CN102633960A - Multi-environmental-sensitivity triblock copolymer and preparation method and application thereof - Google Patents
Multi-environmental-sensitivity triblock copolymer and preparation method and application thereof Download PDFInfo
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- CN102633960A CN102633960A CN2012100954538A CN201210095453A CN102633960A CN 102633960 A CN102633960 A CN 102633960A CN 2012100954538 A CN2012100954538 A CN 2012100954538A CN 201210095453 A CN201210095453 A CN 201210095453A CN 102633960 A CN102633960 A CN 102633960A
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Abstract
The invention provides multi-environmental-sensitivity triblock copolymer, which contains polyethyleneglycol-b-poly (2-dimethylamino ethylmethacrylate)-b-poly (azobenzene) triblock copolymer, which is obtained by initiating azobenzene-contained monomer by polyethyleneglycol-b-poly (2-dimethylamino ethylmethacrylate) diblock copolymer and is shown in a chemical formula. The azobenzene group contains n methylenes, wherein n ranges from 2 to 9. The preparation method of the multi-environmental-sensitivity triblock copolymer includes: using polyethyleneglycol to initiate 2-dimethylamino ethylmethacrylate monomer to obtain the polyethyleneglycol-b-poly (2-dimethylamino ethylmethacrylate) diblock copolymer by atomic transfer radical polymerization; and using the diblock copolymer to further initiate the azobenzene-contained monomer to obtain the polyethyleneglycol-b-poly (2-dimethylamino ethylmethacrylate)-b-poly (azobenzene) triblock copolymer. The triblock copolymer is capable of responding to multi-environments such as light, temperature and pH value, and has bright application prospect in the field of intelligent materials and photoelectric information storage.
Description
Technical field
The present invention relates to the synthetic and preparing technical field of polymkeric substance, concrete is the triblock copolymer that has multiple environment-responsive about a kind of.
Background technology
The environment in recent years responsive polymer has caused the extensive concern of researcher like performances such as pH responsiveness, temperature-responsive, optical Response, ionic strength responsivenesss.This mainly is because the environment-responsive polymkeric substance has the variation that the polymer molecule chain conformation can take place under the situation of subtle change in external environment; Make said material that bigger physical change or chemical transformation further take place, the stimulation of environment generation reaction to external world apace.The macromolecular material that this type has higher environmental sensitivity exists huge application potential in fields such as biological medicine, intelligent material, optoelectronic information storages.
Polyoxyethylene glycol (PEG) has excellent biocompatibility, can be used as the shell of hydrophilic multiple response block copolymer micelle, plays the effect of well stabilized micellar.On biomedicine, the block polymer micelle that has the polyoxyethylene glycol shell can prevent protein adsorption and cell adhesion, and can also stop the identification of system of netted internal film tissue, prevents that micellar is removed in early days in blood environment in addition.
Polymethyl acrylic acid N, N-dimethylaminoethyl (PDMAEMA) are a kind of cationic acrylate derivative polymkeric substance, are the polymers with temperature and pH susceptibility.Tertiary amine groups, carbonyl and the hydrophobic alkyl group of while possess hydrophilic property in the PDMAEMA molecular structure; And two types of groups match each other on the space structure formula; When environment (temperature or pH value) changes, can cause the formation and the destruction of hydrogen bond, thereby cause the variation of polymer phase.In addition, PDMAEMA and DNA have good affinity, have biocompatibility, anticoagulation function, so it are with a wide range of applications on intelligent material.
Azobenzene polymer (PAZO) is owing to there is good nonlinear optics chromophore; Can cause performances such as photic isomery and molecule reorientation through illumination; Can cause the variation of absorbed and refractive isotropic and anisotropic; Thereby the generation optical non-linear effect, therefore, the material that contains azobenzene polymer has broad application prospects at nonlinear optical material and intelligent material field.The research of this respect has obtained developing by leaps and bounds in recent years.
In recent years, poly N-isopropyl acrylamide (PNIPAM) polymkeric substance that will have temperature-responsive combined with the azobenzene polymer with optic response property, formed a kind of copolymer material PEO-that only has temperature and light double-response
b-P (AZO-
Co-NIPAM) existing successful report (Macromol. Rapid Commun. 2010,31,640 – 644).And, have copolymer material multiple environment-responsive, that structure is clear and definite more, simultaneously and received this area researchist's concern along with the development of intelligent material.
