CN103755867A - Preparation method for monodisperse nanometer/micrometer hydrogel microsphere - Google Patents
Preparation method for monodisperse nanometer/micrometer hydrogel microsphere Download PDFInfo
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Abstract
The invention discloses a preparation method for a monodisperse nanometer/micrometer hydrogel microsphere. The preparation method comprises the following steps: mixing comonomers with a solvent so as to obtain a mixed solution, wherein the comonomers at least comprise water-soluble allyl monomers; mechanically stirring and heating the mixed solution until the mixed solution is in a boiling state and maintaining a boiling reflux condition for a predetermined period of time; continuing stirring, adding a radical initiator under a boiling reflux temperature and carrying out precipitation in a boiling reflux state so as to form a monodisperse hydrogel microsphere; and carrying out centrifugation so as to obtain the monodisperse hydrogel microsphere. The method is applicable to preparation of the monodisperse nanometer/micrometer hydrogel microsphere by using the comonomers. According to the method, without usage of a stabilizing agent, the monodisperse microsphere which has a clean surface and does not contain any surfactant and any stabilizing agent can be prepared. The method has the characteristics of simple conditions, simple equipment, easy operation, short reaction time, a high conversion rate, usage of the nontoxic solvent and environment friendliness.
Description
Technical field
The application relates to polymeric microball material, relates in particular to a kind of dispersed nano/micron hydrogel microsphere preparation method.
Background technology
The research of polymeric microball material and application development in recent years are very rapid, due to it unique dimensions possessing and pattern, and the not available specific function of other materials, make polymer microsphere be widely used in multiple fields such as biology, chemistry, medicine, analysis, functional materials.The method of the synthetic polymer microballoon of having reported is mainly divided into letex polymerization, emulsifier-free emulsion polymerization, mini-emulsion polymerization, microemulsion, seeding polymerization, dispersion polymerization, precipitation polymerization, suspension polymerization.Diverse ways can be prepared the microballoon of different size.Emulsion polymerization is the most frequently used method for preparing microsphere, can polymerization obtain tens of microballoons to hundreds of nanometers, but because the use of emulsifying agent can damage the performance of product material.Dispersion polymerization can be prepared from nano level to the uniform microballoon of micron order size distribution, and suspension polymerization can be prepared the micron order microballoon of wide dispersion, but because the use of the dispersion agent of high level has limited the application of microballoon.
Summary of the invention
The technical problem that the application will solve is for the deficiencies in the prior art, and a kind of dispersed nano/micron hydrogel microsphere preparation method is provided.
The technical problem that the application will solve is solved by the following technical programs:
A kind of dispersed nano/micron hydrogel microsphere preparation method, comprising:
Comonomer and solvent are formed to mixing solutions, and described comonomer at least comprises hydrophilic vinyl monomer;
Mechanical stirring also heats described mixing solutions to boiling state, and make boiling reflux maintain the scheduled time;
Maintain stirring, at the temperature of boiling reflux, add radical initiator, under the state of boiling reflux, precipitation forms dispersed nano/micron hydrogel microsphere;
Centrifugation obtains described dispersed nano/micron hydrogel microsphere.
In aforesaid method, the mass percent of described comonomer and described mixing solutions is 1～10%.
In aforesaid method, described comonomer also comprises water-soluble functional vinyl monomer.
In aforesaid method, be also included in the step that adds linking agent in the described mixing solutions that described comonomer and described solvent form, the mass percent of described linking agent and described mixing solutions is 0.001～10%.
In aforesaid method, described linking agent comprises N,N methylene bis acrylamide or Ethylene glycol dimethacrylate.
In aforesaid method, described solvent comprises one or more the mixture in water, ethanol and dimethyl sulfoxide (DMSO).
In aforesaid method, described radical initiator comprises Potassium Persulphate, ammonium persulphate, benzoyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); The mass percent of described radical initiator and described comonomer is 1～10%.
In aforesaid method, described hydrophilic vinyl monomer comprises NIPA, N-caprolactam, N-n-propyl acrylamide, N, N-diethyl acrylamide, N,N methylene bis acrylamide.
In aforesaid method, described water-soluble functional vinyl monomer comprises vinylformic acid, methacrylic acid, acrylamide, hydroxyethyl methylacrylate, 4-vinylphenylboronic acid, 4-vinylphenylboronic acid pinacol ester, vinyl cyanide, NVP or 4-vinylpridine.
