CN104045754B - A kind of synthetic method of visible light-responded property azobenzene polymer - Google Patents
A kind of synthetic method of visible light-responded property azobenzene polymer Download PDFInfo
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Abstract
The present invention relates to the synthetic method of a kind of visible light-responded property azobenzene polymer, including: by 2, 6 dimethoxyanilines and 3, 5 syringol prepare tetramethoxy azophenol through diazo-reaction, and prepare tetramethoxy 4 hexanol epoxide diphenyl diimide with it for raw material and 6 bromine hexanol reactions, by the alcoholysis reaction of acid chloride groups, diphenyl diimide is grafted on poly acryloyl chloride skeleton again, unreacted acid chloride groups is carboxyl by hydrolysis, finally give a kind of azobenzene polymer with visible light-responded property, i.e. 2 (2, 6, 2 ', 6 ' tetramethoxy 4 hexaoxyazobenzene phenoxyls) ethyl acrylate acrylic copolymer.It is an advantage of the current invention that: this synthetic method is simple, the polymer of synthesis is with visible light-responded property azobenzene group, can realize trans to cis conversion under green glow (520nm) irradiates, and irradiate at blue light (420nm) and lower can realize reversely converting, compare the sharpest edges of traditional azobenzene molecule and i.e. need not ultraviolet light and can realize the two-way conversion of isomer.
Description
Technical field
The invention belongs to organic polymer chemistry field, it is provided that a kind of synthesizing visible light response is even
The method of pyridine polymer.
Background technology
Azobenzene compound is as a kind of material with good photosensitive property, at photoresponse high score
The research of sub-material has important function.In recent years, domestic and international computer MSR Information system is about by azo
Benzene chromophore is typed in polymer thus prepares the grinding of azobenzene polymer with optical Response
Studying carefully in the majority, this base polymer has the biggest potential at aspects such as optical information storage, biologic applications
Using value, thus caused the interest of people.
The cis-trans isomerization reaction of azobenzene group is that aromatic azo compound is of greatest concern
Character, the most cis with anti-configuration between phase co-conversion.Research shows, azo group has
Optical activity, it can carry out reversible trans and cis different under conditions of illumination or heating
Structureization changes, and tradition azobenzene molecule needs the regulation and control of ultraviolet light to realize, and ultraviolet light meeting
Biotic environment is produced certain destruction, and this shortcoming strongly limit its molecule in terms of biology
Application, such as self-assembled film loads medicine at organism to the reversible adsorption of protein, micelle
In release etc..
Need design at present badly, prepare some novel optical Response azobenzene molecules, be allowed to have not
Need the isomerization of azobenzene molecule in the irradiation i.e. controllable polymer of ultraviolet light, it is thus possible to control
The characteristic of its hydrophobe difference, in order to making a breakthrough property can enter in terms of the biologic applications of diphenyl diimide
Exhibition.
Summary of the invention
In order to solve the problems referred to above, it is an object of the invention to provide a kind of synthesizing visible light response
The method of the azobenzene polymer of property.
The method comprises the steps of firstly, preparing out 2,6,2 ' 6 '-tetramethoxy azophenol, and then obtain
2,6,2 ' 6 '-tetramethoxy-4 hexanol epoxide diphenyl diimide, it is grafted to gather by post-polymerization
On acryloyl chloride, obtained the azobenzene polymer of this visible light-responded property by hydrolysis.Prepared
Journey is as follows:
The method specifically includes following steps:
Step one: preparation 2,6,2 ' 6 '-tetramethoxy azophenol: by dimethoxyaniline, 36%
Concentrated hydrochloric acid and deionized water according to 1:(1.5～2): the mass ratio of (2～3) mixing, furnishing is stuck with paste
Shape, temperature controls at 0 DEG C；Under stirring, the volume ratio according to 1:2 is slowly added dropwise 1.5mmol/ml
NaNO2Chilled aqueous solution, stirring reaction to solution makes starch KI become indigo plant, is filtrated to get diazonium
Saline solution；The NaOH aqueous solution that syringol is dissolved in 1mmol/ml obtains
1mmol/ml phenol solution, the concentration being added dropwise to prepare by above-mentioned diazonium salt solution is
In the phenol solution of 1mmol/ml, wherein, diazonium saline solution: the volume ratio of phenol solution is 3:2；
