CN102485755A - Preparation method of polyacrylonitrile microballoon with special morphology - Google Patents
Preparation method of polyacrylonitrile microballoon with special morphology Download PDFInfo
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- CN102485755A CN102485755A CN2010105777174A CN201010577717A CN102485755A CN 102485755 A CN102485755 A CN 102485755A CN 2010105777174 A CN2010105777174 A CN 2010105777174A CN 201010577717 A CN201010577717 A CN 201010577717A CN 102485755 A CN102485755 A CN 102485755A
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Abstract
The invention provides a novel preparation method of polyacrylonitrile microballoon. A polymerization system comprises monomer, initiator and disperse medium. Without adding stabilizing agent into the polymerization system and mechanical stirring, a polymer microballoon disperse system is obtained through monomer polymerization with a reaction temperature set at a certain value. Monomers and initiator are dissolved in the disperse medium to form a stable solution, wherein monomer acrylonitrile and disperse medium in the mixed liquor are in a volume ratio of 1:3-1:50; the initiator is organic peroxide or azo compound and has a content, relative to the monomer, of 0.005-5 wt%; the disperse medium is ester, ketone and ethers; the obtained polymer microballoon has a particle size between 50-1000 nm, quite obvious projection on particle surface and is comprised of a plurality of sheet layers. The method is simple and practical, and the system contains no dispersant or emulsifier and is easy for post-treatment. A monodisperse polymer prepared by the method has clean surface, controllable particle size and narrow particle size distribution.
Description
Technical field
The present invention relates to the simple and easy to do preparation method of a kind of special appearance monodisperse polyacrylonitrile microballoon.
Background technology
The application of monodisperse polymer micro-sphere has been penetrated into the every nook and cranny in our life; From bulk products such as coating, paper surface coating, makeup to the micro-capsule that is used for medicine sustained and controlled release, protein separation is with the high additive value product of chromatography media; And got into high leading-edge field in recent years, like fields such as standard metering, electronic information, analytical chemistry, intelligence analyses.
The method of traditional preparation process high molecular polymer microballoon is suspension polymerization, letex polymerization, precipitation polymerization and emulsifier-free emulsion polymerization etc.Suspension polymerization is the big particle diameter polymer microballoon of preparation method commonly used, can generate the approximately particle from 50 μ m to 2mm of particle size range, but since the uncertainty of monomer droplet size control, resulting polymers size distribution broad.The polymer particle monodispersity of emulsion polymerization prepared is better, and rate of polymerization is big, and the polymkeric substance relative molecular mass is high, and the resulting polymers particle diameter is less, but when the needs solid phase prod, needs through operations such as cohesion, washing, dehydration, dryings, and cost is higher.Dispersion copolymerization method is because production technique is simple, and usability is strong, can reasonably solve heat dissipation problem; High solids content; Rate of polymerization is fast, is suitable for various monomers, and can prepare the advantages such as monodisperse polymer particle of different-grain diameter; Caused the great interest of people, dispersion copolymerization method has obtained development at full speed.
Above-mentioned several kinds of polymerization methods can both successfully be prepared polymer particle, but they have a common shortcoming promptly in reaction process, all need add the stability that emulsifying agent or stablizer keep polymeric system, and add-on is generally all bigger.Dispersion agent or emulsifying agent often remain in and are difficult in the product remove, and have influenced the surface property of polymer beads, also environment have been caused pollution simultaneously.
Summary of the invention
This paper has proposed a kind of new method for preparing polymer micro, and has prepared the monodisperse polyacrylonitrile microballoon of special appearance with it.This kind method need not add any emulsifying agent or stablizer just can form stable dispersion system, and the polymer beads of preparation presents monodispersity, within the specific limits controllable granularity.And temperature of reaction has been risen to the boiling point of solvent, simplified experimental installation and operating process.Be a kind of economy, prepare the method for monodisperse polymer micro-sphere efficiently.