In aforesaid method, described churned mechanically speed is 200～400rpm, and the described scheduled time is 10～30 minutes.
Owing to having adopted above technical scheme, the beneficial effect that the application possesses is:
In the application's embodiment, comprise comonomer and solvent are formed to mixing solutions; Mechanical stirring also heats mixing solutions to boiling state, and make boiling reflux maintain the scheduled time; Add radical initiator, under the state of boiling reflux, precipitation forms single disperse water gel micro-ball; Centrifugation obtains single disperse water gel micro-ball.The application is used for using comonomer to prepare dispersed nano/micron hydrogel microsphere.The application need not use stablizer, just can prepare surface cleaning, does not contain the mono-dispersion microballoon of any tensio-active agent and stablizer.It is simple that the present invention has condition, install easy, easy handling, the reaction times is short, transformation efficiency is high, the nontoxic and eco-friendly feature of solvent.
Accompanying drawing explanation
Fig. 1 is the application's schema in one embodiment of dispersed nano/micron hydrogel microsphere preparation method;
Fig. 2: the scanning electron microscope (SEM) of poly--NIPA-altogether-acrylic hydrogel microballoon;
Fig. 3: the scanning electron microscope (SEM) of poly--N-n-propyl acrylamide-altogether-hydroxyethyl methylacrylate-altogether-4-vinylphenylboronic acid pinacol ester hydrogel microsphere.
Embodiment
Below by embodiment, by reference to the accompanying drawings the application is described in further detail.
The application uses boiling precipitation polymerization method to prepare dispersed nano/micron hydrogel microsphere.The particle diameter of Nano/micron hydrogel microsphere prepared by the application's method is to control in hundreds of nanometer in micrometer range, and by adding different functional comonomers, change the surface-functional group of hydrogel microsphere, or by the microsphere surface obtaining after polymerization is modified, can obtain single disperse water gel micro-ball of the functionalization with different surfaces characteristic.The application's the prepared functional nano/micron hydrogel microsphere of method can be put for medicament slow release, support of the catalyst, biosensor and biomolecules, as the carrier of enzyme, protein, antibody etc.
Dispersed nano/micron hydrogel microsphere particle diameter prepared by the application's method is in 100 nanometer～1 micron, monodisperse system number is 0.01～0.069, microsphere surface is clean and with different functional groups, and hydrogel microsphere is 0～10% crosslinked gel-type hydrophilic vinyl monomer homopolymer or the copolymer aquagel microballoon of vinyl monomer and other water-soluble functional vinyl monomers.Functional groups comprises carboxyl (COOH), amino (NH
2), hydroxyl (OH), boronate (B (OH)
2), ester group (COO), amide group (CONH) and itrile group (CN) etc.
As shown in Figure 1, dispersed nano/micron hydrogel microsphere preparation method of the application, its a kind of embodiment, comprises the following steps:
Step 102: comonomer and solvent are formed to mixing solutions, and wherein comonomer at least comprises hydrophilic vinyl monomer.
Hydrophilic vinyl monomer comprises NIPA (NIPAM), N-caprolactam (VCL), N-n-propyl acrylamide (NNPA), N, N-diethyl acrylamide (NDEA), N,N methylene bis acrylamide (MBA).
In step 102, the mixing solutions of hydrophilic vinyl monomer and solvent composition is added in reaction system.Solvent comprises one or more the mixture in water, ethanol and dimethyl sulfoxide (DMSO).The mass percent of comonomer and mixing solutions is 1～10%.
In one embodiment, comonomer can also comprise water-soluble functional vinyl monomer.Water-soluble functional vinyl monomer comprises the functional vinyl monomer that vinylformic acid (AA), methacrylic acid (MAA), acrylamide (AM), hydroxyethyl methylacrylate (HEMA), 4-vinylphenylboronic acid (VPBA), 4-vinylphenylboronic acid pinacol ester (VPBPE), vinyl cyanide (AN), NVP (NVP) or 4-vinylpridine etc. can be water-soluble.
In one embodiment, can also be included in the step that adds linking agent in the mixing solutions that comonomer and solvent form.Linking agent comprises N,N methylene bis acrylamide (MBA) or Ethylene glycol dimethacrylate (EGDMA), and the application's method can also be used other linking agents, and the mass percent of linking agent and comonomer is 0.001～10%.
