CN105218747A - 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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- CN105218747A CN105218747A CN201510685956.4A CN201510685956A CN105218747A CN 105218747 A CN105218747 A CN 105218747A CN 201510685956 A CN201510685956 A CN 201510685956A CN 105218747 A CN105218747 A CN 105218747A
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Abstract
The present invention relates to one utilizes precipitation polymerization method to prepare the method for Mono Chloro Acetic Acid propylene-(α-methacrylic acid)-ethylene glycol dimethacrylate polymer microballoon.Using the Mono Chloro Acetic Acid propylene of certain proportioning and α-methacrylic acid as function monomer; ethylene glycol dimethacrylate (EDMA) is as linking agent; Diisopropyl azodicarboxylate (AIBN) is initiator; with acetonitrile and n-propyl alcohol for solvent system; at certain temperature and speed conditions, carry out Raolical polymerizable, prepare the polymer microballoon with chloracetyl and carboxyl two kinds of functional groups.The method preparation is 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, relate to the method that one precipitation polymerization method prepares Mono Chloro Acetic Acid propylene-(α-methacrylic acid)-ethylene glycol dimethacrylate polymkeric substance poly (ACA-co-MAA-co-EDMA) microballoon.
Background technology
Polymer microsphere (Polymericmicrospheres) is the broad-spectrum parting material of a class, extracts, the separation and concentration of albumen and polypeptide, stratographic analysis, blood purification, the field such as foodstuffs industry and pharmacy be widely used in Industrial Wastewater Treatment, ultrapure water preparation, catalyzed reaction, hydrometallurgy, Separation of Natural Products.The preparation method of polymer microsphere is various, comprises precipitation polymerization, dispersion polymerization, letex polymerization, template, seed swelling etc.Polymer microsphere textural property prepared by different methods is different, and the diameter of microballoon is from nanometer to grade, and size distribution is single dispersing or polydispersion, and pore structure is atresia or porous, and character is hydrophobic or hydrophilic.In the preparation method of polymer microsphere, precipitation polymerization method is simple and convenient the most, reaction process is: the homogeneous system be made up of polymerization single polymerization monomer, initiator, stablizer and dispersion medium starts, after heating, initiator produces free radical, polymerization single polymerization monomer aggregates into chain polymer gradually, dispersion medium is the poor solvent of these polymer molecules, the polymkeric substance of generation will from dispersion medium Precipitation, through cleaning, filter, drying can secure satisfactory grades sub-microballoon.Current, the microballoon preparation of methacrylic has been tending towards ripe, but the preparation research containing halogen functional group's microballoon is less, and the preparation of Mono Chloro Acetic Acid propylene class microballoon have not been reported.
The present invention has developed the method that one prepares poly (ACA-co-MAA-co-EDMA) microballoon, and the method preparation is simple, easy to operate, the microballoon regular shape of preparation, grain size narrowly distributing.
Summary of the invention
The present invention utilizes simple precipitation polymerization method to prepare poly (ACA-co-MAA-co-EDMA) microballoon simultaneously containing chloracetyl and carboxyl two kinds of functional groups first, and the method is simple, and thus obtained microsphere regular shape, particle size distribution range is narrow.
The technical solution used in the present invention comprises the following steps:
The first step, two kinds of function monomer Mono Chloro Acetic Acid propylene ACA, methacrylic ester MAA are dissolved in solvent according to the volume ratio of 1:1-1:3, add linking agent ethylene glycol dimethacrylate EDMA and initiator Diisopropyl azodicarboxylate AIBN again, colourless transparent solution is obtained after Raolical polymerizable occurs in concussion mixing under room temperature, function monomer ACA is the introducing reagent of functional group, the pattern of function monomer MAA subcontrol microballoon and size; Described solvent is the binary system of acetonitrile and n-propyl alcohol, and its volume ratio is 3:1-9:1; The consumption of described linking agent EDMA is 0.5-2 times of two kinds of total consumptions of function monomer, and the consumption of described initiator A IBN is the 0.5-1% of two kinds of function monomer total masses.
