CN108676112A - The preparation method of monodisperse solvent resistant high-carboxyl-content polystyrene microsphere - Google Patents
The preparation method of monodisperse solvent resistant high-carboxyl-content polystyrene microsphere Download PDFInfo
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- CN108676112A CN108676112A CN201810511542.3A CN201810511542A CN108676112A CN 108676112 A CN108676112 A CN 108676112A CN 201810511542 A CN201810511542 A CN 201810511542A CN 108676112 A CN108676112 A CN 108676112A
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- polystyrene microsphere
- monodisperse
- preparation
- solvent resistant
- diacetone acrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Abstract
The present invention provides a kind of preparation method of the high surface-bound carboxylic content polystyrene microsphere of monodisperse solvent resistant, including：With the main polymerisation monomer of styrene, with ethyl methacrylate, Tert-butyl Methacrylate is comonomer, with divinylbenzene, vinyltriethoxysilane, Diacetone Acrylamide is crosslinking agent, trimethylolpropane is chain extender, sodium hydrogensulfite is acrylate solubilizer, is prepared by emulsifier-free emulsion polymerization reaction, when preparation, by styrene, divinylbenzene, Glycerin and deionized water are added in 250mL three-necked flasks, lead to N2High-speed stirred 30min adds Diacetone Acrylamide, ethyl methacrylate and Tert-butyl Methacrylate, after being warming up to 70 85 DEG C, initiator potassium persulfate is added in sodium hydrogensulfite, it reacts 6 24 hours, can be used for preparing monodisperse solvent resistant high-carboxyl-content size tunable polystyrene microsphere.
Description
Technical field
The invention belongs to Emulsifier-free Emulsion Polymerization Technology fields, are related to a kind of high surface carboxyl groups polyphenyl second of monodisperse solvent resistant
The preparation method of alkene microballoon.
Background technology
Emulsion polymerization is to prepare the important method of monodisperse polystyrene microsphere, and the microspherulite diameter homogeneity of preparation is high, shape
Looks integrity degree is good, but because emulsifier is difficult the factors such as removal after it adds emulsifier and reacts in the reaction, makes it in crowd
By various limitations in more biomedical sector applications, in consideration of it, emulsifier-free emulsion polymerization fast development is got up.
Emulsifier-free emulsion polymerization refers to not mixing emulsifier completely in high molecular polymerization process or only mixing micro emulsifier
The emulsion polymerization process of (its concentration is less than critical micelle concentration CMC), compared with conventional emulsion polymerization, emulsifier-free emulsion polymerization product
It has the following advantages：Product can be used directly；Reduce product cost；Eliminate the aftertreatment technology of emulsifier；Emulsion particle
Clean surface, so as to avoid emulsifier to harmful effects such as the optical of product, solvent resistance, film forming and surface naturies,
However the country is significantly larger than monomer dosage by crosslinked polystyrene microsphere dosage of crosslinking agent made from emulsifier-free emulsion polymerization at present,
Cost greatly increases.
Application No. is the patents of 200710164072.X to disclose a kind of preparation side of high cross-linking monodisperse polymer micro-sphere
Method, the dosage of crosslinking agent are about the 60% of monomer dosage, and the dosage of crosslinking agent increases, and on the one hand increase industrialized production preparation
The cost of crosslinked polystyrene microsphere, the exhaust gas of another aspect crosslinking agent, waste liquid also increase the dirt to air and water environment
Dye.In addition domestic less to microsphere surface and internal carboxyl control research, application No. is 201010278715.5 patent disclosures
The preparation method of carboxylic polystyrene microsphere, the carboxyl polystyrene microsphere surfaces externally and internally carboxyl that is prepared by such method
Content is essentially identical, it is difficult to control surfaces externally and internally carboxyl-content from nano-angle, is prepared at present for low cross-linking agent dosage resistance to molten
The polystyrene microsphere of agent, and carboxyl-content such as is unable to control at the drawbacks inside and outside microballoon.
Invention content
In view of this, the purpose of the present invention is exactly of the existing technology in order to solve the problems, such as, prepares high surface carboxyl groups and contain
Amount, the monodisperse polystyrene microsphere of low internal carboxyl-content.
Technical solution is used by the present invention solves above-mentioned the deficiencies in the prior art：A kind of high surface of monodisperse solvent resistant
The preparation method of carboxyl-content polystyrene microsphere, including：With the main polymerisation monomer of styrene, with ethyl methacrylate,
Tert-butyl Methacrylate is that comonomer provides carboxyl functional group simultaneously, with divinylbenzene, vinyltriethoxysilane,
Diacetone Acrylamide is crosslinking agent, and trimethylolpropane is chain extender, and sodium salt is for increasing ethyl methacrylate, methyl-prop
Enoic acid ter-butyl ester is water-soluble, is prepared by emulsifier-free emulsion polymerization reaction.
