CN101215352A - Method for preparing amphoteric ion polymer and pH response type polymer micelle buffer solution thereof - Google Patents
Method for preparing amphoteric ion polymer and pH response type polymer micelle buffer solution thereof Download PDFInfo
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- CN101215352A CN101215352A CNA2008100194779A CN200810019477A CN101215352A CN 101215352 A CN101215352 A CN 101215352A CN A2008100194779 A CNA2008100194779 A CN A2008100194779A CN 200810019477 A CN200810019477 A CN 200810019477A CN 101215352 A CN101215352 A CN 101215352A
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Abstract
The invention relates to an amphiphilic amphoteric ion polymer and a process for preparing pH response type polymer namely micelle buffering liquid, which belongs to the technical field of macromolecule material. Styrenemaleic anhydride amphiphilic polymer are prepared by styrene monomer/maleic anhydride monomer series with strong alternating polymerization tendency in 60-70 degrees through free radical alternating copolymerization reaction for 6-24 hours, and carboxylic acid anhydrides unit in the amphiphilic polymer is utilized to have a reaction with aminopyridine (or aminopyridine which contains substituent group ) to get amphiphilic amphoteric ion polymer, and pH response type polymer namely micelle buffering liquid is prepared by the amphiphilic amphoteric ion polymer which is got through micellization process. Compared with the prior pH response type polymer, the amphiphilic polymer of the invention has the properties of amphoteric ion and weak acid and weak base buffering liquid, and the buffering scope can be changed through adjusting system parameters such as hydrophibic and hydrophobic unit ratio and the like of the polymer. The amphiphilic amphoteric ion polymer nano-micelle can also be applied in the aspects such as medicament loading and releasing, catalyzing and loading and the like.
Description
Technical field
The preparation method of amphoteric ion polymer and pH response type polymer micelle buffer solution thereof belongs to technical field of polymer materials.The present invention relates to the preparation of a kind of amphoteric ion polymer and pH response type polymer micelle buffer solution thereof, its application comprises the existing application and the potential application of nano-micelles such as drug loading release, polymer modification and chemical reaction load.
Background technology
Environment sensitive type parents polymkeric substance is a kind of new functional macromolecule material, in its polymer architecture, introduce various environmental sensitivity primitives, made this parents' polymkeric substance under such as the effect of external stimuluss such as temperature, pH, ionic strength (ionogen), electric field, light, realize that " intelligence " changes.Environment sensitive type parents polymkeric substance has many application in fields such as biomedicine, chemical reaction, environment protection, as the protection carriers of biomacromolecules such as restricted reaction vessel, load release vehicle, catalyzer and enzyme etc.Aspect biological and medical, the carrier made from parents' polymer micelle can be used for various controlled delivery of pharmaceutical agents loads releases.At chemical field, polymer micelle can be used for the particle diameter of nano material and the control of form as template; As microreactor can be used for that the control of polymkeric substance is synthetic, the preparation of catalyzed reaction and high-performance catalyst system; And, can be used for load of photoelectric functional species or the like in the special material field.Therefore, for the preparation and the correlative study of polymer nano micelle, people have given the attention of height.
Amphoteric ion polymer not only contains close and distant water unit simultaneously in its chain link, and contains positively charged ion and negatively charged ion primitive simultaneously, thereby makes such parents' polymkeric substance have more function and application widely.Amphoteric ion polymer system and micella thereof also can be used for rheology modifying, biological adhesive, enzyme inhibitors or the systems such as physiology desalting system and phosphoric acid salt tackiness agent of positively charged ion or acidic system except being used for the known fields of common parents' polymkeric substance such as drug loading release, catalysis load.
Summary of the invention
The objective of the invention is to prepare a kind of amphoteric ion polymer and pH response type polymer micelle buffer solution thereof with easy method.
