CN103396505A - Preparation method of pure cationic nanosphere - Google Patents
Preparation method of pure cationic nanosphere Download PDFInfo
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- CN103396505A CN103396505A CN2013102572941A CN201310257294A CN103396505A CN 103396505 A CN103396505 A CN 103396505A CN 2013102572941 A CN2013102572941 A CN 2013102572941A CN 201310257294 A CN201310257294 A CN 201310257294A CN 103396505 A CN103396505 A CN 103396505A
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Abstract
The invention relates to a preparation method of a pure cationic nanosphere, which is a high molecular polymer nanosphere synthesized by a soap-free emulsion polymerization method. According to the method, a cationic copolymerization monomer is added into a reaction system to undergo copolymerization with a vinyl monomer and a (methyl) acrylate monomer, a water-soluble cationic azo initiator is used to initiate polymerization. By controlling the variety and dosage of the cationic initiator or the cationic monomer, the polymerization reaction rate and the surface charge density of the finally generated nanosphere can be regulated. By adjusting the reaction ratio of the vinyl monomer to the (methyl) acrylate monomer, nanospheres with different glass-transition temperatures can be synthesized. The nanosphere prepared by the method has a simple process, is pure, and has monodisperse and controllable glass-transition temperature, surface charge density and grain size. The grain size of the nanosphere can be controlled within 45nm-200nm, the surface charge density can vary within certain range, and the glass transition temperature ranges from -54DEG C to 100DEG C.
Description
Technical field
The present invention relates to a kind of preparation method of pure cation nanometer ball, relate in particular to and a kind ofly prepare that pure, pure second-order transition temperature, surface charge density, particle diameter list are disperseed and the method for controlled single dispersible cationic nanometer ball, can be widely used in the association areas such as sewage disposal industry, textile printing and dyeing industry, paper-making industry, bio-science, medical diagnosis.
Background technology
Cation nanometer ball surface is with cation groups such as amido, quaternary ammonium salt groups, but strong interaction occurs the electronegative material of effects on surface, thereby is widely used at chemical industry, medical science, biology, electronic information field.
In the majority with surface band anionic functional group of disclosed polymer nanocomposite ball in recent years, for example, Zeng Yanwei adds in patent 200910234001.1 a small amount of, lower than the aniorfic surfactant of micelle-forming concentration, by emulsion polymerization, synthesized the polymer microballoon of a kind of particle diameter less than 100nm, distribution of sizes homogeneous, this kind method is different from emulsifier-free emulsion polymerization, the surfactant concentration that adds in this invention is lower than its micelle-forming concentration, but the tensio-active agent that existence is introduced can increase the difficulty of product removal of impurities.The olefinic monomer that the people such as Yu Jian utilize nano-silicon dioxide particle, olefinic organic hydrocarbon monomer in patent 200410000746 and 200410000747, contain sulfonic group or carboxyl is raw material, by emulsifier-free emulsion polymerization or without the soap suspension polymerization, sulfonic acid or carboxyl function type polymer/SiO2 composite nanoparticle have been prepared, particle diameter is evenly and less than 100nm, product is easy to purifying, nanometer ball surface band anionic functional group in this invention.
There is not the disclosed nanoparticle that utilizes a kind of biodegradable polymer to adopt the soap-free polymerization method to synthesize of patent 201110423118 on surface with the nanoparticle of ionic functional group, can to its size, regulate and control according to actual needs, this soap-free polymerization method is that degradable polymer is dissolved in solvent, and add precipitation agent to form mixing solutions, degradable polymer is along with the volatilization embedding nucleation of solvent subsequently, and constantly the segment around absorption finally forms biodegradable polymer nano particles.Nanoparticle surface in this patent of invention does not have functional group's group, but can be by in polymerization process, ionic species being encapsulated in polymer nano-particle, still owing to there is no getting off in conjunction with being easy to desorption of covalency bonding force between the two.The people such as Li Qingsong have synthesized the three-layer nuclear shell structure magnetic composite nanoparticles by electrostatic self-assembled and seed emulsion polymerization in patent 201010129873, can be applicable to the aspects such as biochemical separation, targeting preparation, immobilized enzyme, immunoassay, catalyticing research, but the limitation of this invention is the nanometer ball surface, there is no cation group.
