CN108102105B - Multi-responsive hyperbranched polymer and preparation method and application thereof - Google Patents
Multi-responsive hyperbranched polymer and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
Abstract
The multi-responsive hyperbranched polymer simultaneously contains azobenzene groups and amide groups on each branched arm, and the chemical structural formula of the polymer is as follows:
the preparation method comprises the following steps: preparing p-diene azobenzene to obtain yellow p-diene azobenzene powder; and preparing the multi-responsive hyperbranched polymer to obtain the yellow solid multi-responsive hyperbranched polymer. The multi-responsive hyperbranched polymer provided by the invention has a novel structure and has triple responsiveness of light, temperature and pH value; the preparation method has reasonable flow, clear reaction and simple and easy operation; the multi-responsive hyperbranched polymer can be applied to the fields of intelligent materials, photoelectric information storage and functional biological drug loading.
Description
Technical Field
The invention relates to the technical field of polymers and preparation thereof, in particular to a multi-responsive hyperbranched polymer and a preparation method and application thereof.
Background
The multi-responsive polymer is a multi-responsive material which can generate polymer molecular chain conformation change under the condition of slight change of external environment, can quickly generate reaction to the stimulation of the external environment, and can generate larger physical change or chemical change along with the change of the external environment. The multi-response material has wide application prospect in the fields of intelligent materials, photoelectric storage, biomedicine and the like. At present, the temperature responsiveness, the pH responsiveness, the light responsiveness, the ionic strength responsiveness, the magnetic field responsiveness and other performances of the multi-responsive polymer are hot points of attention of researchers.
The amide group-containing polymer is a cationic polymer and has temperature and pH sensitivity. The molecular structure of the polymer simultaneously has hydrophilic tertiary amino, carbonyl and hydrophobic alkyl groups, and the two groups are matched with each other in a spatial structural formula, so that hydrogen bonds can be formed and damaged when the environment (temperature or pH value) is changed, and the phase state of a high polymer is changed. In addition, the molecule of the polymer has good affinity with DNA and biocompatibility, so that the polymer has great application value in the field of biomedicine.
Azobenzene has excellent photoresponsive properties as a typical reversible photoisomerization group. The performance of photoisomerization, molecular reorientation and the like can be caused by illumination, so that the isotropy and the anisotropy of absorption and refraction of the material are caused to change, and an optical nonlinear effect is generated, therefore, the polymer material containing the azobenzene has wide application prospect in the aspects of intelligent materials and optical information storage.
The hyperbranched polymer is a novel three-dimensional branched macromolecule, contains a plurality of terminal functional groups and internal cavities, and is simple and convenient to synthesize, so that the hyperbranched polymer has potential application value in the fields of drug carriers, self-assemblies and the like. In recent years, research into hyperbranched polymers has been rapidly advancing. However, there are far less reports of multi-responsive hyperbranched polymers at home and abroad compared with linear polymers or crosslinked network polymers.
Disclosure of Invention
The invention aims to: on the basis of the existing research, a multi-responsive hyperbranched polymer is provided, which has a novel structure and has triple sensitivities of light, temperature and pH value; the second purpose of the invention is to provide a preparation method of the multi-responsive hyperbranched polymer; the third purpose of the invention is to provide a potential application of the multi-responsive hyperbranched polymer in the fields of photoresponse, memory device, intelligent material and the like.
In order to achieve the purpose, the invention adopts the following technical scheme.