The present invention is based on to the carboxylic acid anhydride primitive with contain the understanding that pyridine weak base functionalizing compound can form weak acid and weak base zwitter-ion title complex, work out under room temperature or heating condition, prepare novel amphoteric ion polymer by carboxylic acid anhydride primitive and aminopyridine aminolysis reaction, and utilize the deliquescent difference of the close and distant water section of polymkeric substance to prepare polymer micelle solution with pH response performance and shock-absorbing capacity.
Technical scheme of the present invention: a kind of preparation method of amphoteric ion polymer, shown in reaction formula 1;
Reaction formula 1,
(1) radical polymerization: by phenylethylene/maleic anhydride monomer with strong alternating polymerization tendency, with the anhydrous tetrahydro furan is solvent, in the presence of radical initiator Bendioxide formyl through the free radical alternating copolymerization react phenylethylene-maleic anhydride parents polymkeric substance, the mol ratio of styrene monomer and maleic anhydride is 3-1: 1, the molar ratio that radical initiator Bendioxide formyl mole dosage accounts for total monomer is 0.2%-2%, at 60～70 ℃ of following copolyreaction 6-24h;
(2) aminolysis reaction: carboxylic acid anhydride unit and the aminopyridine of utilizing phenylethylene-maleic anhydride parents polymkeric substance again, or alkylamino pyridine, or alkoxy amino pyridine stirring at room aminolysis reaction 12 hours in anhydrous dimethyl sulphoxide, be warming up to 50 ℃ of reaction 2h again, the concentration of phenylethylene-maleic anhydride parents polymkeric substance is 0.2g/mL, aminopyridine, or alkylamino pyridine, or alkoxy amino pyridine and the unitary molar ratio of carboxylic acid anhydride be 50%-200%, and the aminolysis reaction resulting polymers is through ether sedimentation and the ether extrct pyridine that deaminizes repeatedly, or alkylamino pyridine, or the alkoxy amino pyridine obtains amphoteric ion polymer.
This amphoteric ion is polymerized to random parents polymkeric substance, and contains the alternating polymerization segment.
The application method of this amphoteric ion polymer, this amphoteric ion polymer is carried out the micellization of polymkeric substance according to the classical way of preparation amphoteric ion polymer nano-micelle, preparation amphoteric ion polymer nano-micelle: with this amphoteric ion polymer is that 2-100mg/mL is dissolved in the cosolvent dimethyl sulfoxide (DMSO) of close and distant water base unit with concentration, at the uniform velocity stir the precipitation agent deionized water that progressively slowly drips hydrophobic primitive down in polymers soln, the deionized water consumption is one times of amount of dimethyl sulfoxide (DMSO) consumption; Continue at the uniform velocity to stir 2 hours after dropwising, the deionized water that disposable then adding doubles the dimethyl sulfoxide (DMSO) consumption makes micella stable; Continue to stir that osmose process displaces dimethyl sulfoxide solvent after 2 hours, thereby obtain the nano-micelle aqueous solution of this amphoteric ion polymer.
The nano-micelle aqueous solution of this amphoteric ion polymer, hydroxy-acid group in this polymkeric substance and pyridine group can form weak acid and weak base salt in neutral aqueous solution, see reaction formula 2-B; And in sour environment, then form strong acid pyridinium salt and free carboxy acid's form, see reaction formula 2-A; In alkaline environment, then form the form of carboxylate salt and free pyridine, see reaction formula 2-C;
Promptly the gained system has pH response performance and shock-absorbing capacity after this amphoteric ion polymer nano-micelleization.
The pH response performance of this amphoteric ion polymer nano-micelle aqueous solution and shock-absorbing capacity are adjusted by ratio, initiator and the monomer molar ratio of the close and distant aqueous monomer of phenylethylene/maleic anhydride of regulating the radical polymerization system, the replacement type that reaches aminopyridine and introducing amount.
The application of this amphoteric ion polymer nano-micelle aqueous solution, being used for drug loading release, polymer modification and chemical reaction loaded with nano micellar has to use and potential application the sixth of the twelve Earthly Branches.
Above-mentioned preparation condition all can be realized for this area scientific and technical personnel.
