CN104028303A - Homopolymer nanometer vesicle as well as preparation method and application thereof - Google Patents
Homopolymer nanometer vesicle as well as preparation method and application thereof Download PDFInfo
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- CN104028303A CN104028303A CN201410217730.7A CN201410217730A CN104028303A CN 104028303 A CN104028303 A CN 104028303A CN 201410217730 A CN201410217730 A CN 201410217730A CN 104028303 A CN104028303 A CN 104028303A
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Abstract
The invention provides a homopolymer nanometer vesicle as well as a preparation method and application thereof. The homopolymer nanometer vesicle comprises a homopolymer vesicle and nano silver, wherein the homopolymer vesicle is formed by self-assembling of a homopolymer; nano silver is deposited on the homopolymer vesicle; the homopolymer is formed by polymerizing 4,4'-diaminodiphenyl ether and benzenetetracarboxylic anhydride in the mole ratio of 1 to (0.2-4); the mole ratio of nano silver to carboxyl in the homopolymer is (1-20) to 1. The preparation method of the homopolymer nanometer vesicle comprises the following steps: firstly, carrying out condensation polymerization on anhydride and amine with polyfunctionality at normal temperature so as to generate the homopolymer; then self-assembling the homopolymer to obtain the homopolymer vesicle; and finally, depositing nano silver on the homopolymer vesicle so as to obtain the homopolymer nanometer vesicle. The homopolymer nanometer vesicle is simple and convenient in preparation process, is short in preparation cycle, has pH responsiveness, is relatively high in stability and catalysis, and has wide application prospects in the fields of catalysis and antibiosis.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of vesica and its preparation method and application.
Background technology
In the last few years, the scientist of various countries was keeping keen interest for polymer self-assembling technique always, can form many novelties and have the structure of very large application potential by self-assembling technique, as micella, vesica, disk-like structure, vermicular texture,
Club shaped structure etc.And at this wherein, polymer vesicle, due to the existence of its center cavity, has an enormous advantage it than other structures.Due to the difference of the contained group of polymer, the polymer vesicle to external world variation of environment is made intelligent response, under the impact at pH, temperature, light, magnetic field and Redox Condition, can there is corresponding variation in the form of polymer vesicle, structure or composition.These intelligent responses make the polymer vesicle potentiality that are all widely used in a lot of fields just, as pharmaceutical carrier, microreactor, contrast preparation, metal nanoparticle are prepared template etc.
PH response is in numerous stimuli responsive factors, to study a lot of one type, and also fine control of condition.General pH response group is carboxyl or amino, along with the difference of pH can make carboxyl or amino protonated or deprotonation, thereby causes the variation of its hydrophilic and hydrophobic, reaches the object of controlling polymer vesicle form or structural change.
Although the sight of most people is all to focus on it amphipathic copolymer, along with the carrying out of research, people find that homopolymers also has similar structure and advantage gradually, and because the simplicity of its preparation process is more and more paid close attention to.The homopolymers that had not only contained hydrophilic radical but also contained hydrophobic grouping in some skeletons can self assembly form micella or vesica under certain condition.
Metal nanoparticle has been proved good catalytic performance as Nano Silver, but their easily reunite and easily oxidized defect its catalytic performance is had a greatly reduced quality, and can not preserve for a long time.Therefore it is of great value finding a kind of carrier that can make the permanent preservation of Nano Silver, and some specific polymer vesicles just in time meet these standards, but most copolymer vesica is prepared Nano Silver as template, and not only preparation process is loaded down with trivial details, and catalytic performance is not high.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, main purpose is to provide a kind of not only preparation process easy but also have a very homopolymers nano vesicle of high stability and catalytic.
Another object of the present invention is to provide a kind of preparation method of above-mentioned homopolymers nano vesicle.
The 3rd object of the present invention is to provide the purposes of above-mentioned homopolymers nano vesicle.
For achieving the above object, solution of the present invention is:
A kind of homopolymers nano vesicle, comprises the homopolymers vesica being formed by homopolymers self assembly and is deposited on the Nano Silver on homopolymers vesica, and the structural formula of homopolymers is:
Homopolymers is polymerized with the mol ratio of 1:0.2～4 by 4,4'-diaminodiphenyl ether and pyromellitic acid anhydride, and preferably, homopolymers is polymerized with the mol ratio of 1:1 by 4,4'-diaminodiphenyl ether and pyromellitic acid anhydride.In Nano Silver and homopolymers, the mol ratio of carboxyl is (1～20): 1.The particle diameter of homopolymers vesica is 100～600nm, and the particle diameter of Nano Silver is 2～20nm, and the particle diameter of homopolymers nano vesicle is 102～620nm.