Preferably, the crosslinking agent includes divinylbenzene, Diacetone Acrylamide, N, N- methylene-bisacrylamides,
Bisphenol-A dual-allyl ether, vinyltriethoxysilane, the three kinds or more in vinyltrimethoxysilane account for
Styrene monomer total amount≤20%, but do not include 0.
Preferably, the chain extender accounts for styrene monomer total amount≤7.5%, but does not include 0.
Preferably, the sodium salt includes sodium hydrogensulfite, sodium bicarbonate, sodium thiosulfate, sodium carbonate it is one such or
It is several.
The present invention also provides a kind of preparation methods of the high surface-bound carboxylic content polystyrene microsphere of monodisperse solvent resistant, including
Following steps：By styrene, divinylbenzene, Diacetone Acrylamide, N, N- methylene-bisacrylamides, bisphenol-A diene
Propyl ether, Glycerin and deionized water are added in 250mL three-necked flasks, lead to N2High-speed stirred 30min；Add double third
Ketone acrylamide, ethyl methacrylate and Tert-butyl Methacrylate, sodium hydrogensulfite and deionized water mixed liquor, are warming up to
After 70-85 DEG C, initiator potassium persulfate is added, reacts 6-24 hours.
Compared to the prior art, the preparation side of the high surface-bound carboxylic content polystyrene microsphere of monodisperse solvent resistant of the invention
Method has and prepares high-crosslinking-degree polystyrene microsphere under the conditions of low cross-linking agent dosage, impregnates for a long time in organic solvent resistance to
Corrosion, is not easy to be swollen and decomposed, while internal carboxyl-content is low, the high feature of surface-bound carboxylic content, meanwhile, polyphenyl of the invention
Ethylene microballoon has solvent resistance, the polystyrene of high level of homogeneity, surface high-carboxyl-content, the low characteristic of internal carboxyl-content micro-
Ball.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of the crosslinked carboxy polystyrene microsphere prepared in the embodiment of the present invention 1；
Fig. 2 is the transmission electricity of the crosslinked carboxy polystyrene microsphere for preparing after acetone impregnates for 72 hours in the embodiment of the present invention 1
Mirror picture；
Fig. 3 is the transmission electron microscope picture of outsourcing crosslinked polystyrene microsphere；
Fig. 4 is transmission electron microscope picture of the outsourcing crosslinked polystyrene microsphere after acetone impregnates for 72 hours.
Specific implementation mode
It is described below for disclosing the present invention so that those skilled in the art can realize the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.It defines in the following description
The present invention basic principle can be applied to other embodiments, deformation scheme, improvement project, equivalent program and do not carry on the back
Other technologies scheme from the spirit and scope of the present invention.
Embodiment 1
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 2g styrene, 0.08g divinylbenzenes, 0.01g vinyltriethoxysilane, 0.15g bisphenol-A diallyls
Ether, 0.15g Glycerins and 50ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen 30min
87 DEG C are warming up to simultaneously, adds 0.1g Diacetone Acrylamide, 0.1g ethyl methacrylate and 0.1g methacrylic acid uncles
Butyl ester, 0.1g sodium hydrogensulfites continue after stirring 5min, and potassium peroxydisulfate 20mg is added and causes polymerization.Mixing speed maintains
300rpm, reaction time 12h.
The crosslinked carboxy polystyrene microsphere prepared in the present embodiment 1 and outsourcing crosslinked carboxy polystyrene microsphere are respectively taken
1ml（Solid content 10%）Lotion, after centrifugation, ethyl alcohol is washed 3 times, is dissolved in respectively in 100ml acetone solns, 200rpm is stirred at room temperature 72
Centrifugation is taken out after hour, transmission electron microscope observing is as shown in Figure 1, the crosslinked carboxy polystyrene microsphere that will be prepared in the present embodiment 1
Compared with outsourcing crosslinked carboxy polystyrene microsphere solvent resistance, the results are shown in Figure 2.
Please refer to Fig. 3 and Fig. 4, respectively the transmission electron microscope picture of outsourcing crosslinked polystyrene microsphere and outsourcing crosslinking
Transmission electron microscope picture of the polystyrene microsphere after acetone impregnates for 72 hours, can be seen that from transmission picture and closes through the invention
At polystyrene microsphere in acetone after soaking and stirring 72h, still keep preferable spherical morphology, outsourcing crosslinked polystyrene micro-
Ball warp, which is crossed to impregnate for a long time, has caved in, decomposed phenomenon, from transmission electron microscope it can be appreciated that the crosslinking carboxylic of the present invention
Base polystyrene microballoon resistant to acetone corrosive power is substantially better than outsourcing crosslinked carboxy polystyrene microsphere.