Second step, carries out supersound process by colourless transparent solution, and reactant is mixed and degasification, be homogeneous colourless transparent solution after sonic oscillation.
3rd step, passes into nitrogen deoxygenation, colourless transparent solution is placed in 60 DEG C of-80 DEG C of oil baths and obtains white suspension liquid with the tachyphylaxis 2-5h of 60-100r/min;
4th step, reaction terminate after, by after white suspension liquid suction filtration with methyl alcohol or ethanol purge, after drying poly (ACA-co-MAA-co-EDMA) microballoon; The microballoon regular shape prepared, narrow size distribution, size is between 0.5 μm-3.0 μm.
The present invention utilizes precipitation polymerization process to prepare poly (ACA-co-MAA-co-EDMA) microballoon first, and processing step is simple, use equipment is few, and this microballoon can carry out later stage derivative modification, for Solid-Phase Extraction and chromatographic separation filler.
Accompanying drawing explanation
Accompanying drawing 1 is the stereoscan photograph of poly (ACA-co-MAA-co-EDMA).
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.
Embodiment 1:
The first step, be that the MAA of ACA and 0.48mL of 0.32mL joins volume ratio and is respectively in the acetonitrile of 14mL:6mL, 16mL:4mL, 18mL:2mL and the mixed solvent of n-propyl alcohol by volume, add linking agent EDMA0.8mL and initiator A IBN0.01g, under room temperature, concussion is mixed to get colourless transparent solution;
Second step, carries out ultrasonic vibration 10min by the volumetric flask that colourless transparent solution is housed;
3rd step, passes into nitrogen connection prolong 80r/min in the oil bath of 70 DEG C and obtains white suspension liquid after carrying out reaction 2h;
4th step, by white suspension liquid absolute ethanol washing after reaction terminates, obtains poly (ACA-co-MAA-co-EDMA) microballoon after oven dry; Microsphere Size is 0.5-1.0 μm.
Embodiment 2:
The first step, joins in 18mL acetonitrile and 2mL n-propyl alcohol by 0.2mL:0.6mL, 0.32mL:0.48mL, 0.4mL:0.4mL respectively by ACA and MAA, adds linking agent EDMA0.8mL and initiator A IBN0.01g, and under room temperature, concussion is mixed to get colourless transparent solution;
Second step, carries out ultrasonic vibration 15min by the volumetric flask that colourless transparent solution is housed;
3rd step, passes into after nitrogen connection prolong carries out reaction 2.5h with 80r/min in the oil bath of 70 DEG C and obtains white suspension liquid;
4th step, then carries out suction filtration 5 times by white suspension liquid washed with methanol after reaction terminates, obtains poly (ACA-co-MAA-co-EDMA) microballoon after oven dry.Microsphere Size is 1.0-1.5 μm.
Embodiment 3:
The first step, MAA volume being respectively ACA and 0.48mL of 0.32mL joins in 18mL acetonitrile and 2mL n-propyl alcohol, initiator A IBN0.01g, the volume adding linking agent EDMA is respectively 0.87mL, 0.83mL, 0.8mL, be respectively 12:10,12:11,12:12 with ACA, MAA mixed volume ratio, under room temperature, concussion is mixed to get colourless transparent solution;
Second step, carries out ultrasonic vibration 20min by the volumetric flask that colourless transparent solution is housed;
3rd step, passes into after nitrogen connection prolong carries out reaction 5h with 80r/min in the oil bath of 70 DEG C and obtains white suspension liquid;
4th step, then carries out suction filtration 3 times by white suspension liquid washes of absolute alcohol after reaction terminates, obtains poly (ACA-co-MAA-co-EDMA) microballoon after oven dry.Microsphere Size is 1.2-2.2 μm.