A method of preparing above-mentioned homopolymers nano vesicle, comprises the steps:
(1) synthesis step of homopolymers:
Organic solvent is divided into two parts, by 4,4'-diaminodiphenyl ether is dissolved in a part of organic solvent, 4, the solution that 4'-diaminodiphenyl ether obtains after all dissolving is as the first solution, pyromellitic acid anhydride is dissolved in another part organic solvent and the solution obtaining as the second solution, 4, the mol ratio of 4'-diaminodiphenyl ether and pyromellitic acid anhydride is 1:0.2～4, the second solution is divided into 2～8 equal portions, in 1h, successively equal portions are joined in the first solution, stirring at room temperature 1h, obtains homopolymers solution;
(2) preparation process of homopolymers vesica:
By homopolymers solution dilution to the 0.5～8mg/mL of step (1) gained, the speed with 10～40d/min under vigorous stirring drips the deionized water that is three times in organic solvent volume, obtains the aqueous solution that contains homopolymers vesica after dialysis;
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that step (2) gained is contained to homopolymers vesica evenly mixes with silver nitrate aqueous solution, under stirring condition, adds sodium borohydride aqueous solution, obtains the homopolymers nano vesicle aqueous solution in deionized water after the 24h that dialyses.
Wherein, organic solvent in step (1) is dimethyl formamide, ethyl acetate, methyl-sulfoxide, carrene, one or more in oxolane and chloroform, 4, the addition of 4'-diaminodiphenyl ether is 1～100mmol, 4, the mol ratio of 4'-diaminodiphenyl ether and pyromellitic acid anhydride is 1:1, the volume of part organic solvent is 10～200mL, the volume of another part organic solvent is 20～150mL, in the carboxyl of homopolymers vesica and silver nitrate aqueous solution, the mol ratio of silver ion is 1:(1～20), in sodium borohydride aqueous solution, in sodium borohydride and silver nitrate aqueous solution, the mol ratio of silver ion is (1～40): 1.
In the time that organic solvent is ethyl acetate, 4, the addition of 4'-diaminodiphenyl ether is 5mmol, the volume of part organic solvent is 20mL, and the volume of another part organic solvent is 30mL, and the second solution is divided into 3 equal portions, homopolymers solution dilution is to 0.5mg/mL, speed is 10d/min, and in the carboxyl of homopolymers vesica and silver nitrate aqueous solution, the mol ratio of silver ion is 1:3, and in sodium borohydride aqueous solution, in sodium borohydride and silver nitrate aqueous solution, the mol ratio of silver ion is 5:1.
In the time that organic solvent is dimethyl formamide, 4, the addition of 4'-diaminodiphenyl ether is 20mmol, the volume of part organic solvent is 50mL, and the volume of another part organic solvent is 60mL, and the second solution is divided into 4 equal portions, homopolymers solution dilution is to 3mg/mL, speed is 22d/min, and in the carboxyl of homopolymers vesica and silver nitrate aqueous solution, the mol ratio of silver ion is 1:6, and in sodium borohydride aqueous solution, in sodium borohydride and silver nitrate aqueous solution, the mol ratio of silver ion is 14:1.
In the time that organic solvent is carrene, 4, the addition of 4'-diaminodiphenyl ether is 40mmol, the volume of part organic solvent is 130mL, and the volume of another part organic solvent is 120mL, and the second solution is divided into 6 equal portions, homopolymers solution dilution is to 5mg/mL, speed is 30d/min, and in the carboxyl of homopolymers vesica and silver nitrate aqueous solution, the mol ratio of silver ion is 1:12, and in sodium borohydride aqueous solution, in sodium borohydride and silver nitrate aqueous solution, the mol ratio of silver ion is 24:1.
In the time that organic solvent is methyl-sulfoxide, 4, the addition of 4'-diaminodiphenyl ether is 90mmol, the volume of part organic solvent is 180mL, and the volume of another part organic solvent is 140mL, and the second solution is divided into 7 equal portions, homopolymers solution dilution is to 7mg/mL, speed is 36d/min, and in the carboxyl of homopolymers vesica and silver nitrate aqueous solution, the mol ratio of silver ion is 1:18, and in sodium borohydride aqueous solution, in sodium borohydride and silver nitrate aqueous solution, the mol ratio of silver ion is 37:1.
Above-mentioned homopolymers nano vesicle is applied in the catalyst as aromatic nitro compound in preparation, and preferably, homopolymers nano vesicle is applied in the catalyst for the preparation of the reduction of catalysis tetranitro-phenol.