Step 104: mechanical stirring also heats mixing solutions to boiling state, and make boiling reflux maintain the scheduled time.
Churned mechanically speed is 200～400rpm, and the scheduled time is 10～30 minutes.
Step 106: maintain stirring, at the temperature of boiling reflux, add radical initiator, precipitation forms dispersed nano/micron hydrogel microsphere under the state of boiling reflux.
Radical initiator comprises Potassium Persulphate (KPS), ammonium persulphate (APS), benzoyl peroxide (BPO), Diisopropyl azodicarboxylate (AIBN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) etc.The mass percent of radical initiator and comonomer is 1～10%.
Step 108: centrifugation obtains dispersed nano/micron hydrogel microsphere.Centrifugation obtains, after dispersed nano/micron hydrogel microsphere, can cleaning.In the present embodiment, specifically can make one or more the mixture in water, ethanol and dimethyl sulfoxide (DMSO) clean.
Example one:
One with prolong, churned mechanically 250 milliliters of there-necked flasks in, add 1.2 grams of NIPAs (NIPAM, 1.80 wt%), 60 ml waters.Reacting by heating system, treats that system boiling reflux is about 30 minutes, in system, adds 5 milliliters of aqueous solution that contain 0.042 gram of Potassium Persulphate (KPS, 3.38 wt%), and system is muddy oyster white by the state-transition of transparent and homogeneous.Hydrogel microsphere is precipitated out gradually from reaction system, under fixing mechanical stirring speed and temperature of reaction, continues reaction and after 4 hours, finishes reaction, and more than 32 ℃, centrifugation obtains hydrogel microsphere, then uses 40 ℃ of hot water wash hydrogel microspheres 3 times.
Example two:
One with prolong, churned mechanically 250 milliliters of there-necked flasks in, add 1.5 grams of NIPAs (NIPAM, 1.18 wt%), 0.5g vinylformic acid (AA, 0.39 wt%), 0.0333 gram of N, N DMAA (MBA, 1.6 wt%) and 120 ml waters.Reacting by heating system, treats that system boiling reflux is about 30 minutes, in system, adds 5 milliliters of aqueous solution that contain 0.083 gram of Potassium Persulphate (KPS, 4.15 wt%), and system is muddy oyster white by the state-transition of transparent and homogeneous.Hydrogel microsphere is precipitated out gradually from reaction system, under fixing mechanical stirring speed and temperature of reaction, continues reaction and after 4 hours, finishes reaction, and centrifugation obtains hydrogel microsphere, then washes hydrogel microsphere with water 3 times.Poly--NIPAM-is common-AA hydrogel microsphere scanning electron microscope (SEM) as shown in Figure 2, microspherulite diameter is 183 nanometers, monodisperse system number is 0.024.
Example three:
One with prolong, churned mechanically 250 milliliters of there-necked flasks in, add 1.0 grams of N-n-propyl acrylamide (NNPA, 1.49 wt%), 0.5 gram of hydroxyethyl methylacrylate (HEMA, 0.75 wt%), 0.5 gram of 4-vinylphenylboronic acid pinacol ester (VPBPE, 0.75 wt%), 0.0173 gram of N, N DMAA (MBA, 0.90 wt%) and 55 ml waters and 5 milliliters of ethanol.Reacting by heating system, treats that system boiling reflux is about 30 minutes, in system, adds 5 milliliters of aqueous solution that contain 0.042 gram of Potassium Persulphate (KPS, 2.21 wt%), and system is muddy oyster white by the state-transition of transparent and homogeneous.Hydrogel microsphere is precipitated out gradually from reaction system, under fixing mechanical stirring speed and temperature of reaction, continues reaction and after 4 hours, finishes reaction, and centrifugation obtains hydrogel microsphere, then washes hydrogel microsphere with water 3 times.Poly--NNPA-is common-HEMA-is common-VPBPE hydrogel microsphere scanning electron microscope (SEM) as shown in Figure 3, microspherulite diameter is 143 nanometers, monodisperse system number is 0.039.
Above content is the further description of the application being done in conjunction with concrete embodiment, can not assert that the application's concrete enforcement is confined to these explanations.For the application person of an ordinary skill in the technical field, not departing under the prerequisite of the application's design, can also make some simple deduction or replace.
