CN102432744A - Method for preparing monodispersed functional polymer microspheres - Google Patents
Method for preparing monodispersed functional polymer microspheres Download PDFInfo
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- CN102432744A CN102432744A CN2011102642945A CN201110264294A CN102432744A CN 102432744 A CN102432744 A CN 102432744A CN 2011102642945 A CN2011102642945 A CN 2011102642945A CN 201110264294 A CN201110264294 A CN 201110264294A CN 102432744 A CN102432744 A CN 102432744A
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Abstract
The invention discloses a method for preparing monodispersed functional polymer microspheres, comprising the following steps: dispersing a partial polymerized oil phase with the aid of ultrasonic into a continuous water phase to prepare a suspension, heating up to 80-85 DEG C, and preparing polymer microspheres by using a traditional suspension polymerization method, wherein, the oil phase comprises glycidyl methacrylate and hydroxyethyl methacrylate as functional monomers, ethylene glycol dimethacrylate as a cross-linking agent, a hydrophobic porogenic agent, and an oil soluble initiator, and the water phase comprises a stabilizing agent, a co-stabilizer, and soluble inorganic salt. The method is easy to practice and has no special requirements of reactor structure. The prepared monodispersed functional polymer microspheres have good monodispersity. According to the invention, because of the presence of functional groups consisting of epoxy group and hydroxyl group, a special functional resin can be obtained after chemical modification. The invention can be applied in medicine, selective absorption, immobilized enzyme, and large biological molecule separation and purification and related fields.
Description
Technical field
The present invention relates to the synthetic single divergent function polymer microballoon of improved suspension polymerization, the ultrasonic auxiliary suspension polymerization functionalized polymer microsphere of saying so more specifically.
Background technology
Single divergent function polymer microballoon has broad application prospects in high-technology fields such as biological chemistry, immune medical science, immobilized enzyme, high-effect ionic exchange resin, solid-phase synthesized carrier, chromatograph packing material certificate.The main method of at present synthetic monodisperse polymer micro-sphere has letex polymerization, dispersion polymerization, precipitation polymerization, seed swelling polymerization and glassy membrane emulsion process (SPG) etc.
Emulsion polymerization technology like micro-emulsion polymerization and emulsifier-free emulsion polymerization, is commonly used to prepare the monodisperse polymer micro-sphere of particle diameter less than 1 μ m, but the microballoon of greater particle size is difficult to use this method preparation.Dispersion polymerization is a kind of polymerization method that proposes the beginning of the seventies; The mono-dispersion microballoon particle diameter of its preparation is 2～20 μ m; But dispersion polymerization can't obtain the microballoon of vesicular structure; Its linking agent accounts for monomeric ratio usually less than 3%, increases dosage of crosslinking agent or introduce second monomer size distribution is broadened.
The seed swelling polymerization is a kind of technology of reasonable preparation functional polymer microsphere; In the seeding polymerization process; Microballoon absorbs monomer until reaching the swelling equilibrium state, but microballoon absorbs monomer swell certain limit is arranged, and does not also reach needed size sometimes with a step swelling method; Need to adopt two steps even three steps to accomplish, obvious this continuous steps swelling method can the labor time.In order to address this problem, people have researched and developed some special swelling technology, like two step seed swelling technology of exploitations such as Ugelstad, and the dynamic swelling technology of exploitation such as Okubo.
Suspension polymerization is a kind of traditional method of preparation microballoon; This method preparation is more simple; It requires monomer mixture to be insoluble to dispersion medium, through stirring monomer droplet is dispersed in the medium with the drop form, and the size of oil droplet and distribution of sizes are to decide through stirring velocity.Suspension polymerization can prepare the porous polymer microsphere that particle diameter is 10～1000 μ m, and the common size distribution of the polymer microballoon that obtains is very wide.
In addition, in the suspension polymerization process, usually follow the generation of letex polymerization, especially when microsphere diameter during at 0.1～500 μ m, the letex polymerization odds is bigger, and by product is more, and the size of microspherulite diameter is inhomogeneous.Patent JP-A-55-82125; JP-A-60-8302; JP-A-62-205108, JP-A-61-255355 and CN 101530771A make the polymer microballoon of preparation obtain good dimensional homogeneity with the generation of water-soluble inorganic inhibitor or organic emulsion polymerization retarder inhibition letex polymerization.