Above-mentioned homopolymers nano vesicle is in the application of preparing in antiseptic, and preferably, homopolymers nano vesicle is in the application for the preparation of suppressing in the antiseptic of Escherichia coli or staphylococcus aureus.
Owing to adopting such scheme, the invention has the beneficial effects as follows:
The first, the preparation process of homopolymers nano vesicle of the present invention is very simple, only needs three steps, and only needs 2h left and right to synthesize in a large number, and therefore productivity ratio prior art is significantly improved.
The second, homopolymers nano vesicle of the present invention disperses homogeneous, contain a large amount of unreacted carboxylic groups, can be by regulating pH to control its particle diameter, therefore, along with the difference of pH value of reaction system, can obtain having the homopolymers vesica of larger change of size scope, larger change of size scope can obtain the silver nano-grain of different-grain diameter and pattern when making depositing nano silver, and its catalytic performance is also different, is convenient to therefrom find performance best.
Three, in the homopolymers main chain of homopolymers nano vesicle of the present invention, contain a large amount of rigid structures (being phenyl ring), make the structural stability of homopolymers nano vesicle good, be conducive to the long-term preservation of Nano Silver.
Four, in homopolymers vesica of the present invention surface and film, all contain a large amount of carboxyls, be combined by coordination with silver ion, therefore for the good fixing effect of Nano Silver, make post-depositional Nano Silver have good stability and superior catalytic performance.
Brief description of the drawings
Fig. 1 is homopolymers nano vesicle in the embodiment of the present invention one particle diameter and the PDI distribution relation figure under different pH.
Fig. 2 is transmission electron microscope (TEM) photo of the homopolymers vesica in the embodiment of the present invention one.
Fig. 3 is the transmission electron microscope photo of the homopolymers nano vesicle in the embodiment of the present invention one.
Fig. 4 is the design sketch of the homopolymers nano vesicle catalysis tetranitro-phenol reduction in the embodiment of the present invention one.
Detailed description of the invention
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further illustrated.
The invention provides a kind of homopolymers nano vesicle, formed by homopolymers vesica and the Nano Silver being deposited on homopolymers vesica.
Homopolymers vesica is formed by homopolymers self assembly.This homopolymers is by 4,4'-diaminodiphenyl ether (C
12h
12n
2o, molecular weight is 200.24) and pyromellitic acid anhydride (C
10h
2o
6, molecular weight is 218.12) be polymerized with 0.2～4 mol ratio, but 4, the mol ratio of 4'-diaminodiphenyl ether and pyromellitic acid anhydride is preferably 1:1, because unnecessary monomer can't participate in polymerisation, if the mol ratio while feeding intake is not 1:1, may cause waste.Its reaction equation is as follows:
Homopolymers is formed by polycondensation polymerized by 4,4'-diaminodiphenyl ether and pyromellitic acid anhydride, has many unreacted carboxyls on it, therefore has pH response.The response of pH value is having potential application aspect medicine controllable release, and on this basis can also be further functionalized, thereby also has in other respects potential application.
In Nano Silver and homopolymers, the mol ratio of carboxyl is (1～20): 1.Because there is some difference for the membrane structure of the membrane structure of homopolymers vesica and copolymer vesica, be that close and distant water section in homopolymers vesica film is very not clearly demarcated, therefore can utilize this feature to carry out plated metal nano particle using homopolymers vesica as template, as Nano Silver.Use homopolymers vesica not only can fix well Nano Silver, and preparation process is very easy, stability and catalytic performance are also very high, use copolymer vesica to prepare the loaded down with trivial details and catalytic performance not high problem of preparation process that Nano Silver brings as template thereby overcome.
The particle diameter of homopolymers vesica is 100～600nm, and the particle diameter of Nano Silver is 2～20nm, and the particle diameter of homopolymers nano vesicle is 102～620nm.
The preparation method of above-mentioned homopolymers nano vesicle comprises the steps:
(1) synthesis step of homopolymers:
Organic solvent is divided into two parts, by 4,4'-diaminodiphenyl ether is dissolved in a part of organic solvent, 4, the solution that 4'-diaminodiphenyl ether obtains after all dissolving is as the first solution, then pyromellitic acid anhydride is dissolved in and in another part organic solvent, obtains the second solution, 4, the mol ratio of 4'-diaminodiphenyl ether and pyromellitic acid anhydride is 1:0.2～4, the second solution is divided into 2～8 equal portions, in 1h, successively equal portions are joined in the first solution, stirring at room temperature 1h, obtains homopolymers solution.
