CN105440190B - A kind of preparation method of multiple response azobenzene functionalized polymer - Google Patents
A kind of preparation method of multiple response azobenzene functionalized polymer Download PDFInfo
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Abstract
A kind of preparation method of multiple response azobenzene functionalized polymer, this method gather polymerized monomer dimethylaminoethyl methacrylate by atom transition free radical polymerization reaction synthetic polymer（Methyl）Dimethylaminoethyl acrylate, using m-benzotrifluoride amine and phenol as raw material, pass through the azobenzene small molecule m-trifluoromethyl azophenol of diazo-reaction anamorphic zone phenolic hydroxyl group, again nucleophilic substitution is carried out with dibromobutane, the brombutyl azobenzene of 3 trifluoromethyl of azo small molecule 4 of active bromine is contained in generation one end, then by quaterisation is grafted to azo group under 35 degrees Celsius poly-（Methyl）On dimethylaminoethyl acrylate, the polymethylacrylic acid dimethylaminoethyl of azobenzene functionalization is finally given.This synthetic method is simple and easy, and the more traditional reaction temperature of reaction temperature is low, and the polymer of synthesis not only has temperature-responsive and pH responses, and also has optical Response, is a kind of new polymer with temperature, pH and optical Response.
Description
Technical field
The invention belongs to organic chemistry filed, there is provided a kind of to synthesize with multiple response azobenzene functionalized polymer
Method.
Background technology
Stimulating responsive polymer material refers to that light, heat, electric field, magnetic field, pH, ionic strength, various chemicals can be perceived
The various external conditions such as matter stimulate, and respond rapidly, make the molecular structure of itself that reversible or irreversible change occur, enter
And cause physics, chemical property change a kind of high polymer material.In recent years, because stimulating responsive polymer is in medicine biography
It is defeated, bio-sensing, Chemical Decomposition, cell culture, enzyme immobilization, and the potential application in the field such as biological electro catalysis and by wide
General concern.
In recent years, as the research that deepens continuously of stimulating responsive polymer, stimuli responsive are sent out from single stimulation
Transform into double (more) remise it is sharp.In numerous stimulation means, in addition to temperature and pH stimulate, light is as emerging stimulation means
Advantage with uniqueness.Because except the time of additional light and position can accurately control, the pure property of photochemistry and
Controllability causes optical Response polymer to have good application prospect.
At present, the polymer with temperature, pH and the triple stimuli responsives of light is it has been reported that still such polymer is in illumination
Under the conditions of photodestruciton reaction occurs, photoresponse group comes off from polymeric chain so that the molecular structure and performance of polymer itself
Reversible change without light.With the research that deepens continuously to stimulating responsive polymer system, simple multiple stimulation rings
Answering property polymer can not meet the needs of scientists, and being badly in need of design synthesis, there is multiple stimulation to respond and right simultaneously for some
Environmental stimuli makes the polymeric material of reversible change.
Azobenzene molecule is a kind of typical chromophore molecule, is become as reversible conformation can occur for the change of external condition
Change.Azobenzene compound is as a kind of material with good photosensitive property, in the research field of photoresponsive polymer material
Have a very important role.The cis-trans isomerism reversible reaction that azo chromophore occurs in the presence of light, to polymeric material
The characteristics such as photic covert, photodichroism are brought, are had very in photoswitch, optical information storage and biologic applications etc.
Big potential value.
The reversible photoisomerization performance of azobenzene group is azobenzene compound property of greatest concern, i.e. azobenzene is suitable
Phase co-conversion between formula configuration and anti-configuration.Research shows that azo group has optical activity, in ultraviolet light (340-380
Nanometer) and visible ray (420-490 nanometers) irradiation is lower carries out reversible photoisomerization reaction, or darkroom standing can also realize by
Reverted austenite of the cis-configuration to anti-configuration.Along with azobenzene photo-isomerisation process, the physical dimension of azobenzene molecule and
Dipole moment can also change a lot.If azobenzene molecule is connected to the poly- of temperature/pH responses by chemical method
On compound chain, then temperature/pH the response of novel polymer not only original polymer, the reversible photoisomerization of azobenzene is also had
Energy.This kind of polymer can be used for controlled drug release field, self-assembled film to fields such as the reversible adsorption of protein and desorptions.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the polymer of multiple response azobenzene functionalization.This method
Poly- (methyl) dimethylaminoethyl acrylate with temperature and pH responses is prepared first, then by the azobenzene of photoresponse
Group is grafted on poly- (methyl) dimethylaminoethyl acrylate by quaterisation, obtains the polymer with multiple response.