Through a large amount of discovering, the key of suspension polymerization monodisperse polymer micro-sphere is how to prepare the narrower suspension polymerization drop of size distribution.The nineties, people developed glassy membrane emulsifying technology (SPG), and this technology can prepare that shape is regular, the uniform drop of size, can prepare the narrower polymer microballoon of size distribution in conjunction with suspension polymerization technique.In addition; People also improve traditional suspension polymerization process; As adopt unstable state to stir; The mixing direction and the timed interval through the control stirring rake prepare single divergent function polymer microballoon, or improve the structure of reactor design, prepare single divergent function polymer microballoon through T type pipe method and injection suspension polymerization.But these non-traditional suspension polymerizations have very high requirement to structure of reactor, so industrial applications is restricted.
Summary of the invention
The objective of the invention is to overcome above-mentioned non-traditional suspension polymerization to the exigent deficiency of structure of reactor; Providing a kind of does not have the method for particular requirement, the simple uniform drop of acquisition size to structure of reactor, makes narrow dispersion even single divergent function polymer microballoon in conjunction with suspension polymerization.
One of characteristic of the present invention is, is dissolved with oil phase solution polymerization 0.5～1.5h under 71～75 ℃ of temperature of monomer mixture, increases oil phase viscosity.Another is characterised in that, when ultrasonic aid dispersion, reduces mixing speed and ultrasonic power gradually, obtains the uniform drop of size, under low mixing speed, carries out suspension polymerization.Have following steps:
(1) water preparation continuously: add 1.0～1.4% Z 150PH respectively by the raw material weight degree, 0.5～1.5% gelatin, 1.0～2.5% sodium-chlor; 3.0 the zero(ppm) water of～5.0% sucrose and 91.0～93.5% connects mechanical stirring and water of condensation, is heated to 90 ℃ while stirring; Control mixing speed to Z 150PH dissolves fully; Be made into continuous water, solution left standstill, subsequent use;
(2) prepolymerization: function monomer SY-Monomer G 5.3ml and Rocryl 400 4.8ml, linking agent ethylene glycol dimethacrylate 3.05ml, hydrophobicity pore-creating agent butylacetate and octane are respectively 6.6ml; Oil soluble radical initiator Diisopropyl azodicarboxylate 0.065～0.125g; Supersound process 5min; The limit is slowly stirred the limit and is heated to 71～75 ℃, uses solution polymerization process with oil phase polymerase 10 .5～1.5h, forms pre-polymerization liquid;
(3) ultrasonic aid dispersion: get the continuous water that 105～158ml step (1) makes, join in the pre-polymerization liquid of step (2), ultrasonic auxiliary high-speed stirring 10～20min down;
(4) suspension polymerization: stop ultrasonicly, simultaneously mixing speed is adjusted to 450～550rpm, be warming up to 80～85 ℃, N
2Finish behind the reaction 5h under the atmosphere, obtain microballoon, suction filtration is used hot water, extraction using alcohol three times respectively, and 60 ℃ of following drying under reduced pressure make single divergent function polymer microballoon.
The Z 150PH of said step (1) and gelatin are stablizer, and sucrose is co-stabilizer.
Ultrasonic frequency is 25KHz in the said step (3), adjustable power, and the rotating speed of high-speed stirring is 1000rpm.
Said step (4) makes single divergent function polymer microballoon, and its diameter is controlled between 50～100 microns, and monodispersity is good, and dispersion coefficient is less than 0.1.
The invention has the beneficial effects as follows, provide that a kind of method is simple, the diameter of single divergent function polymer microballoon of structure of reactor not had particular requirement, preparation is controlled between 50～100 microns, monodispersity good, dispersion coefficient is less than the preparation method of single divergent function polymer microballoon of 0.1.The existence of functional groups-epoxy group(ing) and hydroxyl is arranged on the single divergent function polymer microballoon of the present invention, after chemically modified, can obtain the specific functionality resin, be applied to association areas such as medicine, selective adsorption, immobilized enzyme and separation and purification of biological macromolecule.
Description of drawings
Fig. 1 is the infrared absorpting light spectra of single divergent function polymer microballoon;
Fig. 2 is the electron microscope picture of step among the embodiment 3 (3) drop;
Fig. 3 is the electron microscope picture of embodiment 3 the finished product.
Embodiment
The present invention adopts commercially available analytical pure raw material, and specific embodiment is following.
(1) water preparation continuously: in having the 250ml there-necked flask of chuck, add the 2.8g Z 150PH respectively, the 1.0g gelatin; 2.0g sodium-chlor, the zero(ppm) water of 10.0g sucrose and 184.2g connects mechanical stirring and water of condensation; Be heated to 90 ℃ while stirring; Control mixing speed to Z 150PH dissolves fully, and solution left standstill is subsequent use.