In this step, the second solution is divided into 2～8 equal portions, then adds successively at the same time respectively every equal portions, and this operation can be controlled the carrying out of reaction, makes to greatest extent the chain length of polymer be tending towards homogeneous.
(2) preparation process of homopolymers vesica:
By homopolymers solution dilution to the 0.5～8mg/mL of step (1) gained, under vigorous stirring, drip with the speed of 10～40d/min the deionized water that is three times in organic solvent volume, dialysis obtains to remove the aqueous solution that contains homopolymers vesica after above-mentioned organic solvent;
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that step (2) gained is contained to homopolymers vesica evenly mixes with silver nitrate aqueous solution, under stirring condition, add sodium borohydride aqueous solution, after reduction, in deionized water, dialyse 24h to remove sodium nitrate and boric acid, obtain the homopolymers nano vesicle aqueous solution.
Wherein, above-mentioned organic solvent can be dimethyl formamide, ethyl acetate, methyl-sulfoxide, carrene, one or more in oxolane and chloroform, 4, the addition of 4'-diaminodiphenyl ether can be 1～100mmol, the volume of part organic solvent can be 10～200mL, the volume of another part organic solvent can be 20～150mL, in the carboxyl of homopolymers vesica and silver nitrate aqueous solution, the mol ratio of silver ion can be 1:(1～20), in sodium borohydride aqueous solution, in sodium borohydride and silver nitrate aqueous solution, the mol ratio of silver ion can be (1～40): 1.
Embodiment mono-
Organic solvent in the present embodiment can be ethyl acetate, and now, the preparation method of homopolymers nano vesicle comprises the steps:
(1) synthesis step of homopolymers:
1.000g (being 5mmol) 4,4'-diaminodiphenyl ether is dissolved in 20mL ethyl acetate and the solution obtaining after whole 4,4'-diaminodiphenyl ether dissolving as the first solution;
Then, 1.090g (being 5mmol) pyromellitic acid anhydride is dissolved in 30mL ethyl acetate and the solution obtaining as the second solution, the second solution is divided into 3 equal portions, in 1h, successively above-mentioned 3 equal portions are joined in above-mentioned the first solution, stirring at room temperature reaction 1h, obtains the ethyl acetate solution that contains homopolymers.
(2) preparation process of homopolymers vesica:
The ethyl acetate solution that step (1) gained is contained to homopolymers is diluted to 0.5mg/mL, under vigorous stirring, 3 times of deionized waters to ethyl acetate volume are added drop-wise in the ethyl acetate solution that contains homopolymers with the speed of 10d/min (droplet/minute), in deionized water, dialyse 24h to remove ethyl acetate, obtain the aqueous solution that contains homopolymers vesica.In the aqueous solution that contains homopolymers vesica, the concentration of homopolymers vesica is 0.2mg/mL.In this step, by regulating the pH value of reaction system can control particle diameter and the molecular weight distribution (Polydispersity index, PDI) of homopolymers vesica.The pH value of reaction system and the particle diameter of homopolymers vesica and the relation of molecular weight distribution are as shown in Figure 1.The transmission electron microscope photo (TEM) of homopolymers vesica as shown in Figure 2.In this step, the different institute of the drop rate vesica size that obtains may be different, and drop rate is faster, and size is less.
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that contains homopolymers vesica that step (2) is obtained evenly mixes with silver nitrate aqueous solution, making the mol ratio of the carboxyl of silver ion and homopolymers vesica in silver nitrate aqueous solution is 3:1, lucifuge adds the sodium borohydride aqueous solution of newly joining after stirring half an hour, making in silver nitrate aqueous solution the mol ratio of sodium borohydride in silver ion and sodium borohydride aqueous solution is 1:5, after evenly mixing, lucifuge stirs 12h, in deionized water, dialyse 24h to remove sodium nitrate and boric acid, thereby obtain containing the aqueous solution of the homopolymers vesica that has deposited Nano Silver, be homopolymers nano vesicle solution.The TEM photo of this step gained homopolymers nano vesicle as shown in Figure 3.
By using silver nitrate as silver-colored source, the carboxylic acid ion generation coordination of silver ion and homopolymers vesica is assembled silver ion, just can obtain having deposited the homopolymers vesica of Nano Silver by sodium borohydride reduction, the catalytic performance of this compound vesica is fine, therefore, this homopolymers nano vesicle can be applied to for the preparation of the wide spectrum catalyst as aromatic nitro compound, as nitrobenzene, dinitro benzene, nitrotoleune, a nitro-chlorobenzene etc.In the present embodiment, be applied to prepare the catalyst of catalysis tetranitro-phenol reduction.The design sketch of this homopolymers nano vesicle catalysis tetranitro-phenol reduction as shown in Figure 4.