Summary of the invention
The object of the invention is on the basis of existing research, the triblock copolymer that a kind of structure is novel, have multiple environment-responsive to be provided, and this triblock copolymer has light, temperature and pH value multiple environment-responsive; Second purpose of the present invention is; The preparation method of said triblock copolymer is provided; The 3rd purpose of the present invention is to prove that said triblock copolymer can access new application widely in nonlinear optical material, photoresponse, memory device and intelligent material field.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is following.
A kind of multiple environment-responsive triblock copolymer is characterized in that, contain by the polyoxyethylene glycol that has activity functional groups-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer cause contain the azobenzene group monomer obtain polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gathering the nitrogen benzide triblock copolymer, its chemical structural formula is:
In the formula, methylene radical number n=2～9 in the azobenzene group.
A kind of preparation method of multiple environment-responsive triblock copolymer adopts the method (ATRP) of ATRP, it is characterized in that, earlier by polyoxyethylene glycol cause the dimethylaminoethyl methacrylate monomer obtain polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer; Again by the polyoxyethylene glycol that has activity functional groups-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer further cause contain the azobenzene group monomer obtain polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gathering the nitrogen benzide triblock copolymer, the chemical structural formula of said triblock copolymer is:
，
In the formula, methylene radical number n=2～9 in the azobenzene group.
Further, said polyoxyethylene glycol-
bThe preparation process of-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer is: the mixed solvent with methyl-phenoxide, Virahol, methyl alcohol, water or methyl alcohol and water is a solvent, is initiator with polyoxyethylene glycol-Br, removes the oxygen in the system; Add N, N, N'; N', the catalystsystem that N''-pentamethyl-diethylamine triamine and cuprous bromide are formed reacts under nitrogen protection; Temperature of reaction is 20～60 ℃, and the reaction times is 1～12 hour; Crossing the neutral alumina post then, is leacheate with THF (THF), concentrate the back and in normal hexane, precipitate 3 times, and suction filtration, vacuum-drying obtains the PEG-that white sticks shape
b-PDMAEMA polymkeric substance, the general formula of its building-up process is:
Said polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-preparation the process of gathering the nitrogen benzide triblock copolymer is: with methyl-phenoxide, chlorobenzene, toluene or N, dinethylformamide is a solvent, with polyoxyethylene glycol-
b-polymethyl acrylic acid diformazan ammonia ethyl ester di-block copolymer is an initiator, removes the oxygen in the system, adds N, N; N', N', the catalystsystem that N''-pentamethyl-diethyl triamine and cuprous bromide are formed; Under nitrogen protection, react, temperature of reaction is 60～120 ℃, and the reaction times is 6～24 hours; Crossing the neutral alumina post then, is leacheate with THF (THF), concentrates the back and in ether, precipitates; Vacuum-drying 24 hours obtains the triblock copolymer of orange solids, and the general formula of its building-up process is:
In the formula; The R group is:
, wherein n=2～9.
Multiple environment-responsive nitrogen benzide triblock copolymer is in the application in intelligent material field.
Multiple environment-responsive nitrogen benzide triblock copolymer is in the application of optoelectronic information field of storage.
Positively effect of the present invention is:
(1) with polyoxyethylene glycol (PEG), polymethyl acrylic acid N, N-dimethylaminoethyl (PDMAEMA) and azobenzene polymer combine, and utilize atom transfer radical polymerization method successfully to synthesize the clear and definite linear three block copolymer PEG-of a kind of structure
b-PDMAEMA-
b-PAZO, it has triple environment-responsives of optics, temperature and pH value simultaneously.
(2) a kind of simple and practical preparation method of multiple environment-responsive triblock copolymer is provided, through regulating the subject polymer that dimethylaminoethyl acrylate methyl ammonia ethyl ester and the monomeric ratio of nitrogen benzide can also be prepared different dimethylaminoethyl acrylate methyl ammonia ethyl ester content and nitrogen benzide content.
(3) described preparation method can prepare the subject polymer with different block structures through changing the addition sequence of different monomers in the polymerization process.