Aspect the nanometer ball of surface band Cationic functional groups, the people such as Han Min utilize liquid phase reduction take acetone and water as solvent in patent 201110370138, add quaternary ammonium salt cationic surfactant, make how empty shape particle size distribution range at the positively charged ion Pd of 30-50nm nanometer ball, in this patent of invention, introduced the tensio-active agent that is adsorbed in a large number the nanometer ball surface.
In existing invention technology, adopt multiple material to prepare polymer nanocomposite ball dissimilar, different purposes, as the medical targeting nano ball that contains inorganic particulate, polymer/inorganic composite nano ball etc., and in preparation process, add to do dispersion agent into organic solvent, perhaps add ionic emulsifying agent, these materials are difficult for removing.In addition, the synthesis technique more complicated, polymerization time reaches tens hours.
The present invention adopts multiple cationic comonomer with cation group and vinyl monomer, (methyl) acrylate monomer to prepare terpolymer cation nanometer ball with emulsion polymerization, preparation technology is simple, the reaction times is short, prepared cation nanometer ball surface band cationic functional groups, but the synthesizing series particle diameter is at 45nm-200nm with interior nanometer ball, and monodispersity is good; And can be by controlling vinyl monomer, (methyl) acrylate monomer, cationic azo class initiator, the kind of cationic monomer and particle diameter, second-order transition temperature, the surface charge density that consumption regulates and controls the cation nanometer ball; In emulsion polymerization process, do not add other materials such as emulsifying agent, organic dispersing agent, avoid introducing impurity in polymerization system, the nanometer ball that makes is pure, does not need the subsequent purification process.Prepared cation nanometer ball is with a wide range of applications in every field.
Summary of the invention
The present invention is intended to overcome the prior art complexity, the polymer drops particle diameter is large and the wide defect that distributes, avoided in the traditional technology using the defect of the impurity such as emulsifying agent, prepared cationic polymers nanometer ball is pure, narrow diameter distribution, and second-order transition temperature, surface charge density etc. are controlled.
the present invention includes following steps: with whipping appts, prolong, in the 250ml four-hole boiling flask of nitrogen access equipment, add a certain amount of deionized water, logical nitrogen 15min is to remove air wherein, the stirring velocity of whipping appts is 300rpm, after 15min, in four-hole boiling flask, add a certain amount of cation mono liquid solution that has prepared, after 15min, add a certain proportion of vinyl monomer and (methyl) acrylate monomer, all monomers add after complete and start heat up (room temperature rises to 80 ℃), when bath temperature arrives 80 ℃, remain 5min and add the azo cationic initiator solution that has prepared, start simultaneously timing, 80 ℃ of isothermal reaction 3h, react the complete room temperature discharging that is cooled to.
Described vinyl monomer is selected vinylbenzene, vinyl benzoate, vinyl acetate, vinylchlorid, furans ethene, vinylidene chloride, vinyl cyanide, acrylamide.
Described (methyl) acrylate monomer is selected methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate.
Described cationic monomer is selected p-vinyl benzyl trimethyl ammonium chloride, 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, the rare acyl oxypropyl trimethyl of methyl-prop ammonium chloride, dimethylamino-propyl Methacrylamide, dimethylaminoethyl methacrylate, dimethyl diallyl ammonium chloride.
Described water-soluble azo cationoid initiator comprises azo two isobutyl imidazoline salt hydrochlorates, azo diisobutyl amidine dihydrochloride.
Cation nanometer ball prepared by the present invention, can control by the mass ratio that changes vinyl monomer and (methyl) acrylate monomer the second-order transition temperature of nanometer ball, the kind and the content that change cationic monomer, cationic initiator are controlled particle diameter and the surface charge density of cation nanometer ball, thereby prepare pure second-order transition temperature, surface charge density, the dispersion of particle diameter list and controlled single dispersible cationic nanometer ball.
The accompanying drawing explanation
Fig. 1 is discontinuous emulsion polymerization technique.
Fig. 2 is the particle diameter test result of a certain cation nanometer ball.
Fig. 3 is the transmission electron microscope photo (TEM) of a certain cation nanometer ball.
