CN105218747B - A kind of preparation method of Poly (ACA co MAA co EDMA) microballoon - Google Patents
A kind of preparation method of Poly (ACA co MAA co EDMA) microballoon Download PDFInfo
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- CN105218747B CN105218747B CN201510685956.4A CN201510685956A CN105218747B CN 105218747 B CN105218747 B CN 105218747B CN 201510685956 A CN201510685956 A CN 201510685956A CN 105218747 B CN105218747 B CN 105218747B
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- microballoon
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Abstract
The present invention relates to a kind of method for preparing monoxone propylene (α methacrylic acids) ethylene glycol dimethacrylate polymer microballoon using precipitation polymerization method.It regard the monoxone propylene necessarily matched and α methacrylic acids as function monomer; ethylene glycol dimethacrylate (EDMA) is used as crosslinking agent; azodiisobutyronitrile (AIBN) is initiator; using acetonitrile and normal propyl alcohol as dicyandiamide solution; Raolical polymerizable is carried out at certain temperature and speed conditions, the polymer microballoon with two kinds of functional groups of chloracetyl and carboxyl is prepared.This method prepares simple, easy to operate, the microballoon regular shape of preparation, grain size narrowly distributing.
Description
Technical field
The invention belongs to polymer microsphere production technical field, it is related to one kind and chloroethene acid propylene is prepared with precipitation polymerization method
The side of ester-(α-methacrylic acid)-ethylene glycol dimethacrylate polymer poly (ACA-co-MAA-co-EDMA) microballoon
Method.
Background technology
Polymer microsphere (Polymeric microspheres) is the widely used separation material of a class, in industrial wastewater
Processing, ultra-pure water preparation, catalytic reaction, hydrometallurgy, Separation of Natural Products are extracted, separation and concentration, the chromatogram of albumen and polypeptide
The fields such as analysis, blood purification, food industry and pharmacy are widely used.The preparation method of polymer microsphere is various, including heavy
Form sediment polymerization, dispersin polymerization, emulsion polymerization, template, seed swelling etc..Polymer microsphere structural property prepared by distinct methods is not
Together, the diameter of microballoon is from nanometer to grade, and particle diameter distribution is single dispersing or polydispersion, and pore structure is non-porous or porous, property
Matter is hydrophobic or hydrophilic.In the preparation method of polymer microsphere, precipitation polymerization method simple and convenient the most, course of reaction
For：The homogeneous system being made up of polymerized monomer, initiator, stabilizer and decentralized medium starts, and initiator is produced freely after heating
Base, polymerized monomer gradually aggregates into chain polymer, and decentralized medium is the poor solvent of these polymer molecules, the polymerization of generation
Thing will from decentralized medium Precipitation, cleaned, filtering, drying can secure satisfactory grades sub- microballoon.Currently, methacrylic
Prepared by microballoon tended to be ripe, but the preparation research containing halogen functional group's microballoon is less, prepared by monoxone propylene esters microballoon
Have not been reported.
The present invention has developed the method that one kind prepares poly (ACA-co-MAA-co-EDMA) microballoon, and this method prepares letter
It is single, easy to operate, the microballoon regular shape of preparation, grain size narrowly distributing.
The content of the invention
The present invention is prepared first using simple precipitation polymerization method contains two kinds of function bases of chloracetyl and carboxyl simultaneously
Poly (ACA-co-MAA-co-EDMA) microballoon of group, this method is simple, and thus obtained microsphere regular shape, particle size distribution range is narrow.
The technical solution adopted by the present invention comprises the following steps：
The first step, by two kinds of function monomer monoxone propylene ACA, methacrylate MAA according to 1:1-1:3 volume
Than being dissolved in solvent, crosslinking agent ethylene glycol dimethacrylate EDMA and initiator azodiisobutyronitrile AIBN, room are added
The lower concussion mixing of temperature occurs to obtain colourless transparent solution after Raolical polymerizable, and function monomer ACA is the introducing of functional group
Reagent, the pattern and size of function monomer MAA auxiliary control microballoons；The solvent is the binary system of acetonitrile and normal propyl alcohol, its
Volume ratio is 3:1-9:1；The consumption of the crosslinking agent EDMA is 0.5-2 times of two kinds of total consumptions of function monomer, the initiator
AIBN consumption is the 0.5-1% of two kinds of function monomer gross masses.