During dropping, use saturated Na2CO3Solution regulation makes pH value be maintained at 10；After dripping
After continuing stirring 12h, neutralize in PH=6 with dilute HCl, stir 10min；Sucking filtration, will produce
It is neutrality that thing is washed with deionized to filtrate, is dried to obtain 2, and 6,2 ' 6 '-tetramethoxy diphenyl diimide
Phenol；
Step 2: preparation 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide: step one is obtained
The azophenol arrived, 6-bromine hexanol, anhydrous K2CO3, potassium iodide is according to 1:(0.72～1): (2～3):
The mass ratio of (0.1～0.3) and acetone mixing are placed in dry flask, 70 DEG C of oil bath heating, stir
Mix back flow reaction 24 hours；By reacting liquid filtering, concentrating, 50 DEG C are dried 24 hours；With four
After hydrogen furan dissolves, use petroleum ether recrystallization twice, purify further finally by chromatographic column
Obtain 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide；
Step 3: prepare poly acryloyl chloride: by monomer propylene acyl chlorides, be dried 1-4 dioxane
With initiator A IBN (azodiisobutyronitrile) according to 1:(1～2): the matter of (0.03～0.05)
Amount ratio joins in flask, 55 DEG C of successive reactions 20 hours under the protection of nitrogen；Product is used
It is dried petroleum ether precipitation and washes twice, being dried in vacuum drying oven at 60 DEG C and gathered for 6 hours
Acryloyl chloride；
Step 4: preparation 2-(2,6,2 ', 6 '-tetramethoxy-4-hexaoxyazobenzene phenoxyl) third
Olefin(e) acid ethylacrylate-acrylic acid copolymer: the poly acryloyl chloride that step 3 is obtained, triethylamine, and
The diphenyl diimide that step 2 obtains is dissolved in N, N-dimethyl according to the ratio mixing of mol ratio 12:17:1
In Methanamide, 60 DEG C of stirrings are reacted 24 hours under nitrogen protection；Add deionized water to make not
The acid chloride groups of reaction is hydrolyzed to carboxylic acid, reacts 10 minutes；Reactant is according to the volume of 1:20
Than in the concentrated hydrochloric acid pouring 36% into, stir 10 minutes；Cool down, filter to obtain solid, at 50 DEG C of bars
5h it is dried under part；Crude product is dissolved in DMF, pours precipitation secondary in ether into；
Filter, under the conditions of 50 DEG C, be dried 24h obtain 2-(2,6,2 ', 6 '-tetramethoxy-4-hexyloxy is even
Pyridyl phenoxy group) ethyl acrylate-acrylic acid copolymer.
Further, in described step 2, the addition of acetone is every gram of azophenol 80ml third
Ketone；In described step 4, the usage amount of N,N-dimethylformamide is every gram of diphenyl diimide 100ml,
The usage amount of deionized water is every gram of diphenyl diimide 3ml.
Preferably, the azophenol in described step 2, step one obtained, 6-bromine hexanol, nothing
Water K2CO3, potassium iodide mixes according to mass ratio and the acetone of 1:0.72:2:0.1.
Preferably, monomer propylene acyl chlorides, dry 1-4 dioxane and initiation in described step 3
Agent AIBN (azodiisobutyronitrile) joins in flask according to the mass ratio of 1:1:0.03.
Further, described on the polymer that obtains the azobenzene group of grafting be 2,6,2 ' 6 '-four
Methoxyl group-4-hexanol epoxide diphenyl diimide.
Further, on the polymer obtained described in, grafting is that azobenzene group has visible ray
Response, under the green glow that wavelength is 520nm irradiates, trans-azobenzene is changed into cis-structure,
And can realize reversely converting under the blue light illumination that wavelength is 420nm, so that the idol of synthesis
The photoisomerization of pyridine polymer can realize in visible-range.
The invention has the beneficial effects as follows: the isomerization of azobenzene polymer synthesized in the present invention
Can realize in visible-range completely, when irradiating with green glow (520nm), diphenyl diimide is real
Existing trans to cis conversion, and the cis of diphenyl diimide can be realized when blue light (420nm) irradiates
To trans conversion, the sharpest edges comparing tradition azobenzene molecule i.e. need not ultraviolet light, and
It it is the two-way heterogeneous body conversion being realized azobenzene molecule by visible ray.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide that step 2 obtains
(deuterated methanol).
Fig. 2 is the 2-(2,6,2 ', 6 '-tetramethoxy-4-hexaoxyazobenzene phenoxyl) that step 4 obtains
The nuclear magnetic spectrogram (deuterated DMSO) of ethyl acrylate-acrylic acid copolymer.
Fig. 3 is that 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide (DMSO is solvent) is not being shared the same light
(green glow, 520nm, 12mW/cm under according to2；Blue light, 420nm, 8mW/cm2) ultraviolet
-visible ray spectrogram.