Fig. 4 is the second-order transition temperature (Tg) of a certain cation nanometer ball.
Embodiment
Cationic monomer 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride solution or the p-vinyl benzyl trimethyl ammonium chloride solution of preparation 1mol/L, according to demand toward the cation mono liquid solution that adds different volumes (0.5ml, 1ml, 2ml, 3ml, 4ml, 5ml) in polymerization system, add remaining deionized water (in system, the deionized water quality is 100g), logical nitrogen, stir speed (S.S.) 300rpm.Take successively vinylbenzene 9.2g, butyl acrylate 0.8g, be added in reaction system, continues to stir, and start to be warming up to 80 ℃.
Constant temperature 5min after temperature arrives 80 ℃, to the slow certain density initiator azo diisobutyl miaow hydrochloride (the relative vinyl monomer of quality and (methyl) acrylate monomer total amount 1.0%) that prepared of dropping in system, isothermal reaction 3h.React the complete room temperature discharging that is cooled to.
Cationic monomer 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride solution or the p-vinyl benzyl trimethyl ammonium chloride solution of preparation 1mol/L, add 0.5ml cation mono liquid solution (amount of substance that includes cationic monomer is 0.5mmol), add remaining deionized water (in system, the deionized water quality is 100g), logical nitrogen, stir speed (S.S.) 300rpm.Take successively vinylbenzene 9.2g, butyl acrylate 0.8g, be added in reaction system, continues to stir, and start to be warming up to 80 ℃.
Constant temperature 5min after temperature arrives 80 ℃, need to be to the slow certain density initiator azo diisobutyl miaow hydrochloride or azo two isobutyl imidazoline salt hydrochlorates (the relative vinyl monomer of quality and (methyl) acrylate monomer total amount 0.2%, 0.4%, 0.6%, 0.8%, the 1.0%) solution that have prepared of dropping in system, isothermal reaction 3h according to different synthetic results.React the complete room temperature discharging that is cooled to.
Cationic monomer 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride solution or the p-vinyl benzyl trimethyl ammonium chloride solution of preparation 1mol/L, add 0.5ml cation mono liquid solution (amount of substance that includes cationic monomer is 0.5mmol), add remaining deionized water (in system, the deionized water quality is 100g), logical nitrogen, stir speed (S.S.) 300rpm.Take successively vinylbenzene and Butyl Acrylate Monomer, mass ratio is 10:0,9:1,8:2,7:3,6:4,5:5,4:6,3:7,2:8,1:9,0:10, according to different synthetic demands as a result, add the vinylbenzene of different mass ratio and Butyl Acrylate Monomer in entering to reaction system, continue to stir, and start to be warming up to 80 ℃.
Constant temperature 5min after temperature arrives 80 ℃, need to be to slow certain density initiator azo two isobutyl imidazoline salt hydrochlorates (the relative vinyl monomer of quality and (methyl) acrylate monomer total amount 1.0%) solution that prepared of dropping in system, isothermal reaction 3h according to different synthetic results.React the complete room temperature discharging that is cooled to.
Claims (8)
1. the preparation method of a pure cation nanometer ball, its feature comprises the steps: with whipping appts, prolong, in the reactor of nitrogen access equipment, add a certain amount of deionized water, logical nitrogen is to remove air wherein, under agitation add a certain amount of cation mono liquid solution that has prepared, add again a certain proportion of vinyl monomer and (methyl) acrylate monomer, all monomers add after complete and are warming up to design temperature, after homo(io)thermism, add the initiator solution that has prepared, start simultaneously timing isothermal reaction setting-up time, react complete, be cooled to the room temperature discharging, can obtain second-order transition temperature, surface charge density is controlled, the particle diameter list disperses and controlled cation nanometer ball.
2. the preparation method of a kind of pure cation nanometer ball according to claim 1, is characterized in that the temperature of reaction of setting is 70-85 ℃, reaction times of setting is 3-5 hour, and the temperature of reaction of optimization is that 80 ℃, reaction times are 3 hours.