In addition, due to the antibiotic property of Nano Silver, can also serve as broad spectrum antimicrobicide, for Escherichia coli, staphylococcus aureus etc. are all inhibited.
Embodiment bis-
Compared with embodiment mono-, the organic solvent in the present embodiment can be dimethyl formamide, and now, the preparation method of homopolymers nano vesicle comprises the steps:
(1) synthesis step of homopolymers:
4.000g (being 20mmol) 4,4'-diaminodiphenyl ether is dissolved in 50mL dimethyl formamide and the solution obtaining after whole 4,4'-diaminodiphenyl ether dissolving as the first solution;
Then, 4.360g (being 20mmol) pyromellitic acid anhydride is dissolved in 60mL dimethyl formamide and the solution obtaining as the second solution, the second solution is divided into 4 equal portions, in 1h, successively above-mentioned 4 equal portions is joined in above-mentioned the first solution, stirring at room temperature reaction 1h.Obtain the dimethyl formamide solution that contains homopolymers.
(2) preparation process of homopolymers vesica:
The dimethyl formamide solution that step (1) gained is contained to homopolymers is diluted to 3mg/mL, under vigorous stirring, 3 times of deionized waters to dimethyl formamide volume are added drop-wise to the speed of 22d/min in the dimethyl formamide solution that contains homopolymers, in deionized water, dialyse 24h to remove dimethyl formamide, obtain the aqueous solution that contains homopolymers vesica.In the aqueous solution that contains homopolymers vesica, the concentration of homopolymers vesica is 0.8mg/mL.
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that contains homopolymers vesica that step (2) is obtained evenly mixes with silver nitrate aqueous solution, making the mol ratio of the carboxyl of silver ion and homopolymers vesica in silver nitrate aqueous solution is 6:1, lucifuge adds the sodium borohydride aqueous solution of newly joining after stirring half an hour, making in silver nitrate aqueous solution the mol ratio of sodium borohydride in silver ion and sodium borohydride aqueous solution is 1:14, after evenly mixing, lucifuge stirs 12h, in deionized water, dialyse 24h to remove sodium nitrate and boric acid, thereby obtain containing the aqueous solution of the homopolymers vesica that has deposited Nano Silver, be homopolymers nano vesicle solution.
Embodiment tri-
Compared with embodiment mono-, the organic solvent in the present embodiment can be carrene, and now, the preparation method of homopolymers nano vesicle comprises the steps:
(1) synthesis step of homopolymers:
8.000g (being 40mmol) 4,4'-diaminodiphenyl ether is dissolved in 130mL carrene and the solution obtaining after whole 4,4'-diaminodiphenyl ether dissolving as the first solution;
Then, 8.720g (being 40mmol) pyromellitic acid anhydride is dissolved in 120mL carrene and the solution obtaining as the second solution, the second solution is divided into 6 equal portions, in 1h, successively above-mentioned 6 equal portions are joined in above-mentioned the first solution, stirring at room temperature reaction 1h, obtains the dichloromethane solution that contains homopolymers.
(2) preparation process of homopolymers vesica:
The dichloromethane solution that step (1) gained is contained to homopolymers is diluted to 5mg/mL, under vigorous stirring, 3 times of deionized waters to methylene chloride volume are added drop-wise to the speed of 30d/min in the dichloromethane solution that contains homopolymers, in deionized water, dialyse 24h to remove carrene, obtain the aqueous solution that contains homopolymers vesica.In the aqueous solution that contains homopolymers vesica, the concentration of homopolymers vesica is 1.2mg/mL.
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that contains homopolymers vesica that step (2) is obtained evenly mixes with silver nitrate aqueous solution, making the mol ratio of the carboxyl of silver ion and homopolymers vesica in silver nitrate aqueous solution is 12:1, lucifuge adds the sodium borohydride aqueous solution of newly joining after stirring half an hour, making in silver nitrate aqueous solution the mol ratio of sodium borohydride in silver ion and sodium borohydride aqueous solution is 1:24, after evenly mixing, lucifuge stirs 12h, in deionized water, dialyse 24h to remove sodium nitrate and boric acid, thereby obtain containing the aqueous solution of the homopolymers vesica that has deposited Nano Silver, be homopolymers nano vesicle solution.