Fig. 4 be azobenzene polymer (DMF is solvent) under green glow effect (520nm,
12mW/cm2) time dependent ultraviolet-visible light spectrogram, it is followed successively by green glow from top to bottom and shines
Penetrate 0,10,20,30,40,50,60,70,80,90,100,110s gained spectrogram.
Fig. 5 is azobenzene polymer (DMF is solvent) (420nm, 8mW/cm under blue light action2)
Time dependent ultraviolet-visible light spectrogram, is followed successively by green glow from top to bottom and irradiates 110s, indigo plant
Light irradiate 5,10,15,20,25,30,35,40,45,50,55,60s gained spectrum
Figure.
Detailed description of the invention
Embodiment 1
Preparation 2,6,2 ' 6 '-tetramethoxy azophenol: by dimethoxyaniline (1.53g,
0.01mol), concentrated hydrochloric acid (36%, 2.54ml) and deionized water (3ml) mixing, furnishing pasty state,
Temperature controls at about 0 DEG C.It is slowly added dropwise NaNO under stirring2(0.015mol, 1.035g)
10mL chilled aqueous solution.Stirring reaction to solution makes starch KI become indigo plant, is filtrated to get diazol
Solution；Syringol (1.54g, 0.01mol) is dissolved in NaOH (1g, 0.025mol)
In aqueous solution (10ml)；Aforementioned diazonium salt solution is added dropwise in phenol solution, dripped
Cheng Zhong, uses saturated Na2CO3Solution regulation makes pH value be maintained at 10.Continue after dripping to stir
After mixing 12h, it is neutralized to PH=6 with dilute HCl, stirs 10min.Sucking filtration, spends product
Ionized water washing is neutrality to filtrate, is dried.
Preparation 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide: the azo that step one is obtained
Phenol (1g, 3.14mmol), Br (CH2)6OH (0.523ml, 4mmol), anhydrous K2CO3
(2g), potassium iodide (0.1g), and acetone (80ml) mixing be placed in dry flask, 70 DEG C
Oil bath is heated, and is stirred at reflux reaction 24 hours.By reacting liquid filtering, concentrate, be dried.With
After oxolane dissolves, twice of petroleum ether (30～60 DEG C) recrystallization, finally by chromatographic column
Purify further.
Prepare poly acryloyl chloride: by monomer propylene acyl chlorides (10ml), be dried 1-4 dioxane
(10ml) join in flask with initiator A IBN azodiisobutyronitrile (0.302g),
The lower 55 DEG C of successive reactions of protection of nitrogen 20 hours.Product is with dry petroleum ether precipitation and washs
Twice, it is dried 6 hours in vacuum drying oven at 60 DEG C.
Preparation 2-(2,6,2 ', 6 '-tetramethoxy-4-hexaoxyazobenzene phenoxyl) ethyl acrylate
-acrylic copolymer: by poly acryloyl chloride (0.4g, 5.19mmol), triethylamine (8mmol,
1.12ml), and the diphenyl diimide (0.2g, 0.47mmol) that obtains of step 2 is dissolved in DMF (20ml)
In, 60 DEG C of stirrings are reacted 24 hours under nitrogen protection.Add 3ml deionized water and make the most anti-
The acid chloride groups answered is hydrolyzed to carboxylic acid, reacts 10 minutes.Reactant pours concentrated hydrochloric acid (200ml) into
In, stir 10 minutes.Cool down, filter to obtain solid, be dried (50 DEG C, 5h).Crude product is molten
In DMF, pour precipitation secondary in ether into.Filter, be dried (50 DEG C, 24h).
Embodiment 2
Preparation 2,6,2 ', 6 '-tetramethoxy azophenol: by dimethoxyaniline (1.53g,
0.01mol), concentrated hydrochloric acid (36%, 3ml) and deionized water (3.5ml) mixing, furnishing pasty state,
Temperature controls at about 0 DEG C.It is slowly added dropwise NaNO under stirring2(0.023mol, 1.55g) 15mL
Chilled aqueous solution.Stirring reaction to solution makes starch KI become indigo plant, is filtrated to get diazonium salt solution；
Syringol (1.54g, 0.01mol) is dissolved in NaOH (1.5g, 0.038mol) water
In solution (15ml)；Aforementioned diazonium salt solution is added dropwise in phenol solution, drips process
In, use saturated Na2CO3Solution regulation makes pH value be maintained at 10.Stirring is continued after dripping
After 12h, it is neutralized to PH=6 with dilute HCl, stirs 10min.Sucking filtration, product is spent from
The washing of sub-water is neutrality to filtrate, is dried.