Second step, colourless transparent solution is carried out ultrasonically treated, makes reactant well mixed and degasification, after sonic oscillation
For homogeneous colourless transparent solution.
3rd step, is passed through nitrogen deoxygenation, and colourless transparent solution is placed in 60 DEG C of -80 DEG C of oil baths with 60-100r/min's
Tachyphylaxis 2-5h obtains white suspension；
4th step, after reaction terminates, will be cleaned after white suspension suction filtration with methanol or ethanol, and poly is obtained after drying
(ACA-co-MAA-co-EDMA) microballoon；The microballoon regular shape prepared, narrow size distribution, size 0.5 μm -3.0 μm it
Between.
The present invention prepares poly (ACA-co-MAA-co-EDMA) microballoon, processing step first using precipitation polymerization process
Simply, few using equipment, the microballoon can carry out later stage derivative modification, for SPE and chromatographic isolation filler.
Brief description of the drawings
Fig. 1 is the stereoscan photograph for the poly (ACA-co-MAA-co-EDMA) that embodiment 5 is obtained.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.
Embodiment 1：
The first step, the MAA by volume for 0.32mL ACA and 0.48mL is added to volume ratio respectively 14mL:6mL、
16mL:4mL、18mL:2mL acetonitrile and the in the mixed solvent of normal propyl alcohol, add crosslinking agent EDMA 0.8mL and initiator A IBN
0.01g, at room temperature concussion is mixed to get colourless transparent solution；
Second step, the volumetric flask that will be equipped with colourless transparent solution carries out ultrasonic vibration 10min；
3rd step, is passed through nitrogen connection condenser pipe 80r/min in 70 DEG C of oil bath and carries out obtaining white outstanding after reaction 2h
Turbid liquid；
4th step, reaction washs white suspension with absolute ethyl alcohol after terminating, and poly (ACA-co- are obtained after drying
MAA-co-EDMA) microballoon；Microsphere Size is 0.5-1.0 μm.
Embodiment 2：
The first step, 0.2mL is pressed by ACA and MAA respectively:0.6mL、0.32mL:0.48mL、0.4mL:0.4mL is added to
In 18mL acetonitriles and 2mL normal propyl alcohols, crosslinking agent EDMA 0.8mL and initiator A IBN 0.01g are added, concussion at room temperature is mixed
To colourless transparent solution；
Second step, the volumetric flask that will be equipped with colourless transparent solution carries out ultrasonic vibration 15min；
3rd step, is passed through nitrogen and connects condenser pipe in 70 DEG C of oil bath to obtain white after 80r/min progress reactions 2.5h
Color suspension；
White suspension is cleaned 5 times and then carried out suction filtration by the 4th step, reaction after terminating with methanol, and poly is obtained after drying
(ACA-co-MAA-co-EDMA) microballoon.Microsphere Size is 1.0-1.5 μm.
Embodiment 3：
The first step, the MAA for by volume being respectively 0.32mL ACA and 0.48mL is added to 18mL acetonitriles and 2mL normal propyl alcohols
In, initiator A IBN 0.01g, the volume for adding crosslinking agent EDMA is respectively 0.87mL, 0.83mL, 0.8mL, is mixed with ACA, MAA
Zoarium product ratio respectively 12：10、12:11、12:12, concussion at room temperature is mixed to get colourless transparent solution；
Second step, the volumetric flask that will be equipped with colourless transparent solution carries out ultrasonic vibration 20min；
3rd step, is passed through nitrogen and connects condenser pipe in 70 DEG C of oil bath to obtain white after 80r/min progress reactions 5h
Suspension；
4th step, reaction is obtained after terminating by white suspension with washes of absolute alcohol 3 times and then after carrying out suction filtration, drying
Poly (ACA-co-MAA-co-EDMA) microballoon.Microsphere Size is 1.2-2.2 μm.
Embodiment 4：
The first step, the MAA for by volume being respectively 0.32mL ACA and 0.48mL is added to 18mL acetonitriles and 2mL normal propyl alcohols
In, crosslinking agent EDMA 0.8mL and initiator A IBN 0.01g are added, concussion at room temperature is mixed to get colourless transparent solution；
Second step, the volumetric flask that will be equipped with colourless transparent solution carries out ultrasonic vibration 15min；
3rd step, is passed through nitrogen connection condenser pipe and carries out reaction 3h in 70 DEG C of oil bath, rotating speed is respectively 60,80,
100r/min；
Suction filtration is cleaned 3 times and then carried out in 4th step, reaction with methanol after terminating, poly (ACA-co- are just obtained after drying
MAA-co-EDMA) microballoon.Microsphere Size is 1.5-2.2 μm.