The present invention mixes the solution that forms stable homogeneous with monomer, initiator, dispersion medium; Under certain pressure, be heated to certain temperature then; The monomer polymerization that decomposition of initiator becomes radical to cause and is dissolved in the medium forms oligopolymer; Oligopolymer rises to after the critical chain length from medium precipitating and comes out, and coalescence forms the primary nuclei particle each other, grows into monodispersed submicron level polymer microballoon at last.Dispersion medium must satisfy dissolved monomer and initiator, and does not dissolve the polymkeric substance of generation.The present invention starts from the homogeneous system of clear, ends at uniform and stable milky dispersion system.
The present invention is different from the traditional disperse polymerization; Stablizer is one of important composition composition in the dispersion polymerization; Polymer beads is suspended in the dispersion medium by means of sterically hindered effect, coulombic interaction or little crosslinked action of stablizer, forms uniform and stable milky dispersion system.In addition, all need add stirring in the general dispersion polymerization and prevent the generation of gelatin phenomenon, and need not add stirring among the present invention, reduce equipment requirements and production energy consumption.
The present invention also is different from precipitation polymerization, and the characteristic phenomenon of precipitation polymerization (layering appears in polymerization system) is not found in this reaction system.And precipitation polymerization is used for preparing cross-linked polymer microsphere more; Keep the stability of system through adding a large amount of linking agents; Can crosslinking degree play crucial effects to forming the stable polymer microballoon, just can not reach stable and need not add the linking agent system in this reaction system.
The present invention is also different with emulsifier-free emulsion polymerization, and emulsifier-free emulsion polymerization needs the initiator of special construction, hydrophilic monomer to participate in copolymerization.The present invention does not need the initiator and the hydrophilic monomer of special construction.
The preparation method of special appearance polyacrylonitrile microballoon of the present invention: monomer, initiator and dispersion medium are mixed; Wherein, The volume ratio of monomer and dispersion medium is 1: 3～1: 50 in the mixed solution, and initiator content is the 0.005wt%～5wt% of monomer mass, is heated to certain temperature; Monomer polymerization obtains polymkeric substance precipitating from dispersion medium and comes out, and forms monodisperse polymer micro-sphere.
The monomer among the present invention and the volume ratio of dispersion medium preferably 1: 5～1: 30.
Initiator content among the present invention is the 0.05wt%～wt% of monomer mass preferably.
Reaction times of the present invention between 0.5～100h, 0.5～24h preferably.
The used dispersion medium of the present invention is selected from one or more the mixture in ester class, ketone or the ether compound;
Described ester compound is selected from one or more the mixture in ethyl formate, propyl formate, butyl formate, methyl acetate, ETHYLE ACETATE, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, n-amyl acetate, Isoamyl Acetate FCC, methyl-butyrate, ethyl n-butyrate, the tributyl phosphate;
Described ketone compounds is selected from one or more the mixture in acetone, butanone, 2 pentanone, propione, the methyln-hexyl ketone;
Described ether compound is selected from one or more the mixture in ether, propyl ether, butyl ether, amyl ether, isopropyl ether, ethyl isobutyl ether, isoamyl oxide, methyl ethyl ether, methyl-n-butyl ether, the ethylene-propylene ether.
The used monomer of the present invention mainly is a vinyl cyanide, in addition mixture and its copolymerization of one or more in esters of acrylic acid, methyl acrylic ester, vinylbenzene, styrene derivatives, the methylene-succinic acid etc.
Described esters of acrylic acid is selected from one or more the mixture in methyl acrylate, ethyl propenoate, the Bing Xisuandingzhi;
Described methyl acrylic ester is selected from one or more the mixture in TEB 3K, Jia Jibingxisuanyizhi, the NSC 20956.
The used initiator of the present invention is Diisopropyl azodicarboxylate, ABVN, Lucidol or their mixture.
The particle diameter of the prepared monodisperse polymer micro-sphere of the present invention is between 50～1000nm, and microsphere surface is clean, does not contain any emulsifying agent or stablizer, and pattern is special.The polymer microballoon of method preparation all has been widely used in fields such as catalyzer, coating, plastic working, analytical chemistry, environment protection thus.