Claims (10)
1. dispersed nano/micron hydrogel microsphere preparation method, is characterized in that, comprising:
Comonomer and solvent are formed to mixing solutions, and described comonomer at least comprises hydrophilic vinyl monomer;
Mechanical stirring also heats described mixing solutions to boiling state, and make boiling reflux maintain the scheduled time;
Maintain stirring, at the temperature of boiling reflux, add radical initiator, under the state of boiling reflux, precipitation forms dispersed nano/micron hydrogel microsphere;
Centrifugation obtains described dispersed nano/micron hydrogel microsphere.
2. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, is characterized in that, the mass percent of described comonomer and described mixing solutions is 1～10%.
3. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, is characterized in that, described comonomer also comprises water-soluble functional vinyl monomer.
4. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 3, it is characterized in that, also be included in the step that adds linking agent in the described mixing solutions that described comonomer and described solvent form, the mass percent of described linking agent and described mixing solutions is 0.001～10%.
5. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, is characterized in that, described linking agent comprises N,N methylene bis acrylamide or Ethylene glycol dimethacrylate.
6. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, is characterized in that, described solvent comprises one or more the mixture in water, ethanol and dimethyl sulfoxide (DMSO).
7. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, is characterized in that, described radical initiator comprises Potassium Persulphate, ammonium persulphate, benzoyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); The mass percent of described radical initiator and described comonomer is 1～10%.
8. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, it is characterized in that, described hydrophilic vinyl monomer comprises NIPA, N-caprolactam, N-n-propyl acrylamide (NNPA), N, N-diethyl acrylamide, N,N methylene bis acrylamide.
9. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, it is characterized in that, described water-soluble functional vinyl monomer comprises vinylformic acid, methacrylic acid, acrylamide, hydroxyethyl methylacrylate, 4-vinylphenylboronic acid, 4-vinylphenylboronic acid pinacol ester, vinyl cyanide, NVP or 4-vinylpridine.
10. dispersed nano/micron hydrogel microsphere preparation method as claimed in claim 1, is characterized in that, described churned mechanically speed is 200～400rpm, and the described scheduled time is 10～30 minutes.
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| CN107254018A (en) * | 2017-07-24 | 2017-10-17 | 苏州大学 | A kind of degradable monodisperse polymer micro-sphere and preparation method and application |
| CN107903560A (en) * | 2017-11-23 | 2018-04-13 | 中国石油大学(北京) | A kind of polyacrylamide/microballoon plural gel and preparation method thereof |
| CN109251272A (en) * | 2018-08-15 | 2019-01-22 | 中国科学院兰州化学物理研究所 | A kind of method that bionical self-assembling polymers microballoon is used for anti-fog coating |
| CN110050846A (en) * | 2019-04-01 | 2019-07-26 | 浙江远大生物科技有限公司 | A kind of unsaturated fatty-acid compositions and its spray drying preparation of polymer embedding |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107254018A (en) * | 2017-07-24 | 2017-10-17 | 苏州大学 | A kind of degradable monodisperse polymer micro-sphere and preparation method and application |
| CN107903560A (en) * | 2017-11-23 | 2018-04-13 | 中国石油大学(北京) | A kind of polyacrylamide/microballoon plural gel and preparation method thereof |
| CN107903560B (en) * | 2017-11-23 | 2019-05-21 | 中国石油大学(北京) | A kind of polyacrylamide/microballoon plural gel and preparation method thereof |
| CN109251272A (en) * | 2018-08-15 | 2019-01-22 | 中国科学院兰州化学物理研究所 | A kind of method that bionical self-assembling polymers microballoon is used for anti-fog coating |
| CN109251272B (en) * | 2018-08-15 | 2020-11-03 | 中国科学院兰州化学物理研究所 | Method for applying bionic self-assembled polymer microspheres to anti-fog coating |
| CN110050846A (en) * | 2019-04-01 | 2019-07-26 | 浙江远大生物科技有限公司 | A kind of unsaturated fatty-acid compositions and its spray drying preparation of polymer embedding |
| CN110050846B (en) * | 2019-04-01 | 2020-05-19 | 浙江远大生物科技有限公司 | Polymer-embedded unsaturated fatty acid composition and spray drying preparation method thereof |
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