Embodiment 4:
The first step, MAA volume being respectively ACA and 0.48mL of 0.32mL joins in 18mL acetonitrile and 2mL n-propyl alcohol, adds linking agent EDMA0.8mL and initiator A IBN0.01g, and under room temperature, concussion is mixed to get colourless transparent solution;
Second step, carries out ultrasonic vibration 15min by the volumetric flask that colourless transparent solution is housed;
3rd step, passes into nitrogen and connects prolong carry out reaction 3h in the oil bath of 70 DEG C, rotating speed is respectively 60,80,100r/min;
4th step, reaction terminates rear washed with methanol and then carries out suction filtration 3 times, just obtains poly (ACA-co-MAA-co-EDMA) microballoon after oven dry.Microsphere Size is 1.5-2.2 μm.
Embodiment 5:
The first step, MAA volume being respectively ACA and 0.48mL of 0.32mL joins in 18mL acetonitrile and 2mL n-propyl alcohol, adds linking agent EDMA0.8mL and initiator A IBN0.01g, and under room temperature, concussion is mixed to get colourless transparent solution;
Second step, carries out ultrasonic vibration 10min by the volumetric flask that colourless transparent solution is housed;
3rd step, pass into nitrogen connection prolong and in the oil bath of 60 DEG C, 70 DEG C, 80 DEG C, carrying out reaction 2h respectively, rotating speed is 90r/min;
4th step, reaction terminates rear washes of absolute alcohol and then carries out suction filtration 3 times, just obtains poly (ACA-co-MAA-co-EDMA) microballoon after oven dry.Microsphere Size is 2.0-3.0 μm.
Claims (6)
1. a preparation method for Poly (ACA-co-MAA-co-EDMA) microballoon, is characterized in that, comprise the following steps:
The first step, two kinds of function monomer Mono Chloro Acetic Acid propylene ACA, methacrylic ester MAA are dissolved in solvent according to the volume ratio of 1:1-1:3, add linking agent ethylene glycol dimethacrylate EDMA and initiator Diisopropyl azodicarboxylate AIBN, room temperature concussion is mixed to get colourless transparent solution;
Second step, carries out supersound process by colourless transparent solution, is homogeneous colourless transparent solution after supersound process;
3rd step, nitrogen deoxygenation, is obtained by reacting white suspension liquid by colourless transparent solution under the rotating speed of 60-100r/min;
4th step, uses detergent washing by after white suspension liquid suction filtration after reaction terminates, and obtains poly (ACA-co-MAA-co-EDMA) microballoon after drying.
2. the preparation method of a kind of Poly (ACA-co-MAA-co-EDMA) microballoon as claimed in claim 1, it is characterized in that: described solvent is the binary system of acetonitrile and n-propyl alcohol, its volume ratio is 3:1-9:1.
3. the preparation method of a kind of Poly (ACA-co-MAA-co-EDMA) microballoon as claimed in claim 2, it is characterized in that: the consumption of described linking agent EDMA is 0.5-2 times of two kinds of total consumptions of function monomer, and the consumption of described initiator A IBN is the 0.5-1% of two kinds of function monomer total masses.
4. the preparation method of a kind of Poly (ACA-co-MAA-co-EDMA) microballoon as described in claim 1 or 2 or 3, is characterized in that: in the 3rd step, temperature of reaction is 60 DEG C-80 DEG C, and the reaction times is 2-5h.
5. the preparation method of a kind of Poly (ACA-co-MAA-co-EDMA) microballoon as described in claim 1 or 2 or 3, is characterized in that: described washing composition is methyl alcohol or dehydrated alcohol.
6. the preparation method of a kind of Poly (ACA-co-MAA-co-EDMA) microballoon as claimed in claim 4, is characterized in that: described washing composition is methyl alcohol or dehydrated alcohol.
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| CN103554376A (en) * | 2013-10-22 | 2014-02-05 | 上海华明高技术（集团）有限公司 | Preparation method of monodisperse cross-linked polymethyl methacrylate microspheres |
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| CN1067432A (en) * | 1991-03-22 | 1992-12-30 | 罗姆和哈斯公司 | The preparation method of the crosslinked copolymer beads of porous surface |
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