Embodiment tetra-
Compared with embodiment mono-, the organic solvent in the present embodiment can be methyl-sulfoxide.In the present embodiment, the preparation method of homopolymers nano vesicle comprises the steps:
(1) synthesis step of homopolymers:
18.00g (being 90mmol) 4,4'-diaminodiphenyl ether is dissolved in 180mL methyl-sulfoxide and the solution obtaining after whole 4,4'-diaminodiphenyl ether dissolving as the first solution;
Then, 19.62g (being 90mmol) pyromellitic acid anhydride is dissolved in 140mL methyl-sulfoxide and the solution obtaining as the second solution, the second solution is divided into 7 equal portions, in 1h, successively above-mentioned 7 equal portions are joined in above-mentioned the first solution, stirring at room temperature reaction 1h, obtains the dimethyl sulfoxide solution that contains homopolymers.
(2) preparation process of homopolymers vesica:
The dimethyl sulfoxide solution that step (1) gained is contained to homopolymers is diluted to 7mg/mL, under vigorous stirring, 3 times of deionized waters to methyl-sulfoxide volume are added drop-wise to the speed of 36d/min in the dimethyl sulfoxide solution that contains homopolymers, in deionized water, dialyse 24h to remove methyl-sulfoxide, obtain the aqueous solution that contains homopolymers vesica.In the aqueous solution that contains homopolymers vesica, the concentration of homopolymers vesica is 1.8mg/mL.
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that contains homopolymers vesica that step (2) is obtained evenly mixes with silver nitrate aqueous solution, making the mol ratio of the carboxyl of silver ion and homopolymers vesica in silver nitrate aqueous solution is 18:1, lucifuge adds the sodium borohydride aqueous solution of newly joining after stirring half an hour, making in silver nitrate aqueous solution the mol ratio of sodium borohydride in silver ion and sodium borohydride aqueous solution is 1:37, after evenly mixing, lucifuge stirs 12h, in deionized water, dialyse 24h to remove sodium nitrate and boric acid, thereby obtain containing the aqueous solution of the homopolymers vesica that has deposited Nano Silver, be homopolymers nano vesicle solution.
Embodiment five
In the present embodiment, the molar ratio of 4,4'-diaminodiphenyl ether and pyromellitic acid anhydride can also be 1:0.2, and now, the preparation method of homopolymers nano vesicle comprises the steps:
(1) synthesis step of homopolymers:
18.00g (being 90mmol) 4,4'-diaminodiphenyl ether is dissolved in 180mL methyl-sulfoxide and the solution obtaining after whole 4,4'-diaminodiphenyl ether dissolving as the first solution;
Then, 3.924g (being 18mmol) pyromellitic acid anhydride is dissolved in 140mL methyl-sulfoxide and the solution obtaining as the second solution, the second solution is divided into 7 equal portions, in 1h, successively above-mentioned 7 equal portions are joined in above-mentioned the first solution, stirring at room temperature reaction 1h, obtains the dimethyl sulfoxide solution that contains homopolymers.
(2) preparation process of homopolymers vesica:
The dimethyl sulfoxide solution that step (1) gained is contained to homopolymers is diluted to 7mg/mL, under vigorous stirring, 3 times of deionized waters to methyl-sulfoxide volume are added drop-wise to the speed of 36d/min in the dimethyl sulfoxide solution that contains homopolymers, in deionized water, dialyse 24h to remove methyl-sulfoxide, obtain the aqueous solution that contains homopolymers vesica.In the aqueous solution that contains homopolymers vesica, the concentration of homopolymers vesica is 1.3mg/mL.Because the inside has unreacted monomer, the concentration therefore obtaining can be than lower in example four.
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that contains homopolymers vesica that step (2) is obtained evenly mixes with silver nitrate aqueous solution, making the mol ratio of the carboxyl of silver ion and homopolymers vesica in silver nitrate aqueous solution is 18:1, lucifuge adds the sodium borohydride aqueous solution of newly joining after stirring half an hour, making in silver nitrate aqueous solution the mol ratio of sodium borohydride in silver ion and sodium borohydride aqueous solution is 1:37, after evenly mixing, lucifuge stirs 12h, in deionized water, dialyse 24h to remove sodium nitrate and boric acid, thereby obtain containing the aqueous solution of the homopolymers vesica that has deposited Nano Silver, be homopolymers nano vesicle solution.
Embodiment six
Compared with embodiment five, the molar ratio of 4,4'-diaminodiphenyl ether and pyromellitic acid anhydride can also be 1:4, and now, the preparation method of homopolymers nano vesicle comprises the steps:
(1) synthesis step of homopolymers:
18.00g (being 90mmol) 4,4'-diaminodiphenyl ether is dissolved in 180mL methyl-sulfoxide and the solution obtaining after whole 4,4'-diaminodiphenyl ether dissolving as the first solution;
Then, 78.48g (being 360mmol) pyromellitic acid anhydride is dissolved in 140mL methyl-sulfoxide and the solution obtaining as the second solution, the second solution is divided into 7 equal portions, in 1h, successively above-mentioned 7 equal portions are joined in above-mentioned the first solution, stirring at room temperature reaction 1h, obtains the dimethyl sulfoxide solution that contains homopolymers.