Using conductimetric titration method, the crosslinked carboxy polystyrene microsphere prepared in the present embodiment 1 and outsourcing are crosslinked carboxylic
Carboxyl-content compares inside and outside base polystyrene microballoon, the results detailed in following table：
| Title | Surface carboxyl groups（mmol/g） | Embed carboxyl（mmol/g） |
| 1 microballoon of embodiment | 0.7139 | 0.1215 |
| Outsourcing microballoon | 0.2025 | 0.2715 |
It is found that by the method for the invention from list, by monomer and crosslinking agent, after the compounding of chain extender and sodium salt, using nothing
Microsphere surface carboxyl-content made of soap emulsion polymerization is apparently higher than carboxyl-content inside microballoon, effectively controls the crosslinking of carboxyl
Enrichment is orientated, and has preferable effect for control microsphere surface carboxyl-content.
Embodiment 2
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 3g styrene, 0.12g divinylbenzenes, 0.03g vinyltriethoxysilane, 0.2g bisphenol-A dual-allyl ethers,
0.2g Glycerins and 50ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen 30min simultaneously
87 DEG C are warming up to, 0.2g Diacetone Acrylamide, 0.15g ethyl methacrylate and the tertiary fourth of 0.15g methacrylic acids are added
Ester, 0.2g sodium hydrogensulfites continue after stirring 5min, and potassium peroxydisulfate 20mg is added and causes polymerization, mixing speed maintains
300rpm, reaction time 12h.
Embodiment 3
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 4g styrene, 0.18g divinylbenzenes, 0.035g vinyltriethoxysilane, 0.25g bisphenol-A diallyls
Ether, 0.3g Glycerins and 100ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen 30min
85 DEG C are warming up to simultaneously, adds 0.25g Diacetone Acrylamide, 0.15g ethyl methacrylate and 0.15g metering systems
Tert-butyl acrylate, 0.2g sodium hydrogensulfites continue after stirring 5min, and potassium peroxydisulfate 20mg is added and causes polymerization, mixing speed maintains
In 300rpm, reaction time 12h.
Embodiment 4
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 5g styrene, 0.2g divinylbenzenes, 0.038g N, N- methylene-bisacrylamides, 0.3g bisphenol-A diallyls
Ether, 0.35g Glycerins and 100ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen 30min
85 DEG C are warming up to simultaneously, adds 0.35g Diacetone Acrylamide, 0.2g ethyl methacrylate and 0.2g methacrylic acids
The tert-butyl ester, 0.3g sodium hydrogensulfites continue after stirring 5min, and potassium peroxydisulfate 20mg is added and causes polymerization, mixing speed maintains
300rpm, reaction time 18h.
Embodiment 5
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 6g styrene, 0.22g divinylbenzenes, 0.042g N, N- methylene-bisacrylamides, 0.4g bisphenol-As diene third
Base ether, 0.4g Glycerins and 100ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen
30min is warming up to 80 DEG C simultaneously, adds 0.4g Diacetone Acrylamide, 0.3g ethyl methacrylate and 0.3g methyl-props
Enoic acid ter-butyl ester, 0.4g sodium hydrogensulfites continue after stirring 5min, and potassium peroxydisulfate 20mg is added and causes polymerization.Mixing speed is tieed up
It holds in 300rpm, the reaction time is for 24 hours.
Embodiment 6
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 7g styrene, 0.25g divinylbenzenes, 0.05g N, N- methylene-bisacrylamides, 0.5g bisphenol-A diallyls
Ether, 0.45g Glycerins and 100ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen 30min
80 DEG C are warming up to simultaneously, adds 0.55g Diacetone Acrylamide, 0.35g ethyl methacrylate and 0.35g methacrylic acids
The tert-butyl ester, 0.45g sodium hydrogensulfites continue after stirring 5min, and potassium peroxydisulfate 25mg is added and causes polymerization, mixing speed maintains
300rpm, the reaction time is for 24 hours.
Embodiment 7
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 8g styrene, 0.3g divinylbenzenes, 0.055g N, N- methylene-bisacrylamides, 0.52g bisphenol-As diene third
Base ether, 0.55g Glycerins and 100ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen
30min is warming up to 75 DEG C simultaneously, adds 0.65g Diacetone Acrylamide, 0.42g ethyl methacrylate and 0.45g methyl
Tert-butyl acrylate, 0.52g sodium bicarbonates continue after stirring 5min, and potassium peroxydisulfate 30mg is added and causes polymerization, mixing speed dimension
It holds in 300rpm, the reaction time is for 24 hours.