A multi-responsive hyperbranched polymer (hpazaamam) comprising both azobenzene groups and amide groups on each branched arm, having the chemical formula:
a preparation method of a multi-responsive hyperbranched polymer, which adopts a Michael addition polymerization method, is characterized by comprising the following steps:
(1) preparation of p-diolefin azobenzene
Taking tetrahydrofuran as a solvent, adding p-diaminoazobenzene and triethylamine, and uniformly mixing under the protection of nitrogen; slowly injecting acryloyl chloride under the ice bath condition, controlling the temperature of the system to be 0-30 ℃, and reacting for 1-12 hours;
filtering to obtain upper solid;
thirdly, washing with water, centrifuging for 3 times, freeze-drying by liquid nitrogen, and drying in vacuum to obtain yellow paradiene azobenzene (azo BA) powder, wherein the general formula of the synthetic process is as follows:
(2) preparation of a Multi-responsive hyperbranched Polymer
Fully mixing p-diene azobenzene (AzoBA) powder and polyamine monomer 1- (2-aminoethyl) piperazine (AEPZ) by using Dimethylformamide (DMF) as a solvent to perform Michael addition reaction at the temperature of 20-50 ℃ for 24-80 hours;
precipitating with acetone, centrifuging for 3 times, and vacuum drying to obtain yellow solid multi-responsive hyperbranched polymer (HPAzoAMAM), wherein the general formula of the synthetic process is as follows:
the chemical structural formula of the multi-responsive hyperbranched polymer (HPAzoam) is as follows:
furthermore, tetrahydrofuran in the step (1) is used as a reaction medium, and the molar ratio of the p-diaminoazobenzene to the acryloyl chloride is more than 1:1, so that the p-diaminoazobenzene can be completely reacted. Wherein the dosage of triethylamine is consistent with that of acryloyl chloride.
Furthermore, the dimethylformamide solvent in the step (2) is used as a reaction medium, and the molar ratio of the p-diene azobenzene powder to the polyamine monomer 1- (2-aminoethyl) piperazine is controlled within 1:1, so that the crosslinking reaction is prevented.
Further, controlling the temperature of the system to be 30 ℃ in the first 24 hours of the reaction in the step (2), and adding a trace amount of water to increase the compatibility of the reaction system; after 24 hours of reaction, the temperature is raised to 40-50 ℃ to ensure that the reaction is fully carried out.
The application of the multi-responsive hyperbranched polymer (HPAzoam) in the field of intelligent materials.
The application of the multi-responsive hyperbranched polymer (HPAzoam) in the field of photoelectric information storage.
The application of the multi-responsive hyperbranched polymer (HPAzoam) in the field of functional biological drug loading.
The invention has the positive effects that:
(1) provides a multi-responsive hyperbranched polymer, which is a hyperbranched polymer with a novel structure and has triple responsivity of light, temperature and pH value.
(2) The preparation method of the multi-responsive hyperbranched polymer is reasonable in flow, clear in reaction, simple and feasible, and makes full use of the preparation method of Michael addition polymerization.
(3) Provides new application of the multi-responsive hyperbranched polymer in the fields of intelligent materials, photoelectric information storage and functional biological drug loading.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the multi-responsive hyperbranched polymer prepared in embodiment 1 of the present invention.
FIG. 2 is a carbon spectrum of the multi-responsive hyperbranched polymer prepared in example 1 of the present invention.
FIG. 3 is an ultraviolet-visible chromatogram of a multi-responsive hyperbranched polymer DMF solution prepared in embodiment 1 of the invention under 365nm illumination.
FIG. 4 is an ultraviolet-visible chromatogram of a multi-responsive hyperbranched polymer DMF solution prepared in embodiment 1 of the invention under illumination of 450 nm.
FIG. 5 is an SEM image of multi-responsive hyperbranched polymer micelles prepared in example 1 of the present invention.
FIG. 6 is a graph of particle size of the multi-responsive hyperbranched polymer micelle prepared in example 1 of the present invention varying with temperature.
FIG. 7 is a graph of the particle size of the multi-responsive hyperbranched polymer micelle prepared in example 1 of the present invention varying with pH.
Detailed Description
Three specific examples of the multi-responsive hyperbranched polymer of the invention are given below with reference to the accompanying drawings. It should be noted that the practice of the present invention is not limited to the following examples.
Example 1
The preparation method of the multi-responsive hyperbranched polymer adopts a Michael addition polymerization method and comprises the following steps:
(1) preparation of p-Dieneazobenzene (AzoBA)
Adding 50mL of tetrahydrofuran, 1.5032g of p-diaminoazobenzene and 2.08mL of triethylamine in sequence into a 100mL round-bottom flask, and uniformly mixing under the protection of nitrogen; then under the ice bath condition, 1.20mL of acryloyl chloride is slowly dropped by a syringe, and after the dropping is finished, the reaction is stirred at room temperature for 5 hours.