(2) prepolymerization: the 250ml there-necked flask that has chuck is installed in the ultrasonic washing instrument; Add 5.3ml SY-Monomer G (GMA), 4.8ml Rocryl 400 (HEMA), 3.05ml ethylene glycol dimethacrylate (EGDMA); 6.6ml butylacetate; 6.6ml octane, 0.065g Diisopropyl azodicarboxylate (AIBN), supersound process 5min; Connect mechanical stirring and water of condensation, the limit is slowly stirred the limit chuck and is heated to 75 ℃, reaction 0.5h.
(3) ultrasonic aid dispersion: get the continuous water that 132ml step (1) makes, join in the pre-polymerization liquid in the step (2), the adjustment mixing speed is opened supersound process simultaneously to 1000rpm, keeps 10min.
(4) suspension polymerization: stop ultrasonicly, simultaneously mixing speed is adjusted to 550rpm, be warming up to 80 ℃, N
2Finish behind the reaction 5h under the atmosphere, obtain microballoon, suction filtration is used hot water, extraction using alcohol three times respectively, and 60 ℃ of following drying under reduced pressure make single divergent function polymer microballoon.
Single divergent function polymer microballoon is characterized, record: mean diameter is 35 microns, dispersion coefficient 0.078.
Embodiment 2
(1) water preparation continuously: in having the 250ml there-necked flask of chuck, add the 2.0g Z 150PH respectively, the 2.0g gelatin; 3.0g sodium-chlor, 6.0g sucrose, 187.0g zero(ppm) water; Connect mechanical stirring and water of condensation, heat temperature raising to 90 ℃ while stirring, control mixing speed to Z 150PH dissolves fully; Solution left standstill, subsequent use.
(2) prepolymerization: the 250ml there-necked flask that has chuck is installed in the ultrasonic washing instrument; Add 5.3ml SY-Monomer G (GMA), 4.8ml Rocryl 400 (HEMA), 3.05ml ethylene glycol dimethacrylate (EGDMA); 6.6ml butylacetate; 6.6ml octane, 0.065g Diisopropyl azodicarboxylate (AIBN), supersound process 5min; Connect mechanical stirring and water of condensation, the limit is slowly stirred the limit chuck and is heated to 71 ℃, reaction 1.0h.
(3) ultrasonic aid dispersion: get the continuous water that 105ml step (1) makes, join in the pre-polymerization liquid in the step (2), the adjustment mixing speed is opened supersound process simultaneously to 1000rpm, keeps 15min.
(4) suspension polymerization: stop ultrasonicly, simultaneously mixing speed is adjusted to 500rpm, be warming up to 82 ℃, N
2Finish behind the reaction 5h under the atmosphere, obtain microballoon, suction filtration is used hot water, extraction using alcohol three times respectively, and 60 ℃ of following drying under reduced pressure make single divergent function polymer microballoon.
Single divergent function polymer microballoon is characterized, record: mean diameter is 58 microns, dispersion coefficient 0.085.
Embodiment 3
(1) water preparation continuously: in having the 250ml there-necked flask of chuck, add the 2.0g Z 150PH respectively, the 2.0g gelatin; 2.0g sodium-chlor, 10.0 sucrose, 184.0g zero(ppm) water; Connect mechanical stirring and water of condensation, heat temperature raising to 90 ℃ while stirring, control mixing speed to Z 150PH dissolves fully; Solution left standstill, subsequent use.
(2) prepolymerization: the 250ml there-necked flask that has chuck is installed in the ultrasonic washing instrument; Add 5.3ml SY-Monomer G (GMA), 4.8ml Rocryl 400 (HEMA), 3.05ml ethylene glycol dimethacrylate (EGDMA); 6.6ml butylacetate; 6.6ml octane, 0.102g Diisopropyl azodicarboxylate (AIBN), supersound process 5min; Connect mechanical stirring and water of condensation, the limit is slowly stirred the limit chuck and is heated to 71 ℃, reaction 1.5h
(3) ultrasonic aid dispersion: get the continuous water that 132ml step (1) makes, join in the pre-polymerization liquid in the step (2), the adjustment mixing speed is opened supersound process simultaneously to 1000rpm, keeps 20min.
(4) suspension polymerization: stop ultrasonicly, simultaneously mixing speed is adjusted to 450rpm, be warming up to 82 ℃, N
2Finish behind the reaction 5h under the atmosphere, obtain microballoon, suction filtration is used hot water, extraction using alcohol three times respectively, and 60 ℃ of following drying under reduced pressure make single divergent function polymer microballoon.
Single divergent function polymer microballoon is characterized, record: mean diameter is 83 microns, dispersion coefficient 0.090.
