CN102989401A - Backflow sediment polymerization preparation method for polymer gel micro-sphere - Google Patents
Backflow sediment polymerization preparation method for polymer gel micro-sphere Download PDFInfo
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- CN102989401A CN102989401A CN2012105109482A CN201210510948A CN102989401A CN 102989401 A CN102989401 A CN 102989401A CN 2012105109482 A CN2012105109482 A CN 2012105109482A CN 201210510948 A CN201210510948 A CN 201210510948A CN 102989401 A CN102989401 A CN 102989401A
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Abstract
The invention belongs to the field of a novel material and biotechnology and particularly relates to a backflow sediment polymerization preparation method for a polymer gel micro-sphere. A non-dispersion hydrophilic functional micro-sphere is prepared by an improved distillation sedimentation technology, wherein a distillation step is changed into a backflow step, and magnetic agitation is additionally conducted; and in a reaction process, a monomer is additionally dripped so as to increase the diameter of the micro-sphere. The backflow sediment polymerization preparation method disclosed by the invention keeps the advantages that the consumption time of the distillation sedimentation technology is short, an emulsifying agent or a stabilizing agent does not need to be additionally added, the reaction is moderate, the control is easy, and the like; a device is simplified; a gel instability phenomenon in a distillation sedimentation process is reduced; and the controllability and the operability of the reaction are improved. The size of the grain diameter of the prepared polymer gel micro-sphere is uniform; the grain diameter and the yield can be regulated and controlled through changing reaction time, monomer concentration, content of a cross-linking agent and other conditions; and the backflow sediment polymerization preparation method has a good application prospect.
Description
Technical field
The invention belongs to new material and biological technical field, be specifically related to a kind of preparation method of polymer gel microsphere.
Background technology
But owing to have evenly regular form and reactive functionality, single divergent function microballoon has a wide range of applications at aspects such as chromatographic isolation, coating additive, bio-carrier and medicament slow releases.Owing to preparation method's restriction, the preparation of monodisperse hydrophilicity polymer gel microsphere is the focus that people pay close attention to always at present.
There are in the world at present many seminars to adopt the method for distillation precipitation to prepare polymer gel microsphere, need not stir by simple distillation with monomer, solvent and initator, so that polymer is precipitated out from solvent in the process of evaporating solvent, reaction system is heterogeneous by all being phase-changed into, and trigger monomer is assembled nucleation and progressively increased the formation mono-dispersion microballoon.Microballoon profile and surface that this method polymerization obtains are neatly regular, and homogeneity is higher.
The advantage of the distillation precipitation method is that course of reaction is simple, weak point consuming time (being generally 1-2h), and control need not add stabilizing agent or surfactant in the polymerization process easily, and microsphere surface is clean and tidy.Yet need distillation in the course of reaction so that reaction unit is complicated, the process that steams solvent also produces to be polluted and unnecessary waste, does not meet the principle of Green Chemistry; In addition, do not add stirring in the system and produce easily the colloid unstability so that react inhomogeneous, the solvent minimizing may cause monomer conversion and microspherulite diameter to be restricted so that chamber wall is stained with than heteropolymer in still-process.
Therefore, the distillation sedimentation is improved, it is very necessary to develop new preparation polymer gel microsphere method.
Summary of the invention
The object of the invention is to propose a kind of new method for preparing polymer gel microsphere, the precipitation polymerization process that namely refluxes is to overcome existing preparation method's deficiency.
The method for preparing polymer gel microsphere that the present invention proposes is to change the distilation steps in the distillation sedimentation into reflow step, adds and stirs, and can additionally drip monomer increase microspherulite diameter in course of reaction.Concrete steps are as follows:
Get two mouthfuls of flasks, polymerization single polymerization monomer, crosslinking agent, initator are scattered in the solvent, a bottleneck is installed spherical condensation tube, another bottle sealing therein;
Whole device is immersed in the oil bath, opens and stir, be warming up to 60-120 ℃ after constant temperature reflux, after the beginning that refluxes in the very fast system white casse appears, stop behind the reaction 0.5-4h;
White liquid in the flask is poured out, and supernatant liquor is outwelled in centrifugation (for example can the centrifugal 5min of 12000rpm), adds again centrifugation of the ultrasonic dispersion of absolute ethyl alcohol, so repeatedly cleans three times.