Embodiment 5：
The first step, the MAA for by volume being respectively 0.32mL ACA and 0.48mL is added to 18mL acetonitriles and 2mL normal propyl alcohols
In, crosslinking agent EDMA 0.8mL and initiator A IBN 0.01g are added, concussion at room temperature is mixed to get colourless transparent solution；
Second step, the volumetric flask that will be equipped with colourless transparent solution carries out ultrasonic vibration 10min；
3rd step, is passed through nitrogen connection condenser pipe and is carrying out reaction 2h in 60 DEG C, 70 DEG C, 80 DEG C of oil bath respectively, turn
Speed is 90r/min；
Then 4th step, reaction carries out suction filtration after terminating with washes of absolute alcohol 3 times, and poly (ACA- are just obtained after drying
Co-MAA-co-EDMA) microballoon.Microsphere Size is 2.0-3.0 μm.
Claims (3)
1. a kind of preparation method of Poly (ACA-co-MAA-co-EDMA) microballoon, it is characterised in that comprise the following steps：
The first step, by two kinds of function monomer monoxone propylene ACA, methacrylate MAA according to 1:1-1:3 volume ratio is molten
In solvent, crosslinking agent ethylene glycol dimethacrylate EDMA and initiator azodiisobutyronitrile AIBN, room temperature concussion are added
It is mixed to get colourless transparent solution；
Second step, colourless transparent solution is carried out it is ultrasonically treated, it is ultrasonically treated after be homogeneous colourless transparent solution；
Colourless transparent solution is reacted and obtains white suspension by the 3rd step, nitrogen deoxygenation under 60-100r/min rotating speed；
4th step, reaction will be washed after terminating after white suspension suction filtration with detergent, and poly (ACA-co-MAA- are obtained after drying
Co-EDMA) microballoon；
The solvent is the binary system of acetonitrile and normal propyl alcohol, and its volume ratio is 3:1-9:1；
The consumption of the crosslinking agent ethylene glycol dimethacrylate is 0.5-2 times of two kinds of total consumptions of function monomer, described to draw
Send out 0.5-1% of the consumption of agent azodiisobutyronitrile for two kinds of function monomer gross masses.
2. a kind of preparation method of Poly (ACA-co-MAA-co-EDMA) microballoon as claimed in claim 1, it is characterised in that：
Reaction temperature is 60 DEG C -80 DEG C in 3rd step, and the reaction time is 2-5h.
3. a kind of preparation method of Poly (ACA-co-MAA-co-EDMA) microballoon as claimed in claim 1, it is characterised in that：
The detergent is methanol or absolute ethyl alcohol.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3624058A (en) * | 1968-05-06 | 1971-11-30 | Goodrich Co B F | Polymers of vulcanizable alkyl esters of acrylic acid and allyl chloroacetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1036068C (en) * | 1991-03-22 | 1997-10-08 | 罗姆和哈斯公司 | Method of preparing surface-porous crosslinked copolymer beads |
| KR101344854B1 (en) * | 2006-02-10 | 2013-12-31 | 아크조 노벨 엔.브이. | Microspheres |
| CN101591412B (en) * | 2009-06-03 | 2011-05-18 | 中国农业科学院农业质量标准与检测技术研究所 | Method for preparing chloramphenicol molecularly imprinted polymeric microspheres |
| CN102731701A (en) * | 2012-04-23 | 2012-10-17 | 苏州异导光电材料科技有限公司 | Method for preparing mono-disperse polymer functional microspheres with photochemical method |
| CN103554376B (en) * | 2013-10-22 | 2016-01-20 | 上海华明高技术（集团）有限公司 | The preparation method of monodisperse cross-linked poly (methyl methacrylate) micro-sphere |
| CN104829777A (en) * | 2015-05-14 | 2015-08-12 | 扬州三涧科贸有限公司 | Preparation method of micron-sized highly-crosslinked polymethyl methacrylate (PMMA) microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3624058A (en) * | 1968-05-06 | 1971-11-30 | Goodrich Co B F | Polymers of vulcanizable alkyl esters of acrylic acid and allyl chloroacetate |
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