Filtering: filtration through a Buchner funnel and a common analytical filter paper of 9 cm diameter gave a solid as the upper layer.
Washing and centrifuging for 3 times: centrifugation at 9000rpm for 5 minutes each with liquid nitrogen, lyophilization for 5 minutes and vacuum drying (0kPa, 48h) afforded a yellow powder of p-diene azobenzene (AzoBA) of the general formula:
(2) preparation of Multi-responsive hyperbranched Polymer (HPAzoAMAM)
Adding 0.6g of p-diene azobenzene powder into a 20mL screw-top bottle, and fully dissolving the p-diene azobenzene powder by using Dimethylformamide (DMF); 0.33mL of polyamine monomer 1- (2-aminoethyl) piperazine (AEPZ) was added thereto, and the mixture was rapidly stirred at 30 ℃ for 48 hours to conduct Michael addition reaction.
Precipitating with acetone, centrifuging for 3 times: centrifugation was carried out at 9000rpm for 5 minutes each with liquid nitrogen, and lyophilization was carried out for 5 minutes under vacuum (0kPa, 48 hours) to obtain a yellow solid cake product, a multi-responsive hyperbranched polymer (HPAzoam).
The general formula of the synthetic process is as follows:
nuclear magnetic hydrogen (see fig. 1) and carbon (see fig. 2) spectra of the multi-responsive hyperbranched polymer (hpazaamam). The characteristic peaks (7.91; 2.73; 2.62-2.42; 2.08ppm in FIG. 1 correspond to-CONH-; -COCH;)2-；-N(CH2CH2) -and-NH2(ii) a -NH-group). The characteristic peak (56.56; 53.36-52.95 ppm of FIG. 2 corresponds to-N (CH)2CH2)2A group). The nuclear magnetic hydrogen spectrogram and the carbon spectrogram can prove that: the invention is successful in preparing multi-sensitive hyperbranched polymer (HPAzoam).
Each branched arm of the multi-responsive hyperbranched polymer (HPAzoam) simultaneously contains azobenzene groups and amide groups, and the chemical structural formula of the multi-responsive hyperbranched polymer is as follows:
example 2
The preparation method of the multi-responsive hyperbranched polymer is basically the same as that of example 1.
The difference is that:
(1) p-diylazobenzene (AzoBA) was prepared (same as in example 1).
(2) Preparation of Multi-responsive hyperbranched Polymer (HPAzoAMAM)
Adding 0.6g of p-diene azobenzene powder into a 20mL screw-top bottle, and fully dissolving the p-diene azobenzene powder by using Dimethylformamide (DMF); 0.28mL of polyamine monomer 1- (2-aminoethyl) piperazine (AEPZ) was added thereto, and the mixture was rapidly stirred at 30 ℃ for 48 hours to conduct Michael addition reaction.
② precipitating with acetone, centrifuging for 3 times, vacuum drying for 24h to obtain a yellow solid block product, namely the multi-responsive hyperbranched polymer (HPAzoam).
Example 3
The preparation method of the multi-responsive hyperbranched polymer is basically the same as that of example 2.
The difference is that:
(1) preparation of p-Dieneazobenzene (AzoBA)
Adding 50mL of tetrahydrofuran, 1.5032g of p-diaminoazobenzene and 2.96mL of triethylamine in sequence into a 100mL round-bottom flask, and uniformly mixing under the protection of nitrogen; then, under the ice-bath condition, 1.72mL of acryloyl chloride was slowly added dropwise through a syringe, and after the dropwise addition, the reaction was stirred at room temperature for 5 hours.
② (same as example 2).
(same as example 2).
(2) A multi-responsive hyperbranched polymer (hpazaamam) was prepared (same as in example 2).