In course of reaction, as required, also can drip polymerization single polymerization monomer, namely be added dropwise to polymerization single polymerization monomer from the bottleneck that seals with certain speed with syringe pump.
Among the present invention, described polymerization single polymerization monomer is methacrylic acid (MAA), acrylic acid (AA), polyethylene glycol (PEG, Mn=300,475,526,600,800,900,1000), N-2-hydroxypropyl monomethyl acrylamide (HPMA), hydroxyethyl meth acrylate (HEMA), vinylpyridine (Vinylpyridine), vinyl imidazole (Vinylimidazole), NVP (
N-VinyPyrrolidone), the monomer such as N-ethene caprolactam (VCL), NIPA (NIPAM), can homopolymerization, perhaps between them with the various combination copolymerization.
Among the present invention, described crosslinking agent is divinylbenzene (DVB), N, N
-Methylene-bisacrylamide (MBA), GDMA (EGDMA), or N, two (acryloyl) cystamines (BACy) of N'-etc.
Among the present invention, described initator is azodiisobutyronitrile (AIBN), AMBN (AMBN), ABVN (ADVN) or dibenzoyl peroxide (BPO) etc.
Among the present invention, described solvent is single solvent or mixed solvent.Single solvent is ethanol, acetonitrile, water, oxolane, methyl iso-butyl ketone (MIBK) or toluene; Mixed solvent is acetonitrile-ethanol, acetonitrile-oxolane, acetonitrile-water, the ethanol-toluene of different proportion, the composition of methyl iso-butyl ketone (MIBK)-acetonitrile.
Among the present invention, polymeric reaction temperature is 60-120
oC; Reaction time is 0.5-4h.
Among the present invention, the concentration of polymerization reaction system (being the concentration sum of hydrophilic vinyl polymerization monomer and crosslinking agent) is that 0.01 wt % is between the 30wt%.
Among the present invention, the ratio of the consumption of crosslinking agent and crosslinking agent and vinyl polymerization monomer total amount at 5wt% between the 60wt%.
The prepared polymer gel microsphere particle diameter of the present invention be 100nm to 3 μ m, the microballoon yield is 15% to 65%.
Behind the extra dropping monomer, the particle diameter of microballoon increases to 100nm to 500nm in the course of reaction of the present invention.
Backflow precipitation polymerization technology kept distillation sedimentation weak point consuming time, need not to add emulsifying agent or stabilizing agent, reaction temperature and further simplified device on the basis of the advantages such as control easily, avoided solvent contamination, reduced the wall sticking phenomenon in the distillation precipitation process, and because can change more reaction conditions (such as the reaction time, additionally drip monomer etc.) thus improved the controllability of reaction.
Description of drawings
The SEM photo of Fig. 1, PMAA/DVB polymer gel microsphere.
The SEM photo of Fig. 2, PHEMA/DVB polymer gel microsphere.
The TEM photo of Fig. 3, PMMA/MBA polymer gel microsphere.
The SEM photo of Fig. 4, PMAA/DVB polymer gel microsphere: drip the SEM photo that monomer affects the microballoon form: (a) 2h; (b) 4h.
The TEM photo of Fig. 5, PMAA/BACy polymer gel microsphere.
The specific embodiment
Embodiment 1: diameter is 700nm, and the degree of cross linking is the preparation of 37.78% PMAA/DVB polymer gel microsphere.
With 1.212g (1.2mL) MAA, 0.736g(0.8mL) DVB, 0.03896gAIBN (amount of initiator is the 2wt% of monomer total amount) be dissolved in 40mL acetonitrile/oxolane (4:1, v), constant temperature refluxes after being warming up to 90 ℃, white casse occurs in the very fast system after the backflow beginning, stop behind the reaction 2h.White liquid in the flask is poured out, and the centrifugal 5min of 12000rpm outwells supernatant liquor, adds again centrifugation of the ultrasonic dispersion of absolute ethyl alcohol, so repeatedly cleans three times.The SEM photo of the polymer gel microsphere for preparing is seen Fig. 1.
Embodiment 2: diameter is 1.5 μ m, and the degree of cross linking is the preparation of 36.37% PHEMA/DVB polymer gel microsphere.