(4) multiple environment-responsive triblock copolymer of the present invention was owing to both contained the photochromic group azobenzene group; The dimethylaminoethyl acrylate methyl ammonia ethyl ester structure that contains response of pH value and temperature response again; Thereby make it with a wide range of applications in intelligent material, optoelectronic information field of storage; Can be applicable on photoswitch, the optics, have excellent stability and triple environmental response performances.
Description of drawings
Accompanying drawing 1 be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer and polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the hydrogen spectrogram of nitrogen benzide triblock copolymer;
Among the figure, (a) be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester; (b) be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather nitrogen benzide.
Among the figure, (a) be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester; (b) be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather nitrogen benzide.
Accompanying drawing 3 be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the UV, visible light color atlas of nitrogen benzide triblock copolymer under UV-light illumination.
Accompanying drawing 5 be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the graphic representation that nitrogen benzide triblock copolymer micellar particle diameter changes with the pH value.
Embodiment
Below in conjunction with embodiment the present invention is further described, still, enforcement of the present invention is not limited to following embodiment.
Embodiment 1
A kind of preparation of multiple environment-responsive triblock copolymer, its concrete steps are:
(1) adopt method (ATRP) synthesizing polyethylene glycol of ATRP-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester (PEG-
b-PDMAEMA) di-block copolymer
In 50ml reaction eggplant bottle, initiator polyoxyethylene glycol (PEG-Br) 0.5g (0.25mmol) and monomer dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) 1.965g (12.5mmol) are dissolved in the 5ml Virahol, after oxygen is removed in the freezing circulation of bleeding of process; Add N, N, N'; N', the catalystsystem that N''-pentamethyl-diethyl triamine and cuprous bromide are formed, 30 ℃ of reactions of temperature are 3 hours under nitrogen protection; Crossing the neutral alumina post then, is leacheate with THF (THF), concentrates the back and in normal hexane, precipitates 3 times; Suction filtration, vacuum-drying obtains the PEG-that white sticks shape
b-PDMAEMA polymkeric substance, productive rate are 90%.
(2) adopt the method synthesizing polyethylene glycol of ATRP-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather [6-(4-methoxyl group nitrogen benzide-4'-oxygen base) N-Hexyl methacrylate] triblock copolymer (PEG-
b-PDMAEMA-
b-PAZO)
In 50ml reaction eggplant bottle, add PEG-
b-PDMAEMA 1.0g (0.15mmol), [6-(4-methoxyl group nitrogen benzide-4'-oxygen base) N-Hexyl methacrylate] be monomer 2.97g (7.5mmol), N (AZO), N, N'; N', the catalystsystem that N''-pentamethyl-diethyl triamine and cuprous bromide are formed is after oxygen is removed in the freezing circulation of bleeding of process; 90 ℃ of reactions of temperature are 18 hours under nitrogen protection; Crossing the neutral alumina post then, is leacheate with THF (THF), concentrates the back and in ether, precipitates; Vacuum-drying 24 hours obtains the triblock copolymer of orange solids.
Fig. 1 be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer and polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the hydrogen spectrogram of nitrogen benzide triblock copolymer.The characteristic peak of (a) among Fig. 1 (4.07,3.64,2.62,2.30,1.94,1.82,1.14,0.83ppm) proved PEG-
bThe success of-PDMAEMA di-block copolymer is synthetic; The characteristic peak of (b) among Fig. 1 (7.81,7.01,4.07,3.64,2.62,2.30,1.94,1.82,1.42,1.14,0.83ppm) proved triblock copolymer (PEG-of the present invention
b-PDMAEMA-
b-PAZO) success is synthetic.
Fig. 2 be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer and polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the gel permeation chromatography figure of nitrogen benzide triblock copolymer.As shown in Figure 2, triblock copolymer PEG-of the present invention
b-PDMAEMA-
bThe molecular weight ratio PEG-of-PAZO
b-PDMAEMA molecular weight is big, has proved that the success of triblock copolymer of the present invention is synthetic.
The structure of the di-block copolymer that multiple environment-responsive triblock copolymer of the present invention is adopted is confirmed with the efficient gel chromatographic process through nmr analysis: the subject polymer that can prepare different dimethylaminoethyl acrylate methyl ammonia ethyl ester content and different nitrogen benzide content through adjusting dimethylaminoethyl acrylate methyl ammonia ethyl ester and the monomeric ratio of nitrogen benzide.