In the case where ultraviolet light and visible ray alternately irradiate, anti-configuration and the possibility of reversal of cis-configuration can occur this polymer for molecular structure
Change.
The technical scheme of this preparation method is：With a kind of preparation side of the polymer of multiple response azobenzene functionalization
Method, described method and step include：
Step 1 prepares poly- (methyl) dimethylaminoethyl acrylate：Schlenk bottle is dried in vacuo and is full of nitrogen, will
Cuprous bromide, 1,1,4,7,10,10- hexamethyls trien and dimethylaminoethyl methacrylate are 1 in molar ratio:
1:100 ratio is added in Schlenk bottle, uses both above-mentioned cuprous bromide and base dimethylaminoethyl acrylate quality sum
5~10 times of anhydrous tetrahydro furan dissolving, be well mixed after, stop inflated with nitrogen, clog bottleneck with rubber stopper.Through liquid nitrogen three times
The circulation of freezing-suction-defrosting, after air in emptying bottle, Schlenk bottle is heated slowly to 40 degrees Celsius, treats temperature stabilization
Afterwards, reacted in ethyl α bromoisobutyrate addition system 24 hours under 40 degrees Celsius with micro input syringe.Reaction terminates
Afterwards, substantial amounts of dchloromethane product is added, then reactant mixture is removed into catalyst, gained filtrate with neutral alumina column
Revolving removes most of solvent, is precipitated in substantial amounts of n-hexane twice, filtering, product is placed in into 45 degrees Celsius of vacuum drying chambers
Middle drying 24 hours, obtain pure poly- (methyl) dimethylaminoethyl acrylate；
Step 2 prepares m-benzotrifluoride azophenol：By m-trifluoromethyl azobenzene point, 38% concentrated hydrochloric acid and go from
Sub- water is according to 1:(2~2.2):The mass ratio mixing of (3.5~4), is placed in ice-water bath, is tuned into pasty state, and stirring is lower to press 2.5:1
2.9mmol/ml natrium nitrosums chilled aqueous solution is slowly added dropwise into above-mentioned solution in volume ratio, and stirring reaction to solution makes starch iodate
Potassium test paper becomes blue, the diazonium salt solution of filtering；The sodium hydrate aqueous solution that phenol is dissolved in 3mmol/ml obtains 3mmol/ml benzene
Phenol solution, above-mentioned diazonium salt solution is slowly dropped in phenol solution dropwise, is added dropwise to complete after continuing reaction 24 hours, uses salt
PH value of solution is adjusted to 2-3 by acid, is filtered, and product is washed with deionized to filtrate in neutrality, is dried, is obtained crude product, will slightly produce
Thing is recrystallized with n-hexane, is dried to obtain pure m-trifluoromethyl azophenol；
Step 3 prepares 3- trifluoromethyl -4- brombutyl azobenzenes：By the m-trifluoromethyl azobenzene obtained by step 2
Phenol is 1 in molar ratio with 1,4- dibromobutanes:3~5 mixing, are added in acetone soln, are deposited in Anhydrous potassium carbonate and KI
In case, reaction solution is poured into 1000 milliliters of deionized water by 63 degrees Celsius of back flow reactions 24 hours, reaction after terminating,
Orange-yellow oily little particle is obtained, freeze-drying, it is even to be finally recrystallized to give pure 3- trifluoromethyl -4- brombutyls with n-hexane
Pyridine；
Step 4 prepares poly- (methyl) dimethylaminoethyl acrylate of multiple response azobenzene functionalization：Made with step 3
Poly- (methyl) dimethylaminoethyl acrylate made from the 3- trifluoromethyls -4- brombutyls azobenzene and step 1 obtained is raw material, is pressed
Certain mol ratio after reaction terminates, precipitates 2 in 35 degrees Celsius of stirring reaction 24 hours in tetrahydrofuran in n-hexane
It is secondary, it is placed in 45 degrees Celsius of vacuum drying ovens after drying 24 hours, obtains the poly- (first that orange/yellow solid is azobenzene functionalization
Base) dimethylaminoethyl acrylate.
Further, polymeric reaction temperature is 40 degrees Celsius in the step 1, and the reaction time is 24 hours；The step
The dimethylaminoethyl methacrylate used in one is handled by being evaporated under reduced pressure.