Preparation 2,6,2 ', 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide: the idol that step one is obtained
Pyridine phenol (1g, 3.14mmol), Br (CH2)6OH (0.65ml, 5mmol), anhydrous K2CO3
(2.5g), potassium iodide (0.15g), and acetone (80ml) mixing be placed in dry flask, 70 DEG C
Oil bath is heated, and is stirred at reflux reaction 24 hours.By reacting liquid filtering, concentrate, be dried.With
After oxolane dissolves, twice of petroleum ether (30～60 DEG C) recrystallization, finally by chromatographic column
Purify further and obtain 2,6,2 ', 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide.
Prepare poly acryloyl chloride: by monomer propylene acyl chlorides (10ml), be dried 1-4 dioxane
(15ml) join in flask with initiator A IBN azodiisobutyronitrile (0.382g),
The lower 55 DEG C of successive reactions of protection of nitrogen 20 hours.Product is with dry petroleum ether precipitation and washs
Twice, it is dried in vacuum drying oven at 60 DEG C and obtains poly acryloyl chloride in 6 hours.
Preparation 2-(2,6,2 ', 6 '-tetramethoxy-4-hexaoxyazobenzene phenoxyl) ethyl acrylate
-acrylic copolymer: by poly acryloyl chloride (0.8g, 10.38mmol), triethylamine (16mmol,
2.24ml), and the diphenyl diimide (0.4g, 0.94mmol) that obtains of step 2 is dissolved in DMF (40ml)
In, 60 DEG C of stirrings are reacted 24 hours under nitrogen protection.Add 3ml deionized water and make the most anti-
The acid chloride groups answered is hydrolyzed to carboxylic acid, reacts 10 minutes.Reactant pours concentrated hydrochloric acid (400ml) into
In, stir 10 minutes.Cool down, filter to obtain solid, under the conditions of 50 DEG C, be dried 5h.Thick product
Thing is dissolved in DMF, pours precipitation secondary in ether into；Filter, under the conditions of 50 DEG C, be dried 24h.
The step 2 diphenyl diimide monomer of the present invention and the structure of step 4 azobenzene polymer are passed through
Nuclear-magnetism (accompanying drawing 1 and accompanying drawing 2) is proven.
The visible light-responded property of the diphenyl diimide monomer of the present invention is shown in accompanying drawing 3, it can be seen that green glow
(520nm) irradiating 10 minutes, 330nm peak declines, and azobenzene molecule is cis to trans turn
Change；After blue light (420nm) irradiates 10 minutes, 330nm peak rising, azobenzene molecule is anti-
Formula is to cis conversion；Its uv-vis spectra reversible change, illustrates that it has visible light-responded
Property.
The visible light-responded property of the azobenzene polymer of the present invention is shown in accompanying drawing 4 and accompanying drawing 5, permissible
See that the irradiation along with green glow, 325nm peak are gradually reduced, illustrate that azobenzene molecule is cis to instead
Formula converts；Along with blue light illumination, 325nm peak is gradually increasing, and azobenzene molecule is trans to cis
Convert；Its uv-vis spectra reversible change, illustrates that it has visible light-responded property.
Claims (6)
1. the synthetic method of a visible light-responded property azobenzene polymer, it is characterised in that: described method step is as follows:
Step one: preparation 2,6,2 ' 6 '-tetramethoxy azophenol: dimethoxyaniline, the concentrated hydrochloric acid of 36% and deionized water being mixed according to the mass ratio of 1:1.5 ~ 2:2 ~ 3, furnishing pasty state, temperature controls at 0 DEG C；It is slowly added dropwise the NaNO of 1.5mmol/mL according to the volume ratio of 1:2 under stirring2Chilled aqueous solution, stirring reaction to solution makes starch KI become indigo plant, is filtrated to get diazonium salt solution；The NaOH aqueous solution that syringol is dissolved in 1mmol/mL obtains 1mmol/mL phenol solution, is added dropwise to by above-mentioned diazonium salt solution in the phenol solution that concentration is 1mmol/mL prepared, wherein, and diazonium saline solution: the volume ratio of phenol solution is 3:2；During dropping, use saturated Na2CO3Solution regulation makes pH value be maintained at 10；After continuing stirring 12h after dripping, neutralize in pH=6 with dilute HCl, stir 10min；Sucking filtration, being washed with deionized by product to filtrate is neutrality, is dried to obtain 2, and 6,2 ' 6 '-tetramethoxy azophenol；
Step 2: preparation 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide: the azophenol that step one is obtained, 6-bromine hexanol, anhydrous K2CO3,