A kind of preparation of multiple environment-responsive triblock copolymer, embodiment 2 is with the difference of embodiment 1: in step (1), 60 ℃ of reactions of temperature are 1 hour under nitrogen protection; In step (2), 120 ℃ of reactions of temperature are 6 hours under nitrogen protection.Other preparation process and condition are with embodiment 1.
Embodiment 3
A kind of preparation of multiple environment-responsive triblock copolymer, embodiment 3 is with the difference of embodiment 1: in step (1), 20 ℃ of reactions of temperature are 12 hours under nitrogen protection; In step (2), 60 ℃ of reactions of temperature are 24 hours under nitrogen protection.Other preparation process and condition are with embodiment 1.
Multiple environment-responsive triblock copolymer multiple environment-responsive of the present invention can be analyzed
(1) optical property analysis
The triblock copolymer 0.01g of embodiment preparation is dissolved in the dioxane, is made into the 0.02g/L polymers soln, the polymers soln that pipettes 3ml is dissolved in the quartz colorimetric utensil, measures with the ultraviolet-visible photometer:
1. utilize 365nm wavelength UV-irradiation polymers soln, under the different UV-light light application times resulting ultraviolet-visible spectrogram see accompanying drawing 3 (polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the UV, visible light color atlas of nitrogen benzide triblock copolymer under UV-light illumination), wherein, wavelength 351nm's is the transconfiguration of nitrogen benzide, wavelength 448nm's is the cis-structure of nitrogen benzide.Along with the increase of irradiation time, wavelength is that the absorption peak of 351nm weakens gradually, and wavelength is that the absorption peak of 448nm strengthens gradually, and anti-transformation along isomery can take place under illumination this expression azo-benzene units, and simultaneously, the blue shift phenomenon has taken place the crest of transconfiguration.When light application time reached 600s, the intensity of absorption peak was almost constant.
2. utilize 450nm wavelength blue light to carrying out illumination through the polymers soln behind the ultraviolet lighting 900s, as accompanying drawing 4 (polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the UV, visible light color atlas of nitrogen benzide triblock copolymer under blue light illumination); Increase along with the blue light light application time; Wavelength is that the nitrogen benzide transconfiguration absorption peak strength of 351nm increases gradually, and wavelength is that the nitrogen benzide cis-configuration absorption peak strength of 448nm is less gradually.This expression has reached the variation that cis-trans isomerism has taken place the stable nitrogen benzide of cis-configuration under the blue light, final 32s is the virgin state of the polymers soln that recovers.
(2) pH value sensitive property analysis
Adopt the dioxane solution of 0.2g/L triblock copolymer,, dialyse and obtain the triblock copolymer micellar aqueous solution after three days stirring the deionized water that slowly drips 40% (massfraction) simultaneously fast.Get 1ml micellar solution, dilute 8 times after, the pH value that the HCl aqueous solution through dripping 1mol/L or the NaOH aqueous solution are regulated micellar aqueous solution is measured the pH value after stablizing with pH meter, obtains the triblock copolymer micellar aqueous solution of different pH values.
Accompanying drawing 5 be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the curve that nitrogen benzide triblock copolymer micellar particle diameter changes with the pH value, wherein, the micella particle reduces along with the increase of pH value gradually, is that 9.0 o'clock hydrodynamic radius begin to diminish in the pH value.
(3) the temperature sensitive performance is analyzed
Adopt the dioxane solution of 0.2g/L triblock copolymer,, dialyse and obtain the triblock copolymer micellar aqueous solution after three days stirring the deionized water that slowly drips 40% (massfraction) simultaneously fast.Get 1ml micellar solution, dilute 8 times after, through the water bath with thermostatic control controlled temperature,, make its temperature rise to 50 ℃ from 20 ℃ to micellar aqueous solution heating, per 5 ℃ is an interval, constant temperature 2 hours, the particle diameter of test micellar aqueous solution.
Accompanying drawing 6 be polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gather the temperature variant graphic representation of nitrogen benzide triblock copolymer micellar particle diameter, wherein, the micella particle reduces along with the increase of temperature gradually, and between 30 ℃～35 ℃, undergos mutation.
Can analyze through above multiple environment-responsive; Multiple environment-responsive triblock copolymer of the present invention was owing to both contained the photochromic group azobenzene group; The dimethylaminoethyl acrylate methyl ammonia ethyl ester structure that contains response of pH value and temperature response again; Thereby make it with a wide range of applications, can be applicable on photoswitch and the optics, have excellent stability and triple environmental response performances in intelligent material, optoelectronic information field of storage.