Preferably, by m-benzotrifluoride azophenol made from step 2, Isosorbide-5-Nitrae-dibromobutane, anhydrous in the step 3
Potassium carbonate and KI are according to 1:5:10:0.8 mol ratio and acetone mixing.
Preferably, by (methyl) dimethylaminoethyl acrylate poly- made from step 1 and step 3 system in the step 4
3- trifluoromethyl -4- brombutyl the azobenzenes obtained are according to 5:1 mol ratio is added in flask；The polymerization obtained in the step 4
What is be grafted on thing is that azobenzene group is 3- trifluoromethyl -4- brombutyl azobenzenes；Reaction temperature is taken the photograph for 35 in the step 4
Family name's degree；The polymer that is obtained in the step 4 while there is light, pH and temperature-responsive.
The advantage of the invention is that the azobenzene group of photoresponse is incorporated into poly- (methyl) dimethylaminoethyl acrylate
In segment, it is shown below；The synthetic method of the present invention is simple and easy, and the more traditional reaction temperature of reaction temperature is low, makes polymer
Not only there is the Thermo-sensitive and pH sensitiveness of poly- (methyl) dimethylaminoethyl acrylate, while also have the reversible light of azobenzene concurrently
Isomerization property is caused, is a kind of new polymer with temperature, pH and optical Response.
Brief description of the drawings
Fig. 1 is that the hydrogen of obtained polymethylacrylic acid dimethylaminoethyl composes nuclear magnetic spectrum.
Fig. 2 is that the hydrogen of obtained final product composes nuclear magnetic spectrum.
Fig. 3 is that obtained final product is dissolved in tetrahydrofuran in ultraviolet light (365nm, 5mW/m2) stimulate under ultraviolet suction
Receive spectrogram.
Fig. 4 is that obtained final product final product is dissolved in tetrahydrofuran in visible ray (450nm, 7mW/m2) under stimulation
UV absorption spectrogram.
Fig. 5 is the UV absorption of obtained final product with the collection of illustrative plates of pH change.
Fig. 6 is the obtained change in fluorescence of final product in a heated condition.
Embodiment
Embodiment 1
Prepare poly- (methyl) dimethylaminoethyl acrylate：8 are added in 10 milliliters of dry Schlenk (schlenk) bottles
Milliliter anhydrous tetrahydro furan, nitrogen protection under conditions of, successively into schlenk bottles add complexant 1, Isosorbide-5-Nitrae, 7,10,
0.144 gram of 10- hexamethyls trien (HMTETA), monomer methacrylic acid dimethylaminoethyl (DMAEMA) 8.334
Gram, after 15 minutes, 0.076 gram of catalyst cuprous bromide (CuBr) is added, stops inflated with nitrogen afterwards, bottleneck is clogged with rubber stopper.
Circulation through liquid nitrogen frozen-suction-defrosting three times, after air in emptying bottle, it is Celsius that schlenk bottles are heated slowly to 40
Degree, after temperature stabilization, with micro input syringe by 0.065 milliliter of initiator ethyl α bromoisobutyrate (EBIB), taken the photograph 40
Reacted 24 hours under family name's degree.After reaction terminates, schlenk bottles are quenched with liquid nitrogen, terminating reaction, add substantial amounts of CH2Cl2Dilution
Product, then reactant mixture is removed into catalyst with neutral alumina column, gained filtrate revolving removes most of solvent, a large amount of
N-hexane in precipitate twice, filtering, by product be placed in 40 degrees Celsius of vacuum drying chambers dry 24 hours.
Embodiment 2
Prepare m-benzotrifluoride azophenol：3.22 grams of m-benzotrifluoride amine, 6 are added in 250 milliliters of three-necked flask
The dense HCl (38%) of milliliter and 12 ml deionized waters.1.394 grams of NaNO are added in 100 milliliters of flasks2With 7 milliliters of deionizations
Water, stirring and dissolving.Under 0-5 degrees celsius, sodium nitrite solution is slowly dropped into m-benzotrifluoride amine/hydrochloric acid solution simultaneously
Stirring, time for adding are 2 hours, are stirred for making within 2 hours its reaction complete after being added dropwise to complete, can finally make starch potassium iodide paper
When turing blue, filtration product, filtrate (yellow) cooling is stand-by, obtains diazonium salt solution.