The multi-responsiveness function analysis of the multi-responsiveness hyperbranched polymer prepared by the invention comprises the following steps:
(1) light responsivity analysis
Dissolving the multi-responsive hyperbranched polymer prepared in example 1 in DMF to prepare 0.05g/L polymer solution; 2.5mL of the polymer solution was placed in a quartz cuvette and measured with an ultraviolet-visible spectrophotometer.
The polymer solution is irradiated by 365nm ultraviolet light, and the DMF solution of the multi-response hyperbranched polymer is subjected to an ultraviolet visible chromatogram under 365nm illumination (see figure 3), wherein the wavelength of 376nm is an absorption peak of a trans-configuration of azobenzene, and the wavelength of 453nm is an absorption peak of a cis-configuration of azobenzene. The absorption peak at 376nm gradually decreases and the absorption peak at 453nm gradually increases with the increase of the illumination time, which indicates that the azobenzene group can be trans-cis-isomeric under the ultraviolet illumination. When the illumination time reached 23s, the intensity of the absorption peak did not change any more.
Secondly, irradiating the polymer solution subjected to ultraviolet irradiation for 60s by using blue light with the wavelength of 450nm, as shown in FIG. 4: with the increase of the illumination time of blue light, the trans-configuration absorption peak of azobenzene with the wavelength of 376nm is gradually enhanced, and the cis-configuration absorption peak of azobenzene with the wavelength of 453nm is gradually weakened. This indicates that: the azobenzene which has reached cis-configuration under purple light can be returned to trans-configuration under blue light irradiation.
The above results of the photoresponsiveness analysis show that: the azobenzene group of the multi-responsive hyperbranched polymer can cause photoinduced isomerization through illumination, thereby causing the properties of molecular reorientation and the like, and therefore, the multi-responsive hyperbranched polymer has wide application prospect in the fields of intelligent materials and optical information storage.
(2) Temperature responsiveness analysis
Dissolving the multi-responsive hyperbranched polymer prepared in the embodiment 1 of the invention in DMF to prepare 0.5g/L polymer solution; taking 2mL of the polymer solution, dropwise adding 1mL of deionized water while rapidly stirring, adding a large amount of water for fixation, and dialyzing for 3 days to obtain a micelle aqueous solution with stable polymer, wherein the morphology of the obtained micelle is shown in figure 5. And then diluting the micelle aqueous solution by 10 times, heating the micelle aqueous solution by controlling the temperature through a constant-temperature water bath to ensure that the temperature is increased from 10 ℃ to 40 ℃, keeping the temperature for 6 hours every 5 ℃, and testing the particle size of the micelle in the micelle aqueous solution. Referring to FIG. 6, the graph of the micelle particle size of the multi-responsive hyperbranched polymer of the present invention changes with temperature, wherein the micelle particle size gradually decreases with increasing temperature, and the mutation occurs between 20 ℃ and 30 ℃.
(3) pH responsive assay
Dissolving the multi-responsive hyperbranched polymer prepared in the embodiment 1 of the invention in DMF to prepare 0.5g/L polymer solution; and (3) taking 2mL of the polymer solution, dropwise adding 1mL of deionized water while rapidly stirring, adding a large amount of water for fixation, and dialyzing for 3 days to obtain the stable micelle aqueous solution of the polymer (the shape of the obtained micelle is shown in figure 5). And then diluting the micelle solution by 10 times, adjusting the pH value of the micelle by dropwise adding 0.01mL of HCl aqueous solution and NaOH aqueous solution, stabilizing for 24 hours to obtain multi-response hyperbranched polymer micelle aqueous solutions with different pH values, and measuring the pH value by using a pH meter. FIG. 7 is a graph showing the change of micelle size with pH for the multi-responsive hyperbranched polymer of the present invention. The curves in fig. 7 show that: there is a critical pH at which the micelles break down. When the pH value of the solution is lower than the critical pH value, the particle size of the micelle is increased along with the increase of the pH value; when the solution pH is higher than the critical pH, the micelle particle size is slowly reduced to be constant along with the increase of the pH.