The above is merely preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the inventive method; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (5)
1. a multiple environment-responsive triblock copolymer is characterized in that, contain by the polyoxyethylene glycol that has activity functional groups-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer cause contain the azobenzene group monomer obtain polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gathering the nitrogen benzide triblock copolymer, its chemical structural formula is:
In the formula, methylene radical number n=2～9 in the azobenzene group.
2. the preparation method of a multiple environment-responsive triblock copolymer adopts the method for ATRP, it is characterized in that, earlier by polyoxyethylene glycol cause the dimethylaminoethyl methacrylate monomer obtain polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer; Again by the polyoxyethylene glycol that has activity functional groups-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer further cause contain the azobenzene group monomer obtain polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-gathering the nitrogen benzide triblock copolymer, the chemical structural formula of said triblock copolymer is:
In the formula, methylene radical number n=2～9 in the azobenzene group.
3. the preparation method of multiple environment-responsive triblock copolymer according to claim 2 is characterized in that:
Said polyoxyethylene glycol-
bThe preparation process of-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer is:
Mixed solvent with methyl-phenoxide, Virahol, methyl alcohol, water or methyl alcohol and water is a solvent, is initiator with polyoxyethylene glycol-Br, removes the oxygen in the system; Add N, N, N'; N', the catalystsystem that N''-pentamethyl-diethylamine triamine and cuprous bromide are formed reacts under nitrogen protection; Temperature of reaction is 20～60 ℃, and the reaction times is 1～12 hour; Crossing the neutral alumina post then, is leacheate with the THF, concentrates back deposition 3 times in normal hexane, suction filtration, vacuum-drying, obtain the polyoxyethylene glycol of the glutinous shape of white-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester di-block copolymer, the general formula of its building-up process is:
Said polyoxyethylene glycol-
b-polymethyl acrylic acid n n dimetylaniline ethyl ester-
b-preparation the process of gathering the nitrogen benzide triblock copolymer is:
With methyl-phenoxide, chlorobenzene, toluene or N, dinethylformamide is a solvent, with polyoxyethylene glycol-
b-polymethyl acrylic acid diformazan ammonia ethyl ester di-block copolymer is an initiator, removes the oxygen in the system, adds N, N; N', N', the catalystsystem that N''-pentamethyl-diethyl triamine and cuprous bromide are formed; Under nitrogen protection, react, temperature of reaction is 60～120 ℃, and the reaction times is 6～24 hours; Crossing the neutral alumina post then, is leacheate with the THF, concentrates the back and in ether, precipitates; Vacuum-drying 24 hours obtains the triblock copolymer of orange solids, and the general formula of its building-up process is:
In the formula; The R group is:
, wherein n=2～9.
4. multiple environment-responsive nitrogen benzide triblock copolymer is in the application in intelligent material field.
5. multiple environment-responsive nitrogen benzide triblock copolymer is in the application of optoelectronic information field of storage.
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| CN109369864B (en) * | 2018-08-15 | 2020-02-11 | 厦门大学 | Preparation method of block copolymer with photoresponse, reduction response and pH response |
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| CN111393686A (en) * | 2020-03-13 | 2020-07-10 | 中山大学 | Modified block copolymer with ultraviolet light induced crystal form transformation and preparation method and application thereof |
| CN111393686B (en) * | 2020-03-13 | 2021-06-08 | 中山大学 | Modified block copolymer with ultraviolet light induced crystal form transformation and preparation method and application thereof |
| EP4166645A4 (en) * | 2020-06-12 | 2024-01-10 | Nissan Chemical Corporation | Biocompatible coating film containing block copolymer |
| CN112062906A (en) * | 2020-08-07 | 2020-12-11 | 北京工业大学 | Preparation method of nuclear shell structure environment response type polymer |
| CN112062906B (en) * | 2020-08-07 | 2022-06-21 | 北京工业大学 | Preparation method of nuclear shell structure environment response type polymer |
| CN113416287A (en) * | 2021-06-17 | 2021-09-21 | 四川大学 | Block copolymer for photochromic and thermochromic intelligent window, and preparation method and application thereof |
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