution; Then Zirconium oxide powder is mixed with chloric acid gold solution, stir and obtain mixed solution; Add in mixing solutions by Methionin again, sodium borohydride aqueous solution, hydrochloric acid soln, after 0.5 hour, add in mixed solution by stirring at room temperature 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 potassium hydroxide is prepared; Then add containing nitro monomer, toluene, Virahol, photocatalyst successively in the aqueous isopropanol of potassium hydroxide, ultrasonic disperse 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 containing 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 ~ 10mg/mL;
(3), in argon gas atmosphere, under xenon lamp radiation, above-mentioned polymerization system is carried out 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;
The chemical structural formula of described backbone chain type azobenzene polymer is the one in following structural formula:
Wherein x>2; Y>2, z>2.
4. preparation method according to claim 3, is characterized in that: in step (1), the particle diameter of Zirconium oxide powder is 20 ~ 100nm.
5. preparation method according to claim 3, is characterized in that: after step (1), step (3) complete, carry out purification processes to product respectively, described purge process comprises the following steps:
The purification processes of (i) photocatalyst: after reaction terminates, suction filtration, with water, washing with alcohol filter cake, by the filter cake vacuum-drying under 60 DEG C of conditions after washing, namely obtaining purple product is photocatalyst;
(ii) purification processes of backbone chain type azobenzene polymer: after the completion of reaction, add and with the tetrahydrofuran (THF) of reaction solution equal volume amounts, reaction solution is diluted, then by the reaction solution instillation methyl alcohol after dilution or normal hexane, and add saturated aqueous common salt polymkeric substance is settled, leave standstill after 12 ~ 24 hours, suction filtration, then the filter cake tetrahydrofuran (THF) obtained is dissolved, then suction filtration; Utilize methyl alcohol sedimentation to obtain solids the filtrate obtained, through suction filtration, obtain henna product, be backbone chain type azobenzene polymer.
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