(2) preparation process of homopolymers vesica:
The dimethyl sulfoxide solution that step (1) gained is contained to homopolymers is diluted to 7mg/mL, under vigorous stirring, 3 times of deionized waters to methyl-sulfoxide volume are added drop-wise to the speed of 36d/min in the dimethyl sulfoxide solution that contains homopolymers, in deionized water, dialyse 24h to remove methyl-sulfoxide, obtain the aqueous solution that contains homopolymers vesica.In the aqueous solution that contains homopolymers vesica, the concentration of homopolymers vesica is 1.8mg/mL.
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that contains homopolymers vesica that step (2) is obtained evenly mixes with silver nitrate aqueous solution, making the mol ratio of the carboxyl of silver ion and homopolymers vesica in silver nitrate aqueous solution is 18:1, lucifuge adds the sodium borohydride aqueous solution of newly joining after stirring half an hour, making in silver nitrate aqueous solution the mol ratio of sodium borohydride in silver ion and sodium borohydride aqueous solution is 1:37, after evenly mixing, lucifuge stirs 12h, in deionized water, dialyse 24h to remove sodium nitrate and boric acid, thereby obtain containing the aqueous solution of the homopolymers vesica that has deposited Nano Silver, be homopolymers nano vesicle solution.
In sum, preparation method of the present invention utilizes two kinds of acid anhydrides and amine with polyfunctionality to carry out at normal temperatures polycondensation reaction, the homopolymers solution obtaining directly utilizes exchange of solvent method can obtain disperseing the very homopolymers vesica of homogeneous, and without purification, preparation method is very simple.Owing to there being unreacted carboxyl to exist in homopolymers, the homopolymers vesica therefore obtaining has pH response.Along with the difference of pH value, can obtain the homopolymers nano vesicle of the different-grain diameter that disperses homogeneous.Preparation method's step of this homopolymers nano vesicle is few, the cycle is short, once can prepare in a large number, and all contain a large amount of carboxyls due on surface and film, therefore can be used as template preparation and stabilized nanoscale silver, has wide practical use at catalytic field.
The above-mentioned description to embodiment is can understand and use the present invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various amendments to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art are according to announcement of the present invention, and not departing from improvement and the amendment that category of the present invention makes all should be within protection scope of the present invention.
Claims (10)
1. a homopolymers nano vesicle, is characterized in that: comprise the homopolymers vesica being formed by homopolymers self assembly and be deposited on the Nano Silver on described homopolymers vesica, the structural formula of described homopolymers is:
In described Nano Silver and described homopolymers, the mol ratio of carboxyl is (1～20): 1.
2. homopolymers nano vesicle according to claim 1, it is characterized in that: described homopolymers is by 4,4'-diaminodiphenyl ether and pyromellitic acid anhydride are polymerized with the mol ratio of 1:0.2～4, preferably, described homopolymers is polymerized with the mol ratio of 1:1 by 4,4'-diaminodiphenyl ether and pyromellitic acid anhydride; Or the particle diameter of described homopolymers vesica is 100～600nm, the particle diameter of described Nano Silver is 2～20nm, and the particle diameter of described homopolymers nano vesicle is 102～620nm.
3. a method of preparing homopolymers nano vesicle as claimed in claim 1 or 2, is characterized in that: comprise the steps:
(1) synthesis step of homopolymers:
Organic solvent is divided into two parts, by 4,4'-diaminodiphenyl ether is dissolved in a part of organic solvent, 4, the solution that 4'-diaminodiphenyl ether obtains after all dissolving is as the first solution, pyromellitic acid anhydride is dissolved in another part organic solvent and the solution obtaining as the second solution, described 4, the mol ratio of 4'-diaminodiphenyl ether and described pyromellitic acid anhydride is 1:0.2～4, described the second solution is divided into 2～8 equal portions, in 1h, described equal portions are joined in described the first solution successively, stirring at room temperature 1h, obtains homopolymers solution;
(2) preparation process of homopolymers vesica:
By homopolymers solution dilution to the 0.5～8mg/mL of step (1) gained, the speed with 10～40d/min under vigorous stirring drips the deionized water that is three times in described organic solvent volume, obtains the aqueous solution that contains homopolymers vesica after dialysis;
(3) synthesis step of homopolymers nano vesicle:
The aqueous solution that step (2) gained is contained to homopolymers vesica evenly mixes with silver nitrate aqueous solution, under stirring condition, adds sodium borohydride aqueous solution, obtains the homopolymers nano vesicle aqueous solution in deionized water after the 24h that dialyses.