3. the preparation method of a kind of pure cation nanometer ball according to claim 1, is characterized in that vinyl monomer comprises vinylbenzene, vinyl benzoate, vinyl acetate, vinylchlorid, furans ethene, vinylidene chloride, vinyl cyanide, acrylamide; (methyl) acrylate monomer comprises methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate.
4. the preparation method of a kind of pure cation nanometer ball according to claim 1, it is characterized in that vinyl monomer and the mass ratio x:y of (methyl) acrylate monomer are the ratio of 10:0,9:1,8:2,7:3,6:4,5:5,4:6,3:7,2:8,1:9,0:10, the second-order transition temperature that kind by controlling two kinds of different monomers and consumption can regulate and control nanometer ball, modification scope is-54 ℃-105 ℃.
5. the preparation method of a kind of pure cation nanometer ball according to claim 1, it is characterized in that using multiple water-soluble cationic monomer and water-soluble azo cationoid initiator, water-soluble cationic monomer comprises p-vinyl benzyl trimethyl ammonium chloride, 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methacryloyl oxypropyl trimethyl ammonium chloride, dimethylamino-propyl Methacrylamide, dimethylaminoethyl methacrylate, dimethyl diallyl ammonium chloride; Water-soluble azo cationoid initiator comprises azo two isobutyl imidazoline salt hydrochlorates, azo diisobutyl amidine dihydrochloride.
6. the preparation method of a kind of pure cation nanometer ball according to claim 1, the consumption that it is characterized in that water-soluble cationic monomer is 0.5mmol, 1.0mmol, 2.0mmol, 3.0mmol, 4.0mmol, 5.0mmol; Initiator amount is 0.2%, 0.4%, 0.6%, 0.8%, 1.0%(is with respect to vinyl monomer and acrylate monomer total amount).
7. the preparation method of a kind of pure cation nanometer ball according to claim 1, is characterized in that polymerization process does not add emulsifying agent, adopts emulsifier-free emulsion polymerization method synthesizing cationic nanometer ball.
8. the preparation method of a kind of pure cation nanometer ball according to claim 1, is characterized in that adopting interrupter method polymerization technique synthesizing cationic nanometer ball.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031210A (en) * | 2014-06-23 | 2014-09-10 | 中国科学院化学研究所 | Method for preparing quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion |
| CN104313903A (en) * | 2014-10-30 | 2015-01-28 | 青岛大学 | Color polymer microspheres prepared from active dye |
| CN104831489A (en) * | 2015-05-22 | 2015-08-12 | 天津工业大学 | Method for modifying bluish dogbane fibers through nanometer polymer particles |
| CN107955092A (en) * | 2016-10-14 | 2018-04-24 | 中国科学院青岛生物能源与过程研究所 | A kind of gas hydrate nanometer accelerating agent of size tunable and preparation method thereof |
| CN112573885A (en) * | 2020-12-12 | 2021-03-30 | 南京霄祥工程技术有限公司 | Self-leveling mortar and preparation method thereof |
-
2013
- 2013-06-26 CN CN2013102572941A patent/CN103396505A/en active Pending
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| 张金枝等: "功能型阳离子聚合物乳液的性能研究", 《湖北大学学报（自然科学版）》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031210A (en) * | 2014-06-23 | 2014-09-10 | 中国科学院化学研究所 | Method for preparing quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion |
| CN104031210B (en) * | 2014-06-23 | 2016-08-17 | 中国科学院化学研究所 | The preparation method of the monodisperse polystyrene microsphere emulsion of quaternary ammonium salt surface modification |
| CN104313903A (en) * | 2014-10-30 | 2015-01-28 | 青岛大学 | Color polymer microspheres prepared from active dye |
| CN104831489A (en) * | 2015-05-22 | 2015-08-12 | 天津工业大学 | Method for modifying bluish dogbane fibers through nanometer polymer particles |
| CN107955092A (en) * | 2016-10-14 | 2018-04-24 | 中国科学院青岛生物能源与过程研究所 | A kind of gas hydrate nanometer accelerating agent of size tunable and preparation method thereof |
| CN112573885A (en) * | 2020-12-12 | 2021-03-30 | 南京霄祥工程技术有限公司 | Self-leveling mortar and preparation method thereof |
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Application publication date: 20131120 |