With 1.2876g (1.2mL) HEMA, 0.736g(0.8mL) DVB, 0.04047g AIBN (amount of initiator is the 2wt% of monomer total amount) be dissolved in the 40mL acetonitrile, constant temperature refluxes after being warming up to 90 ℃, white casse occurs in the very fast system after the backflow beginning, stop behind the reaction 2h.White liquid in the flask is poured out, with the centrifugal 5min of 12000rpm, supernatant liquor is outwelled, add again centrifugation of the ultrasonic dispersion of absolute ethyl alcohol, so repeatedly clean three times.The SEM photo of the polymer gel microsphere for preparing is seen Fig. 2.
Embodiment 3: diameter is 320nm, and the degree of cross linking is the preparation of 20% PMMA/MBA polymer gel microsphere.
1.000g MMA, 0.250g MBA, 25mg AIBN (amount of initiator is the 2wt% of monomer total amount) are dissolved in the 40mL acetonitrile, be warming up to 90 ℃ after constant temperature reflux, after the beginning that refluxes in the very fast system white casse appears, stop behind the reaction 2h.White liquid in the flask is poured out, with the centrifugal 5min of 12000rpm, supernatant liquor is outwelled, add again centrifugation of the ultrasonic dispersion of absolute ethyl alcohol, so repeatedly clean three times.The TEM photo of the polymer gel microsphere for preparing is seen Fig. 3.
Embodiment 4: diameter is 1.2 μ m, and the degree of cross linking is the preparation (by extra dropping comonomer) of 37.78% PMAA/DVB polymer gel microsphere.
With 1.212g (1.2mL) MAA, 0.736g(0.8mL) DVB, 0.03896g AIBN (amount of initiator is the 2wt% of monomer total amount) be dissolved in the 40mL acetonitrile, constant temperature refluxes after being warming up to 90 ℃, white casse occurs in the very fast system after the backflow beginning, the speed with 2mL/h is added dropwise to the 2mL comonomer (V identical with the raw material proportioning after the sampling when 2h
MAA/ V
DVB=3/2), reacts again end in a hour (total 4h consuming time) after dripping.White liquid in the flask is poured out, with the centrifugal 5min of 12000rpm, supernatant liquor is outwelled, add again centrifugation of the ultrasonic dispersion of absolute ethyl alcohol, so repeatedly clean three times.The SEM photo of the polymer gel microsphere for preparing is seen Fig. 4.
Embodiment 5: diameter is 150nm, and the degree of cross linking is the preparation of 20% PMAA/BACy polymer gel microsphere.
160mgMAA, 40mgBACy, 4mgAMBN (amount of initiator is the 2wt% of monomer total amount) are dissolved in the 20mL acetonitrile, be warming up to 100 ℃ after constant temperature reflux, after the beginning that refluxes in the very fast system white casse appears, stop behind the reaction 2h.White liquid in the flask is poured out, with the centrifugal 5min of 12000rpm, supernatant liquor is outwelled, add again centrifugation of the ultrasonic dispersion of absolute ethyl alcohol, so repeatedly clean three times.The TEM photo of the polymer gel microsphere for preparing is seen Fig. 5.
Claims (7)
1. the preparation method of a polymer gel microsphere is characterized in that: adopt backflow precipitation polymerization technology, concrete steps are as follows:
Get two mouthfuls of flasks, polymerization single polymerization monomer, crosslinking agent, initator are scattered in the solvent, a bottleneck is installed spherical condensation tube, another bottle sealing therein;
Whole device is immersed in the oil bath, opens and stir, be warming up to 60-120 ℃ after constant temperature reflux, after the beginning that refluxes in the system white casse appears, stop behind the reaction 0.5-4h;
White liquid in the flask is poured out, and supernatant liquor is outwelled in centrifugation, adds again centrifugation of the ultrasonic dispersion of absolute ethyl alcohol, so repeatedly cleans three times.
2. the preparation method of polymer gel microsphere according to claim 1 is characterized in that also dripping comonomer in course of reaction.