The hyperbranched structure of the multi-responsive hyperbranched polymer of the invention endows the polymer with the characteristic of large capacity, and the colloidal particles can be used as drug carriers. Meanwhile, the compound contains amide groups, has good affinity with DNA and has biocompatibility. Due to the temperature and pH responsiveness, hydrogen bonds are formed and destroyed when the environment (temperature or pH value) is changed, so that the phase state of the macromolecule is changed, and the effect of drug release or targeted transportation in organisms is finally influenced. Therefore, the method has great application value in the aspect of controlled release in the field of functional biological medicine carrying.
Through the analysis of the response performance of the above three components (light responsiveness, temperature responsiveness and pH responsiveness), the multi-responsiveness hyperbranched polymer disclosed by the invention contains both the light responsiveness azobenzene group and the temperature and pH responsiveness amide group, so that the multi-responsiveness hyperbranched polymer can be used for cell drug loading in the fields of intelligent materials, photoswitches in the photoelectric information storage field, optical devices and functional biological drug loading.
The above description is only a preferred embodiment of the present invention, and it should be noted that, without departing from the method of the present invention, a person skilled in the art may make several improvements and improvements, and these improvements and improvements should also be considered as protection scope of the present invention.
Claims (8)
1. A multi-responsive hyperbranched polymer (hpazaamam) comprising both azobenzene groups and amide groups on each branched arm, having the chemical formula:
wherein m:
2. the method of claim 1, wherein the Michael addition polymerization is performed, and the method comprises the following steps:
(1) preparation of p-diolefin azobenzene
Taking tetrahydrofuran as a solvent, adding p-diaminoazobenzene and triethylamine, and uniformly mixing under the protection of nitrogen; slowly injecting acryloyl chloride under the ice bath condition, controlling the temperature of the system to be 0-30 ℃, and reacting for 1-12 hours;
filtering to obtain upper solid;
thirdly, washing with water, centrifuging for 3 times, freeze-drying by liquid nitrogen, and drying in vacuum to obtain yellow paradiene azobenzene (azo BA) powder, wherein the general formula of the synthetic process is as follows:
(2) preparation of a Multi-responsive hyperbranched Polymer
Fully mixing p-diene azobenzene (AzoBA) powder and polyamine monomer 1- (2-aminoethyl) piperazine (AEPZ) by using Dimethylformamide (DMF) as a solvent to perform Michael addition reaction at the temperature of 20-50 ℃ for 24-80 hours;
precipitating with acetone, centrifuging for 3 times, and vacuum drying to obtain yellow solid multi-responsive hyperbranched polymer (HPAzoAMAM), wherein the general formula of the synthetic process is as follows:
wherein m:
the chemical structural formula of the multi-responsive hyperbranched polymer (HPAzoam) is as follows:
wherein m:
3. the preparation method of the multi-responsive hyperbranched polymer as claimed in claim 2, wherein the tetrahydrofuran in step (1) is used as a reaction medium, and the molar ratio of the p-diaminoazobenzene to the acryloyl chloride is greater than 1:1, so as to ensure that the p-diaminoazobenzene can react completely; wherein the dosage of triethylamine is consistent with that of acryloyl chloride.
4. The method for preparing the multi-responsive hyperbranched polymer according to claim 2, wherein the dimethylformamide solvent in the step (2) is used as a reaction medium, and the molar ratio of the p-diene azobenzene powder to the polyamine monomer 1- (2-aminoethyl) piperazine is controlled to be within 1:1, so that the occurrence of a crosslinking reaction is prevented.
5. The method for preparing the multi-responsive hyperbranched polymer according to claim 2, wherein the temperature of the reaction system is controlled to be 30 ℃ in the first 24 hours of the reaction in the step (2), and a trace amount of water is added to increase the compatibility of the reaction system; after 24 hours of reaction, the temperature is raised to 40-50 ℃ to ensure that the reaction is fully carried out.
6. Use of the multi-responsive hyperbranched polymer according to claim 1 or 2 in the field of smart materials.
7. Use of the multi-responsive hyperbranched polymer according to claim 1 or 2 in the field of optoelectronic information storage.
8. Use of the multi-responsive hyperbranched polymer of claim 1 or 2 in the field of functional drug delivery.
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