Beneficial effect of the present invention: the present invention prepares a kind of amphoteric ion polymer and pH response type polymer micelle buffer solution thereof with simple and direct method.The present invention is based on the carboxylic acid anhydride primitive and contains the understanding that pyridine weak base functionalizing compound can form weak acid and weak base zwitter-ion title complex, work out under room temperature or heating condition, aminolysis reaction by carboxylic acid anhydride primitive and aminopyridine basic cpd is prepared amphoteric ion polymer, and utilizes the deliquescent difference of the close and distant water section of polymkeric substance to prepare the polymer micelle solution with pH response performance and shock-absorbing capacity in the aqueous solution.The present invention comes from a kind of brand-new thinking, and method is easy, and is respond well, has immeasurable application prospect.Each step and the method that the present invention relates to, those skilled in the art all can realize.
Description of drawings
Fig. 1. the pH response performance and the shock-absorbing capacity of amphoteric ion polymer micellar solution.
Embodiment
One, polymerization process
The phenylethylene/maleic anhydride monomer is with 3-1: 1 molar ratio is a solvent with the anhydrous tetrahydro furan, is initiator with the Bendioxide formyl, and 60-70 ℃ of following thermal-initiated polymerization, stopped reaction gets a polymers soln after 6-24 hour after removing system oxygen.The gained system through ether sedimentation separate the phenylethylene-maleic anhydride polymkeric substance.
Two, aminolysis process
A certain amount of phenylethylene-maleic anhydride polymkeric substance (0.2g/mL) is dissolved among the anhydrous dimethyl sulphoxide DMSO, a certain amount of aminopyridine (the unitary mol ratio of aminopyridine and carboxylic acid anhydride is 50%-200%) is added wherein, under the room temperature stirring reaction after 12 hours reheat to 50 ℃ reaction 2 hours with guarantee aminolysis reaction fully.Stopped reaction, resulting polymers gets amphoteric ion polymer after the extracting repeatedly through ether sedimentation and ether.
Three, the micellization process of polymkeric substance
The amphoteric ion polymer of gained is dissolved in certain amount among the cosolvent dimethyl sulfoxide (DMSO) DMSO of close and distant water unit (concentration of polymkeric substance is 2mg/mL-100mg/mL), at the uniform velocity stirs the precipitation agent deionized water (being one times of amount of DMSO consumption) that progressively in polymers soln, slowly drips hydrophobic primitive down; Continue at the uniform velocity to stir 2 hours after dropwising, the deionized water that disposable then adding doubles the DMSO consumption makes micella stable; Continue to stir that osmose process displaces the DMSO solvent after 2 hours, thereby obtain the micellar aqueous solution of this amphoteric ion polymer.
Embodiment 1: with 2/1 polymerization of phenylethylene/maleic anhydride monomer mole ratio, be example through 2-aminopyridine aminolysis again.Reaction formula is:
With the phenylethylene/maleic anhydride monomer polymerization, be the amphoteric ion polymer pH response process of example gained through 2-aminopyridine aminolysis again.Reaction formula is:
1.1 phenylethylene-maleic anhydride polymkeric substance
The phenylethylene/maleic anhydride monomer is solvent with 2/1 ratio with the anhydrous tetrahydro furan, is initiator with the Bendioxide formyl, and at 65 ℃ of following initiated polymerizations, stopped reaction gets a polymers soln after 12 hours after removing system oxygen.The gained system gets the phenylethylene-maleic anhydride polymkeric substance through precipitate and separate.
1.2 the 2-aminopyridine aminolysis process of phenylethylene-maleic anhydride polymkeric substance
With 2g phenylethylene-maleic anhydride polymer dissolution in the 10mL dry DMF, with excessive 2-amino
Pyridine (with the ratio of carboxylic acid anhydride be 200%) add wherein, under the room temperature stirring reaction after 12 hours reheat to 50 ℃ reaction 2 hours with guarantee aminolysis reaction fully.Stopped reaction, resulting polymers get amphoteric ion polymer after the ether repeated precipitation.