Embodiment 4
(1) water preparation continuously: in having the 250ml there-necked flask of chuck, add the 2.0g Z 150PH respectively, the 3.0g gelatin; 5.0g sodium-chlor, 8.0g sucrose, 182g zero(ppm) water; Connect mechanical stirring and water of condensation, heat temperature raising to 90 ℃ while stirring, control mixing speed to Z 150PH dissolves fully; Solution left standstill, subsequent use.
(2) prepolymerization: the 250ml there-necked flask that has chuck is installed in the ultrasonic washing instrument; Add 5.3ml SY-Monomer G (GMA), 4.8ml Rocryl 400 (HEMA), 3.05ml ethylene glycol dimethacrylate (EGDMA); 6.6ml butylacetate; 6.6ml octane, 0.125g Diisopropyl azodicarboxylate (AIBN), supersound process 5min; Connect mechanical stirring and water of condensation, the limit is slowly stirred the limit chuck and is heated to 71 ℃, reaction 1.5h.
(3) ultrasonic aid dispersion: get the continuous water that 158ml step (1) makes, join in the pre-polymerization liquid in the step (2), the adjustment mixing speed is opened supersound process simultaneously to 1000rpm, keeps 15min.
(4) suspension polymerization: stop ultrasonicly, simultaneously mixing speed is adjusted to 500rpm, be warming up to 85 ℃, N
2Finish behind the reaction 5h under the atmosphere, obtain microballoon, suction filtration is used hot water, extraction using alcohol three times respectively, and 60 ℃ of following drying under reduced pressure make single divergent function polymer microballoon.
Single divergent function polymer microballoon is characterized, record: mean diameter is 66 microns, dispersion coefficient 0.080.
Fig. 1 is the infrared absorpting light spectra of single divergent function polymer microballoon, 3450.38cm among the figure
-1Be the charateristic avsorption band of hydroxyl, 904.86cm
-1, 847.09cm
-1Be the charateristic avsorption band of epoxy bond, do not have the charateristic avsorption band of carbon-carbon double bond, show: the copolymerzation with cross-linking reaction has taken place in GMA, HEMA, EGDMA, has generated functional polymer microsphere;
Fig. 2 is the electron microscope picture of step among the embodiment 3 (3) drop, and Fig. 2 can explain, has obtained the uniform drop of size through ultrasonic aid dispersion.
Fig. 3 is the electron microscope picture of embodiment 3 the finished product, and Fig. 3 can explain that the finished product are monodispersed.This also explained novel method provided by the invention to structure of reactor do not have particular requirement, simple, can obtain the uniform drop of size, make single divergent function polymer microballoon.
Claims (4)
1. method for preparing single divergent function polymer microballoon has following steps:
(1) water preparation continuously: add 1.0～1.4% Z 150PH respectively by the raw material weight degree, 0.5～1.5% gelatin, 1.0～2.5% sodium-chlor; 3.0 the zero(ppm) water of～5.0% sucrose and 91.0～93.5% connects mechanical stirring and water of condensation, is heated to 90 ℃ while stirring; Control mixing speed to Z 150PH dissolves fully; Be made into continuous water, solution left standstill, subsequent use;
(2) prepolymerization: function monomer SY-Monomer G 5.3ml and Rocryl 400 4.8ml, linking agent ethylene glycol dimethacrylate 3.05ml, hydrophobicity pore-creating agent butylacetate and octane are respectively 6.6ml; Oil soluble radical initiator Diisopropyl azodicarboxylate 0.065～0.125g; Supersound process 5min; The limit is slowly stirred the limit and is heated to 71～75 ℃, uses solution polymerization process with oil phase polymerase 10 .5～1.5h, forms pre-polymerization liquid;
(3) ultrasonic aid dispersion: get the continuous water that 105～158ml step (1) makes, join in the pre-polymerization liquid of step (2), ultrasonic auxiliary high-speed stirring 10～20min down;
(4) suspension polymerization: stop ultrasonicly, simultaneously mixing speed is adjusted to 450～550rpm, be warming up to 80～85 ℃; Finish behind the reaction 5h under the N2 atmosphere, obtain microballoon, suction filtration; Use hot water, extraction using alcohol three times respectively, 60 ℃ of following drying under reduced pressure make single divergent function polymer microballoon.
2. according to the method for preparing single divergent function polymer microballoon of claim 1, it is characterized in that the Z 150PH of said step (1) and gelatin are stablizer, sucrose is co-stabilizer.
3. according to the method for preparing single divergent function polymer microballoon of claim 1, it is characterized in that ultrasonic frequency is 25KHz in the said step (3), adjustable power, the rotating speed of high-speed stirring is 1000rpm.