Potassium iodide is placed in dry flask according to mass ratio and the acetone mixing of 1:0.72 ~ 1:2 ~ 3:0.1 ~ 0.3, and 70 DEG C of oil bath heating are stirred at reflux reaction 24 hours；By reacting liquid filtering, concentrating, 50 DEG C are dried 24 hours；After dissolving with oxolane, use petroleum ether recrystallization twice, purify further finally by chromatographic column and obtain 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide；
Step 3: prepare poly acryloyl chloride: by monomer propylene acyl chlorides, be dried Isosorbide-5-Nitrae-dioxane and initiator A IBN(azodiisobutyronitrile) join in flask according to the mass ratio of 1:1 ~ 2:0.03 ~ 0.05,55 DEG C of successive reactions 20 hours under the protection of nitrogen；Product is with dry petroleum ether precipitation and washes twice, and is dried and obtains poly acryloyl chloride in 6 hours at 60 DEG C in vacuum drying oven；
Step 4: preparation 2-(2; 6; 2 '; 6 '-tetramethoxy-4-hexaoxyazobenzene phenoxyl) ethyl acrylate-acrylic acid copolymer: the poly acryloyl chloride that step 3 is obtained; triethylamine; the diphenyl diimide obtained with step 2 is dissolved in DMF according to the ratio mixing of mol ratio 12:17:1, and 60 DEG C of stirrings are reacted 24 hours under nitrogen protection；Adding deionized water makes unreacted acid chloride groups be hydrolyzed to carboxylic acid, reacts 10 minutes；Reactant is poured in the concentrated hydrochloric acid of 36% according to the volume ratio of 1:20, stirs 10 minutes;Cool down, filter to obtain solid, under the conditions of 50 DEG C, be dried 5h;Crude product is dissolved in DMF, pours precipitation secondary in ether into;Filter, under the conditions of 50 DEG C, be dried 24h obtain 2-(2,6,2 ', 6 '-tetramethoxy-4-hexaoxyazobenzene phenoxyl) ethyl acrylate-acrylic acid copolymer.
Method the most according to claim 1, it is characterised in that: in described step 2, the addition of acetone is every gram of azophenol 80mL acetone；In described step 4, the usage amount of N,N-dimethylformamide is every gram of diphenyl diimide 100mL
The usage amount of deionized water is every gram of diphenyl diimide 3mL.
Method the most according to claim 1, it is characterised in that: the azophenol in described step 2, step one obtained, 6-bromine hexanol, anhydrous K2CO3, potassium iodide mixes according to mass ratio and the acetone of 1:0.72:2:0.1.
Method the most according to claim 1, it is characterised in that: monomer propylene acyl chlorides, dry Isosorbide-5-Nitrae-dioxane and initiator A IBN(azodiisobutyronitrile in described step 3) join in flask according to the mass ratio of 1:1:0.03.
Method the most according to claim 1, it is characterised in that on the polymer obtained described in:, the azobenzene group of grafting is 2,6,2 ' 6 '-tetramethoxy-4-hexanol epoxide diphenyl diimide.
Method the most according to claim 1, it is characterized in that: described on the polymer that obtains grafting be that azobenzene group has visible light-responded property, under the green glow that wavelength is 520nm irradiates, trans-azobenzene is changed into cis-structure, and can realize reversely converting under the blue light illumination that wavelength is 420nm, so that the photoisomerization of the azobenzene polymer of synthesis can realize in visible-range.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1975552A (en) * | 2006-12-11 | 2007-06-06 | 苏州大学 | Third order non-linear optical material monomer, its polymer and production |
| CN103193989A (en) * | 2013-02-28 | 2013-07-10 | 北京科技大学 | Preparation method of light/pH-sensitive amphiphilic azobenzene polymer micelles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012077228A (en) * | 2010-10-04 | 2012-04-19 | Kumamoto Univ | New liquid crystal polymer and optical element using the same |
-
2014
- 2014-06-18 CN CN201410273225.4A patent/CN104045754B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1975552A (en) * | 2006-12-11 | 2007-06-06 | 苏州大学 | Third order non-linear optical material monomer, its polymer and production |
| CN103193989A (en) * | 2013-02-28 | 2013-07-10 | 北京科技大学 | Preparation method of light/pH-sensitive amphiphilic azobenzene polymer micelles |
Non-Patent Citations (1)
| Title |
|---|
| "Azobenzene Photoswitching without Ultraviolet Light";Andrew A. Beharry et al.;《J. Am. Chem. Soc.》;20111114;第133卷;19684-19687 * |
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