4. the method for preparing homopolymers vesica according to claim 3, it is characterized in that: the organic solvent in step (1) is dimethyl formamide, ethyl acetate, methyl-sulfoxide, carrene, one or more in oxolane and chloroform, described 4, the addition of 4'-diaminodiphenyl ether is 1～100mmol, described 4, the mol ratio of 4'-diaminodiphenyl ether and described pyromellitic acid anhydride is 1:1, the volume of described a part of organic solvent is 10～200mL, the volume of described another part organic solvent is 20～150mL, in the carboxyl of described homopolymers vesica and described silver nitrate aqueous solution, the mol ratio of silver ion is 1:(1～20), in described sodium borohydride aqueous solution, in sodium borohydride and described silver nitrate aqueous solution, the mol ratio of silver ion is (1～40): 1.
5. the method for preparing homopolymers vesica according to claim 4, it is characterized in that: in the time that described organic solvent is ethyl acetate, described 4, the addition of 4'-diaminodiphenyl ether is 5mmol, the volume of described a part of organic solvent is 20mL, the volume of described another part organic solvent is 30mL, described the second solution is divided into 3 equal portions, described homopolymers solution dilution is to 0.5mg/mL, described speed is 10d/min, in the carboxyl of described homopolymers vesica and described silver nitrate aqueous solution, the mol ratio of silver ion is 1:3, in described sodium borohydride aqueous solution, in sodium borohydride and described silver nitrate aqueous solution, the mol ratio of silver ion is 5:1.
6. the method for preparing homopolymers vesica according to claim 4, it is characterized in that: in the time that described organic solvent is dimethyl formamide, described 4, the addition of 4'-diaminodiphenyl ether is 20mmol, the volume of described a part of organic solvent is 50mL, the volume of described another part organic solvent is 60mL, described the second solution is divided into 4 equal portions, described homopolymers solution dilution is to 3mg/mL, described speed is 22d/min, in the carboxyl of described homopolymers vesica and described silver nitrate aqueous solution, the mol ratio of silver ion is 1:6, in described sodium borohydride aqueous solution, in sodium borohydride and described silver nitrate aqueous solution, the mol ratio of silver ion is 14:1.
7. the method for preparing homopolymers vesica according to claim 4, it is characterized in that: in the time that described organic solvent is carrene, described 4, the addition of 4'-diaminodiphenyl ether is 40mmol, the volume of described a part of organic solvent is 130mL, the volume of described another part organic solvent is 120mL, described the second solution is divided into 6 equal portions, described homopolymers solution dilution is to 5mg/mL, described speed is 30d/min, in the carboxyl of described homopolymers vesica and described silver nitrate aqueous solution, the mol ratio of silver ion is 1:12, in described sodium borohydride aqueous solution, in sodium borohydride and described silver nitrate aqueous solution, the mol ratio of silver ion is 24:1.
8. the method for preparing homopolymers vesica according to claim 4, it is characterized in that: in the time that described organic solvent is methyl-sulfoxide, described 4, the addition of 4'-diaminodiphenyl ether is 90mmol, the volume of described a part of organic solvent is 180mL, the volume of described another part organic solvent is 140mL, described the second solution is divided into 7 equal portions, described homopolymers solution dilution is to 7mg/mL, described speed is 36d/min, in the carboxyl of described homopolymers vesica and described silver nitrate aqueous solution, the mol ratio of silver ion is 1:18, in described sodium borohydride aqueous solution, in sodium borohydride and described silver nitrate aqueous solution, the mol ratio of silver ion is 37:1.
Homopolymers nano vesicle as claimed in claim 1 or 2 in preparation as the application in the catalyst of aromatic nitro compound, preferably, the application of described homopolymers nano vesicle in the catalyst for the preparation of catalysis tetranitro-phenol reduction.
10. homopolymers nano vesicle as claimed in claim 1 or 2 is in the application of preparing in antiseptic, and preferably, described homopolymers nano vesicle is in the application for the preparation of suppressing in the antiseptic of Escherichia coli or staphylococcus aureus.
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| CN104628916A (en) * | 2015-01-16 | 2015-05-20 | 同济大学 | Homopolymer nano vesicle as well as preparation method and application thereof |
| CN104628916B (en) * | 2015-01-16 | 2017-04-12 | 同济大学 | Homopolymer nano vesicle as well as preparation method and application thereof |
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