1.88 grams of phenol, 1.2 grams of NaOH and 10 ml deionized waters are added in 250 milliliters of beaker, at 0-5 degrees Celsius
Under the conditions of, by 10 milliliters of 1.88 grams of Na2CO3The aqueous solution is added drop-wise in phenol/sodium hydroxide solution, will be above-mentioned heavy after stirring completely
Nitrogen salt is added drop-wise in phenol solution, and time for adding is 2 hours, is stirred for making for 2 hours its reaction complete after being added dropwise to complete, during dropwise addition
There is red azo benzene Precipitation.Add hydrochloric acid that pH value of solution is adjusted into 2-3.Filter out product, by product be washed with deionized to
Filtrate is dried in neutrality, obtains crude product.Crude product is recrystallized with n-hexane.
Synthetic route is shown below：
Prepare 3- trifluoromethyl -4- brombutyl azobenzenes：Trifluoro between adding 0.532 gram in 250 milliliters of three-necked flask
Methyl- phenol, 2.16 grams of 1,4- dibromobutanes, 2.73 grams of anhydrous Ks2CO3, 0.28 gram of KI and 50 milliliter of acetone, 63 degrees Celsius
Constant temperature is stirred at reflux 48 hours.Reaction solution is poured into 1000 milliliters of deionized water by reaction after terminating, and stands 1 day, observable
To there is orange-yellow oily little particle to be deposited to beaker bottom, while adrift orange-yellow grease on the water surface, collect on the water surface
With the grease at the bottom, it is freeze-dried 3 days, removal does not remove clean water, you can obtains crude product.Finally recrystallized with n-hexane
Crude product.
Synthetic route is shown below：
Embodiment 2
Prepare poly- (methyl) dimethylaminoethyl acrylate of azobenzene functionalization：3- trifluoromethyl -4- brombutyls is even
Pyridine (0.16 gram) and PDMAEMA (0.314 gram) repeat unit press 1:In 5 mol ratio input flask, 10 milliliters of THF are added
Reacted 24 hours under 35 degrees Celsius.After reaction terminates, precipitation capacity time, after supernatant is outwelled, is placed in 40 and takes the photograph in n-hexane
After being dried 24 hours in family name's degree vacuum drying oven, product is obtained.
Synthetic route is shown below：
Step one polymer of the present invention, the structure of step 3 azo benzene monomer and step 4 azobenzene polymer pass through core
Magnetic spectrum figure (accompanying drawing 1, accompanying drawing 3 and accompanying drawing 4) is proven.
Product optical Response synthesized by the present invention is shown in accompanying drawing 5 and 6, it can be seen that with prolonging for ultraviolet light time
Long, wavelength is that the absorption peak of 352 nanometers gradually weakens and absorption peak that wavelength is 442 nanometers gradually strengthens, explanation
Under ultraviolet light isomerization reaction occurs for trans-azobenzene, is gradually converted into cis-azobenzene；Radiation of visible light is used afterwards
Sample, with the increase of light irradiation time, the absworption peak of the nanometers of wavelength 352 gradually strengthens and the absorption of the nanometers of wavelength 442
Peak gradually weakens, and cis-azobenzene is gradually converted into trans-azobenzene under visible light illumination；Its ultraviolet-visible irradiation spectrum
Reversible change, illustrate that it has reversible optical Response.