Description of drawings
The electron scanning micrograph and the transmission electron microscope photo (magnification 10000) of the polymer microballoon of Fig. 1 embodiment 2 preparations
The transmission electron microscope photo (magnification 10000) of the polymer microballoon of Fig. 2 embodiment 4 preparations
The transmission electron microscope photo (magnification 10000) of the polymer microballoon of Fig. 3 embodiment 6 preparations
The transmission electron microscope photo (magnification 10000) of the polymer microballoon of Fig. 4 embodiment 7 preparations
Embodiment
Embodiment 1
120mL vinyl cyanide, 600mL ETHYLE ACETATE, the 120mg Lucidol joins in the reaction vessel.Then, reaction vessel is put into 82 ℃ water bath with thermostatic control, boiling reaction two hours, can obtain particle diameter is 500nm, the microballoon that monodispersity is good.
Embodiment 2
180mL vinyl cyanide, 1800mL ETHYLE ACETATE, the 180mg Diisopropyl azodicarboxylate joins in the reaction vessel.Then, reaction vessel is put into 82 ℃ water bath with thermostatic control, boiling reaction two hours, can obtain particle diameter is 300nm, the microballoon that monodispersity is good.
Embodiment 3
40mL vinyl cyanide, 2000mL ETHYLE ACETATE, the 40mg ABVN joins in the reaction vessel.Then, reaction vessel is put into 82 ℃ water bath with thermostatic control, boiling reaction two hours, can obtain particle diameter is 150nm, the microballoon that monodispersity is good.
Embodiment 4
99mL vinyl cyanide, 1mL vinylbenzene, 1000mL ETHYLE ACETATE, 100mg Diisopropyl azodicarboxylate join in the reaction vessel.Then, reaction vessel is put into 82 ℃ water bath with thermostatic control, boiling reaction two hours, can obtain particle diameter is 200nm, the microballoon that monodispersity is good.
Embodiment 5
100mL vinyl cyanide, 300mL ETHYLE ACETATE, 100mg Diisopropyl azodicarboxylate join in the reaction vessel.Then, reaction vessel is put into 75 ℃ water bath with thermostatic control, reacted two hours, can obtain particle diameter is 1 μ m, the microballoon that monodispersity is good.
Embodiment 6
50mL vinyl cyanide, 500mL methyl acetate, 50mg Diisopropyl azodicarboxylate join in the reaction vessel.Then, reaction vessel is put into 60 ℃ water bath with thermostatic control, boiling reaction two hours, can obtain particle diameter is 170nm, the microballoon that monodispersity is good.
Embodiment 7
100mL vinyl cyanide, 1000mL butylacetate, 100mg Diisopropyl azodicarboxylate join in the reaction vessel.Then, be added to boiling reaction two hours, can obtain particle diameter is 250nm, the microballoon that monodispersity is good.
Claims (9)
1. the preparation method of a special appearance polyacrylonitrile microballoon is characterized in that: monomer, initiator are dissolved in the solution that forms stable homogeneous in the dispersion medium; Wherein, The volume ratio of monomer and dispersion medium was at 1: 3～1: 50 in the mixed solution; Initiator is 0.005wt%～5wt% with respect to monomeric content; At the boiling point of dispersion medium or react 0.5～100h below the boiling temperature, the polymerisate that monomer polymerization obtains precipitating from dispersion medium is come out then, forms white milky dispersion system;
Described dispersion medium is selected from one or more the mixture in ester class, ketone or the ether compound;
Used monomer mainly is a vinyl cyanide, in addition mixture and its copolymerization of one or more in esters of acrylic acid, methyl acrylic ester, vinylbenzene, styrene derivatives, the methylene-succinic acid etc.;
Used initiator is Diisopropyl azodicarboxylate, ABVN, Lucidol or their mixture.
2. method according to claim 1 is characterized in that: the volume ratio of described monomer and dispersion medium was at 1: 3～1: 50.
3. method according to claim 1 is characterized in that: described initiator is 0.005wt%～5wt% with respect to monomeric content.
4. method according to claim 1 is characterized in that: said temperature is Celsius 30 to spend to the scope of the boiling point of dispersion medium.
5. method according to claim 1 is characterized in that: the described reaction times is 0.5～100h.