1.3 the micellization process of amphoteric ion polymer
Among the amphoteric ion polymer 100mg dissolving 10mLDMSO with gained, at the uniform velocity stir the precipitation agent deionized water 10mL that progressively in polymers soln, slowly drips hydrophobic primitive down; Continue at the uniform velocity to stir 2 hours after dropwising, disposable then adding 20mL deionized water makes micella stable; Continue to stir that osmose process displaces the DMSO solvent after 2 hours, thereby obtain the micellar aqueous solution of this amphoteric ion polymer.
1.4 the pH response performance and the shock-absorbing capacity of amphoteric ion polymer micellar solution
Polymer micelle solution is mixed mutually with the solution of certain pH value, and the pH value that adds the back system with micellar solution is an X-coordinate, and the pH value before adding with micellar solution is an ordinate zou, gets the pH response curve.As shown in Figure 1, the pH value is the heavy system of acid less than 3 system, and polymer latex intrafascicular carboxylic acid group assemble under the repulsion of strong acid, thereby makes whole polymer micelle contraction, the pH value of micellar solution with adding strength of acid to be line style related; Be between 3～12 in the pH value, whole micellar system is buffer status, and considerable change does not take place micella; Greater than 12 zones, polymer micelle is the molten state of alkali in the pH value, and the pH value of micellar solution is the line style variation with the intensity of add alkali.
Claims (6)
1. the preparation method of an amphoteric ion polymer is characterized in that shown in reaction formula 1;
Reaction formula 1,
(1) radical polymerization: by phenylethylene/maleic anhydride monomer with strong alternating polymerization tendency, with the anhydrous tetrahydro furan is solvent, in the presence of radical initiator Bendioxide formyl through the free radical alternating copolymerization react phenylethylene-maleic anhydride parents polymkeric substance, the mol ratio of styrene monomer and maleic anhydride is 3-1: 1, the molar ratio that radical initiator Bendioxide formyl mole dosage accounts for total monomer is 0.2%-2%, at 60～70 ℃ of following copolyreaction 6-24h;
(2) aminolysis reaction: carboxylic acid anhydride unit and the aminopyridine of utilizing phenylethylene-maleic anhydride parents polymkeric substance again, or alkylamino pyridine, or alkoxy amino pyridine stirring at room aminolysis reaction 12 hours in anhydrous dimethyl sulphoxide, be warming up to 50 ℃ of reaction 2h again, the concentration of phenylethylene-maleic anhydride parents polymkeric substance is 0.2g/mL, aminopyridine, or alkylamino pyridine, or alkoxy amino pyridine and the unitary molar ratio of carboxylic acid anhydride be 50%-200%, and the aminolysis reaction resulting polymers is through ether sedimentation and the ether extrct pyridine that deaminizes repeatedly, or alkylamino pyridine, or the alkoxy amino pyridine obtains amphoteric ion polymer.
2. the amphoteric ion polymer of claim 1 method preparation is characterized in that polymkeric substance is random parents polymkeric substance, and contains the alternating polymerization segment.
3. the application method of the amphoteric ion polymer of claim 1 method preparation, it is characterized in that preparing the amphoteric ion polymer nano-micelle: with this amphoteric ion polymer is that 2-100mg/mL is dissolved in the cosolvent dimethyl sulfoxide (DMSO) of close and distant water base unit with concentration, at the uniform velocity stir the precipitation agent deionized water that progressively slowly drips hydrophobic primitive down in polymers soln, the deionized water consumption is one times of amount of dimethyl sulfoxide (DMSO) consumption; Continue at the uniform velocity to stir 2 hours after dropwising, the deionized water that disposable then adding doubles the dimethyl sulfoxide (DMSO) consumption makes micella stable; Continue to stir that osmose process displaces dimethyl sulfoxide solvent after 2 hours, thereby obtain the nano-micelle aqueous solution of this amphoteric ion polymer.