Claims (6)
1. a kind of preparation method of multiple response azobenzene functionalized polymer, it is characterised in that preparation process is as follows：Step
One, prepares poly-（Methyl）Dimethylaminoethyl acrylate：Schlenk bottle is dried in vacuo and is full of nitrogen, by cuprous bromide, 1
, 1,4,7,10,10- hexamethyl trien and dimethylaminoethyl methacrylate are 1 in molar ratio:1:100
Ratio add Schlenk bottle in, use the 5 of both above-mentioned cuprous bromide and dimethylaminoethyl methacrylate quality sum
~10 times of anhydrous tetrahydro furan dissolving, after being well mixed, stops inflated with nitrogen, bottleneck is clogged with rubber stopper；It is cold through liquid nitrogen three times
The circulation of jelly-suction-defrosting, after air in emptying bottle, Schlenk bottle is heated slowly to 40 degrees Celsius, treats temperature stabilization
Afterwards, ethyl α bromoisobutyrate is pressed in 1 molar ratio addition system with micro input syringe, it is small that 24 is reacted under 40 degrees Celsius
When；After reaction terminates, substantial amounts of dchloromethane product is added, then reactant mixture is removed with neutral alumina column and is catalyzed
Agent, gained filtrate revolving remove most of solvent, precipitated in substantial amounts of n-hexane twice, filtering, it is Celsius that product are placed in into 45
Spend in vacuum drying chamber and dry 24 hours, obtain pure gather（Methyl）Dimethylaminoethyl acrylate；
Step 2 prepares m-benzotrifluoride azophenol：It is 1 in molar ratio using m-benzotrifluoride amine and phenol as raw material:1 is mixed
Close, m-trifluoromethyl azophenol is prepared by diazo coupling reaction under 0-5 degrees Celsius of low temperature；After reaction terminates, use
Deionized water is washed to filtrate and recrystallized in neutrality, then by crude product with n-hexane, and it is even to be dried to obtain pure m-trifluoromethyl
Pyridine phenol；
Step 3 prepares 3- trifluoromethyl -4- bromine butoxyazobenzenes：By the m-trifluoromethyl azobenzene obtained by step 2
Phenol and 1,4- dibromobutane are 1 in molar ratio:3-1:5 mixing, are added in acetone soln, in Anhydrous potassium carbonate and KI
In the presence of, 63 degrees Celsius of back flow reactions 24 hours；Reaction solution is poured into 1000 milliliters of deionized water by reaction after terminating
In, orange-yellow oily little particle is obtained, is freeze-dried, pure 3- trifluoromethyl -4- bromine fourths is finally recrystallized to give with n-hexane
Base azobenzene；
Step 4 prepares the poly- of multiple response azobenzene functionalization（Methyl）Dimethylaminoethyl acrylate：With step 3 system
Gather made from the 3- trifluoromethyls -4- bromines butoxyazobenzene and step 1 obtained（Methyl）Dimethylaminoethyl acrylate is original
Material, is stirred 24 hours in 35 degrees Celsius by certain mol ratio in tetrahydrofuran, and after reaction terminates, two are precipitated in n-hexane
It is secondary, it is placed in 45 degrees Celsius of vacuum drying ovens after drying 24 hours, it is the poly- of azobenzene functionalization to obtain orange/yellow solid（First
Base）Dimethylaminoethyl acrylate.
2. according to the method for claim 1, it is characterised in that：The dimethylaminoethyl used in the step 1
Ethyl ester is handled by being evaporated under reduced pressure.
3. according to the method for claim 1, it is characterised in that：By m-benzotrifluoride made from step 2 in the step 3
Azophenol, 1,4- dibromobutanes, Anhydrous potassium carbonate and KI are according to 1:5:10:0.8 mol ratio and acetone mixing.
4. according to the method for claim 1, it is characterised in that：It will gather in the step 4 made from step 1（Methyl）Third
3- trifluoromethyls -4- bromine butoxyazobenzenes are according to 5 made from olefin(e) acid dimethylaminoethyl and step 3:1 mol ratio adds
In flask.
5. according to the method for claim 1, it is characterised in that：What is be grafted on the polymer obtained in the step 4 is even
Pyridine group is 3- trifluoromethyl -4- bromine butoxyazobenzenes.
6. according to the method for claim 1, it is characterised in that：The polymer that is obtained in the step 4 at the same have light,
PH and temperature-responsive.
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| CN106054528A (en) * | 2016-06-07 | 2016-10-26 | 北京大学 | Preparation and fast light control method for nano pattern based on organic polymer |
| CN107099007B (en) * | 2017-04-24 | 2019-03-12 | 浙江理工大学 | Polymer composite vesica of Amphipathilic block polymer, light and pH double-response and its preparation method and application |
| CN108219089B (en) * | 2018-01-22 | 2019-05-03 | 浙江大学 | Target the preparation of multifunctional polymer nano-probe and its to the application in cell imaging containing TK |
| CN109384869B (en) * | 2018-10-11 | 2021-03-19 | 苏州大学 | Fluorine-containing azobenzene amphiphilic polymer, visible light response polymer nanotube and preparation method thereof |
| CN109535361B (en) * | 2018-11-12 | 2021-09-03 | 中山大学 | Ultraviolet light irradiation mechanical response waterborne polyurethane and preparation method thereof |
| CN110498884B (en) * | 2019-08-28 | 2021-06-15 | 河北大学 | PH response polymer and preparation method thereof |
| CN111129350B (en) * | 2019-12-26 | 2022-07-12 | Tcl华星光电技术有限公司 | Display panel and display panel manufacturing method |
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