6. method according to claim 1; It is characterized in that: described alkyl esters compound, ketone compounds and ether compound mainly comprise one or more the mixture that is selected from ethyl formate, propyl formate, butyl formate, methyl acetate, ETHYLE ACETATE, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, n-amyl acetate, Isoamyl Acetate FCC, methyl-butyrate, ethyl n-butyrate, tributyl phosphate, acetone, butanone, 2 pentanone, propione, methyln-hexyl ketone, ether, propyl ether, butyl ether, amyl ether, isopropyl ether, ethyl isobutyl ether, isoamyl oxide, methyl ethyl ether, methyl-n-butyl ether, the ethylene-propylene ether.
7. method according to claim 1 is characterized in that: described esters of acrylic acid is selected from one or more the mixture in methyl acrylate, ethyl propenoate, the Bing Xisuandingzhi;
Described methyl acrylic ester is selected from one or more the mixture in TEB 3K, Jia Jibingxisuanyizhi, the NSC 20956.
8. method according to claim 1 is characterized in that: the pattern of described polymer beads is that tree peony is flower-shaped.
9. method according to claim 1 is characterized in that: the diameter of described monodisperse polymer micro-sphere is between 50～1000nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613699A (en) * | 2013-09-25 | 2014-03-05 | 长兴化学工业股份有限公司 | Polymer particles, method for producing same and use thereof |
| 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 |
| CN103764726A (en) * | 2011-08-30 | 2014-04-30 | 巴斯夫欧洲公司 | Water-based polymer emulsions for opaque films and coatings applications |
| CN105777999A (en) * | 2016-03-18 | 2016-07-20 | 河北科技师范学院 | Thermotropic shape memory polymer and preparation method thereof |
| CN114532585A (en) * | 2022-03-01 | 2022-05-27 | 湖北中烟工业有限责任公司 | Essence slow-release microcapsule and preparation method and application thereof |
-
2010
- 2010-12-01 CN CN2010105777174A patent/CN102485755A/en active Pending
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| 《河北科技师范学院学报》 20100315 王东军等 "无稳定剂存在时聚丙烯腈-co-苯乙烯微球的制备" 第12-14、26页 1-9 第24卷, 第1期 * |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9701829B2 (en) | 2011-08-30 | 2017-07-11 | Basf Se | Water-based polymer emulsions for opaque films and coatings applications on flexible substrates |
| US9663650B2 (en) | 2011-08-30 | 2017-05-30 | Basf Se | Water-based polymer emulsions for opaque films and coatings applications |
| CN103764726A (en) * | 2011-08-30 | 2014-04-30 | 巴斯夫欧洲公司 | Water-based polymer emulsions for opaque films and coatings applications |
| CN103781825A (en) * | 2011-08-30 | 2014-05-07 | 巴斯夫欧洲公司 | Water-based polymer emulsions for opaque films and coatings applications on flexible substrates |
| CN103781825B (en) * | 2011-08-30 | 2015-11-25 | 巴斯夫欧洲公司 | The aqueous-based polymers emulsion of the opaque coating on flexible parent metal and coatings applications |
| CN103764726B (en) * | 2011-08-30 | 2015-11-25 | 巴斯夫欧洲公司 | For the aqueous-based polymers emulsion of opaque coating and coatings applications |
| US10106679B2 (en) | 2011-08-30 | 2018-10-23 | Basf Se | Water-based polymer emulsions for opaque films and coatings applications on flexible substrates |
| CN103613699B (en) * | 2013-09-25 | 2016-07-06 | 长兴材料工业股份有限公司 | Polymer particles, method for producing same and use thereof |
| CN103613699A (en) * | 2013-09-25 | 2014-03-05 | 长兴化学工业股份有限公司 | Polymer particles, method for producing same and use thereof |
| 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 |
| CN105777999B (en) * | 2016-03-18 | 2018-09-14 | 河北科技师范学院 | Thermotropic shape-memory polymer and preparation method thereof |
| CN105777999A (en) * | 2016-03-18 | 2016-07-20 | 河北科技师范学院 | Thermotropic shape memory polymer and preparation method thereof |
| CN114532585A (en) * | 2022-03-01 | 2022-05-27 | 湖北中烟工业有限责任公司 | Essence slow-release microcapsule and preparation method and application thereof |
| CN114532585B (en) * | 2022-03-01 | 2023-09-29 | 湖北中烟工业有限责任公司 | Essence slow-release microcapsule and preparation method and application thereof |
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Application publication date: 20120606 |