4. the nano-micelle aqueous solution of the amphoteric ion polymer of claim 3 method preparation is characterized in that hydroxy-acid group and the pyridine group in this polymkeric substance can form weak acid and weak base salt in neutral aqueous solution, sees reaction formula 2-B; And in sour environment, then form strong acid pyridinium salt and free carboxy acid's form, see reaction formula 2-A; In alkaline environment, then form the form of carboxylate salt and free pyridine, see reaction formula 2-C;
Reaction formula 2,
Promptly the gained system has pH response performance and shock-absorbing capacity after this amphoteric ion polymer nano-micelleization.
5. the amphoteric ion polymer nano-micelle aqueous solution according to claim 4 is characterized in that the pH response performance of gained amphoteric ion polymer nano-micelle and shock-absorbing capacity are ratio, initiator and the monomer molar ratio by the close and distant aqueous monomer of phenylethylene/maleic anhydride of regulating the radical polymerization system, the replacement type that reaches aminopyridine and introducing amount and adjusted.
6. the application of the described amphoteric ion polymer nano-micelle of claim 4 aqueous solution, it is characterized in that being used for drug loading release, polymer modification and chemical reaction loaded with nano micellar has to use and potential application the sixth of the twelve Earthly Branches.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880357A (en) * | 2010-07-09 | 2010-11-10 | 南京工业大学 | Polystyrene-graft-succinic carboxylic acid resin |
| CN102718976A (en) * | 2012-06-29 | 2012-10-10 | 江南大学 | Preparation method of in-situ induced hyaluronic acid micelle |
| CN101776635B (en) * | 2010-02-02 | 2013-09-18 | 江南大学 | Preparation method of molecular recognition sensor by electro-deposition |
| CN103865217A (en) * | 2014-03-14 | 2014-06-18 | 江南大学 | Polyvinyl alcohol membrane material with formaldehyde detection effect and preparation method thereof |
| CN104084088A (en) * | 2014-07-07 | 2014-10-08 | 江南大学 | Application of branched amphipathic polymer self-assembling micelle as emulsifying agent |
| WO2021078082A1 (en) * | 2019-10-22 | 2021-04-29 | 南京师范大学 | Use of zwitterion or zwitterionic polymer as ph buffer material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101776635B (en) * | 2010-02-02 | 2013-09-18 | 江南大学 | Preparation method of molecular recognition sensor by electro-deposition |
| CN101880357A (en) * | 2010-07-09 | 2010-11-10 | 南京工业大学 | Polystyrene-graft-succinic carboxylic acid resin |
| CN101880357B (en) * | 2010-07-09 | 2012-05-09 | 南京工业大学 | Polystyrene-graft-succinic carboxylic acid resin |
| CN102718976A (en) * | 2012-06-29 | 2012-10-10 | 江南大学 | Preparation method of in-situ induced hyaluronic acid micelle |
| CN102718976B (en) * | 2012-06-29 | 2017-04-26 | 江南大学 | Preparation method of in-situ induced hyaluronic acid micelle |
| CN103865217A (en) * | 2014-03-14 | 2014-06-18 | 江南大学 | Polyvinyl alcohol membrane material with formaldehyde detection effect and preparation method thereof |
| CN103865217B (en) * | 2014-03-14 | 2016-02-17 | 江南大学 | A kind of have polyvinyl alcohol mould material detecting formaldehyde effect and preparation method thereof |
| CN104084088A (en) * | 2014-07-07 | 2014-10-08 | 江南大学 | Application of branched amphipathic polymer self-assembling micelle as emulsifying agent |
| WO2021078082A1 (en) * | 2019-10-22 | 2021-04-29 | 南京师范大学 | Use of zwitterion or zwitterionic polymer as ph buffer material |
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Assignee: Wuxi Ed adhesive material Co., Ltd. Assignor: Jiangnan University Contract record no.: 2011320000957 Denomination of invention: Method for preparing amphoteric ion polymer and pH response type polymer micelle buffer solution thereof Granted publication date: 20100324 License type: Exclusive License Open date: 20080709 Record date: 20110711 |
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