Embodiment 8
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 9g styrene, 0.45g divinylbenzenes, 0.06g N, N- methylene-bisacrylamides, 0.55g bisphenol-As diene third
Base ether, 0.65g Glycerins and 100ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen
30min is warming up to 75 DEG C simultaneously, adds 0.7g Diacetone Acrylamide, 0.5g ethyl methacrylate and 0.5g methyl-props
Enoic acid ter-butyl ester, 0.65g sodium bicarbonates continue after stirring 5min, and potassium peroxydisulfate 40mg is added and causes polymerization, mixing speed maintains
In 300rpm, the reaction time is for 24 hours.
Embodiment 9
The method that the present embodiment prepares monodisperse polystyrene microsphere includes the following steps：
By 10g styrene, 0.5g divinylbenzenes, 0.07g N, N- methylene-bisacrylamides, 0.65g bisphenol-As diene third
Base ether, 0.75g Glycerins and 100ml deionized waters are added in 250mL three-necked flasks, stir 300rpm, lead to nitrogen
30min is warming up to 75 DEG C simultaneously, adds 0.75g Diacetone Acrylamide, 0.55g ethyl methacrylate and 0.55g methyl
Tert-butyl acrylate, 0.68g sodium bicarbonates continue after stirring 5min, and potassium peroxydisulfate 40mg is added and causes polymerization, mixing speed dimension
It holds in 300rpm, the reaction time is for 24 hours.
It should be understood by those skilled in the art that the embodiment of the present invention shown in foregoing description and attached drawing is only used as illustrating
And it is not intended to limit the present invention.The purpose of the present invention has been fully and effectively achieved.The function and structural principle of the present invention exists
It shows and illustrates in embodiment, under without departing from the principle, embodiments of the present invention can have any deformation or modification.
Claims (5)
1. a kind of high surface-bound carboxylic content polystyrene microsphere of monodisperse solvent resistant, which is characterized in that preparation method is：With benzene
The main polymerisation monomer of ethylene, with ethyl methacrylate, Tert-butyl Methacrylate is that comonomer provides carboxyl official simultaneously
It can roll into a ball, with divinylbenzene, vinyltriethoxysilane, Diacetone Acrylamide is crosslinking agent, and trimethylolpropane is to expand
Chain agent, for sodium salt for increasing ethyl methacrylate, Tert-butyl Methacrylate is water-soluble, is reacted and is made by emulsifier-free emulsion polymerization
It is standby to form.
2. the high surface-bound carboxylic content polystyrene microsphere of monodisperse solvent resistant according to claim 1, which is characterized in that institute
It includes divinylbenzene to state crosslinking agent, Diacetone Acrylamide, N, N- methylene-bisacrylamides, bisphenol-A dual-allyl ether,
Vinyltriethoxysilane, the three kinds or more in vinyltrimethoxysilane, account for styrene monomer total amount≤
20%, but do not include 0.
3. the high surface-bound carboxylic content polystyrene microsphere of monodisperse solvent resistant according to claim 1, which is characterized in that institute
It states chain extender and accounts for styrene monomer total amount≤7.5%, but do not include 0.
4. the preparation method of the high surface carboxyl groups polystyrene microsphere of monodisperse solvent resistant according to claim 1, feature
It is, the sodium salt includes sodium hydrogensulfite, sodium bicarbonate, sodium thiosulfate, and sodium carbonate is one such or several.
5. the preparation method of the high surface carboxyl groups polystyrene microsphere of monodisperse solvent resistant according to claim 1, feature
It is, preparation method includes the following steps：
Step（1）：By styrene, divinylbenzene, Diacetone Acrylamide, N, N- methylene-bisacrylamides, bisphenol-A pair
Allyl ether, Glycerin and deionized water are added in 250mL three-necked flasks, lead to N2High-speed stirred 30min；
Step（2）：Add Diacetone Acrylamide, ethyl methacrylate and Tert-butyl Methacrylate, sodium hydrogensulfite
With deionized water mixed liquor, after being warming up to 70-85 DEG C, initiator potassium persulfate is added, reacts 6-24 hours.
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| CN109705288A (en) * | 2019-01-10 | 2019-05-03 | 苏州泽漫生物技术有限公司 | The preparation method of super-hydrophobic superoleophobic magnetic composite microsphere |
| CN111574652A (en) * | 2019-02-18 | 2020-08-25 | 中国科学院化学研究所 | Monodisperse carboxyl functional polymer microsphere based on redox reaction initiation, and preparation method and application thereof |
| CN111961160A (en) * | 2020-08-04 | 2020-11-20 | 中国石油大学(华东) | Active polymer for high-molecular gel plugging agent, and preparation method and application thereof |
| CN113150200A (en) * | 2021-03-16 | 2021-07-23 | 苏州为度生物技术有限公司 | Preparation method and application of carboxyl latex microspheres |
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Application publication date: 20181019 |