3. the preparation method of polymer gel microsphere according to claim 1 and 2 is characterized in that:
Described polymerization single polymerization monomer is methacrylic acid, acrylic acid, polyethylene glycol, N-2-hydroxypropyl monomethyl acrylamide, hydroxyethyl meth acrylate, vinylpyridine, vinyl imidazole, NVP, N-ethene caprolactam, NIPA, perhaps homopolymerization, or between them with the various combination copolymerization;
Described crosslinking agent is divinylbenzene, N, N
-Methylene-bisacrylamide, GDMA or N, two (acryloyl) cystamines of N'-;
Described initator is azodiisobutyronitrile, AMBN, ABVN or dibenzoyl peroxide;
Described solvent is single solvent or mixed solvent, and wherein, single solvent is ethanol, acetonitrile, water, oxolane, methyl iso-butyl ketone (MIBK) or toluene; Mixed solvent is the composition of acetonitrile and ethanol, acetonitrile and oxolane, acetonitrile and water, ethanol and toluene, methyl iso-butyl ketone (MIBK) and acetonitrile.
4. the preparation method of polymer gel microsphere according to claim 1 and 2 is characterized in that the concentration of the concentration sum of hydrophilic polymeric monomer and crosslinking agent in the described polymerization reaction system is that 0.01 wt % is between the 30wt%.
5. the preparation method of polymer gel microsphere according to claim 1 and 2, the ratio that it is characterized in that the consumption of described crosslinking agent and crosslinking agent and vinyl polymerization monomer total amount at 5wt% between the 60wt%.
6. the preparation method of polymer gel microsphere according to claim 1 is characterized in that described polymer gel microsphere particle diameter between 100nm-3 μ m, and the microballoon yield is between 15% to 65%.
7. the preparation method of polymer gel microsphere according to claim 2, it is characterized in that described polymer gel microsphere particle diameter at 100nm between the 500nm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755867A (en) * | 2013-12-12 | 2014-04-30 | 中国科学院深圳先进技术研究院 | Preparation method for monodisperse nanometer/micrometer hydrogel microsphere |
| CN106883340A (en) * | 2017-02-28 | 2017-06-23 | 北京科技大学 | A kind of preparation method and applications of triple responsive nano gels |
| CN107297222A (en) * | 2017-06-14 | 2017-10-27 | 东南大学 | A kind of preparation of poly ion liquid solid acid catalyst and its application process |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN110590996A (en) * | 2019-10-14 | 2019-12-20 | 湖南工学院 | Reflux precipitation polymerization preparation method and application of sulfonic group-containing polymer microspheres |
| CN110713563A (en) * | 2019-10-14 | 2020-01-21 | 湖南工学院 | Method for preparing fluorescent polymer microspheres by utilizing reflux precipitation polymerization and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101850218A (en) * | 2010-02-09 | 2010-10-06 | 厦门大学 | Preparation method of QAS polymer anion exchange membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101850218A (en) * | 2010-02-09 | 2010-10-06 | 厦门大学 | Preparation method of QAS polymer anion exchange membrane |
Non-Patent Citations (1)
| Title |
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| KAIGUANG YANG ET AL.: "One-Pot Synthesis of Hydrophilic Molecularly Imprinted Nanoparticles", 《MACROMOLECULES》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755867A (en) * | 2013-12-12 | 2014-04-30 | 中国科学院深圳先进技术研究院 | Preparation method for monodisperse nanometer/micrometer hydrogel microsphere |
| CN106883340A (en) * | 2017-02-28 | 2017-06-23 | 北京科技大学 | A kind of preparation method and applications of triple responsive nano gels |
| CN106883340B (en) * | 2017-02-28 | 2019-08-06 | 北京科技大学 | A kind of preparation method and applications of triple responsive nano gels |
| CN107297222A (en) * | 2017-06-14 | 2017-10-27 | 东南大学 | A kind of preparation of poly ion liquid solid acid catalyst and its application process |
| CN107297222B (en) * | 2017-06-14 | 2020-03-31 | 东南大学 | Preparation and application method of polyion liquid solid acid catalyst |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN110590996A (en) * | 2019-10-14 | 2019-12-20 | 湖南工学院 | Reflux precipitation polymerization preparation method and application of sulfonic group-containing polymer microspheres |
| CN110713563A (en) * | 2019-10-14 | 2020-01-21 | 湖南工学院 | Method for preparing fluorescent polymer microspheres by utilizing reflux precipitation polymerization and application |
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Application publication date: 20130327 |