4. according to the method for preparing single divergent function polymer microballoon of claim 1, it is characterized in that said step (4) makes single divergent function polymer microballoon, its diameter is controlled between 50～100 microns, and monodispersity is good, and dispersion coefficient is less than 0.1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028252A (en) * | 2014-05-20 | 2014-09-10 | 四川师范大学 | Stationary-phase filler with polyacrylate matrix and preparation method thereof |
| CN104275166A (en) * | 2013-07-05 | 2015-01-14 | 无锡加莱克色谱科技有限公司 | Anion exchange chromatographic filler for purification of low molecular weight heparin, preparation method, chromatographic column filled thereby and purification method |
| CN104497205A (en) * | 2014-11-27 | 2015-04-08 | 成都锦汇科技有限公司 | Separation medium for purifying proteins, and preparation method thereof |
| CN105063092A (en) * | 2015-09-02 | 2015-11-18 | 常州市长宇实用气体有限公司 | Method for preparing lithospermum erythrorhizon natural dyestuff through immobilized enzyme |
| CN105175624A (en) * | 2015-10-23 | 2015-12-23 | 蓝星（成都）新材料有限公司 | Polymeric microsphere and preparation method thereof |
| CN109793916A (en) * | 2019-01-17 | 2019-05-24 | 苏州恒瑞宏远医疗科技有限公司 | A kind of preparation method of the Polyvinyl Alcohol Embolization microballoon of uniform particle diameter |
| CN111068362A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Preparation method of hydrophobic and oleophylic porous material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256843A (en) * | 1978-06-08 | 1981-03-17 | Toyo Soda Manufacturing Company, Limited | Hydrophilic separating carrier and preparation thereof |
| EP0467339A1 (en) * | 1990-07-18 | 1992-01-22 | Mitsubishi Kasei Corporation | Water-swellable crosslinked polymer particles and process for their production |
| WO2000064953A1 (en) * | 1999-03-19 | 2000-11-02 | Vinod Chintamani Malshe | A process for production of micro-porous microspheres of polymers and polymeric pigments therefrom |
| CN1351896A (en) * | 2001-11-09 | 2002-06-05 | 天津大学 | Method for preparing microspheric PGDT separating medium with two kinds of pore forms |
-
2011
- 2011-09-07 CN CN2011102642945A patent/CN102432744A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256843A (en) * | 1978-06-08 | 1981-03-17 | Toyo Soda Manufacturing Company, Limited | Hydrophilic separating carrier and preparation thereof |
| EP0467339A1 (en) * | 1990-07-18 | 1992-01-22 | Mitsubishi Kasei Corporation | Water-swellable crosslinked polymer particles and process for their production |
| WO2000064953A1 (en) * | 1999-03-19 | 2000-11-02 | Vinod Chintamani Malshe | A process for production of micro-porous microspheres of polymers and polymeric pigments therefrom |
| CN1351896A (en) * | 2001-11-09 | 2002-06-05 | 天津大学 | Method for preparing microspheric PGDT separating medium with two kinds of pore forms |
Non-Patent Citations (1)
| Title |
|---|
| GÜLAY BAYRAMOĞLU等: "Immobilization of Candida rugosa lipase onto spacer-arm attached poly(GMA-HEMA- EGDMA) microspheres", 《FOOD CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104275166A (en) * | 2013-07-05 | 2015-01-14 | 无锡加莱克色谱科技有限公司 | Anion exchange chromatographic filler for purification of low molecular weight heparin, preparation method, chromatographic column filled thereby and purification method |
| CN104028252A (en) * | 2014-05-20 | 2014-09-10 | 四川师范大学 | Stationary-phase filler with polyacrylate matrix and preparation method thereof |
| CN104497205A (en) * | 2014-11-27 | 2015-04-08 | 成都锦汇科技有限公司 | Separation medium for purifying proteins, and preparation method thereof |
| CN105063092A (en) * | 2015-09-02 | 2015-11-18 | 常州市长宇实用气体有限公司 | Method for preparing lithospermum erythrorhizon natural dyestuff through immobilized enzyme |
| CN105175624A (en) * | 2015-10-23 | 2015-12-23 | 蓝星（成都）新材料有限公司 | Polymeric microsphere and preparation method thereof |
| CN111068362A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Preparation method of hydrophobic and oleophylic porous material |
| CN109793916A (en) * | 2019-01-17 | 2019-05-24 | 苏州恒瑞宏远医疗科技有限公司 | A kind of preparation method of the Polyvinyl Alcohol Embolization microballoon of uniform particle diameter |
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