CN105001367A - Crosslinked monodispersed polymer functional microspheres and preparation method thereof - Google Patents
Crosslinked monodispersed polymer functional microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polymer functional microspheres, and discloses crosslinked monodispersed polymer functional microspheres and a preparation method thereof. The microspheres are prepared through the following steps: an acrylate monomer, an initiator, a stabilizer and an alcohol water solution are well mixed, and the mixture is divided into a component A and a component B. A crosslinking agent is added into the component A, and the mixture is uniformly mixed; after heating and stirring, the component A with the crosslinking agent is dropped into the component B; and a thermostatic reaction is carried out, such that the crosslinked monodispersed polymer functional microspheres are obtained. According to the invention, a crosslinking agent-monomer mixed liquid post-dropping semi-continuous dispersion polymerization method is adopted. The obtained microspheres have the advantages of high crosslink density, uniform particle size, and good solvent resistance. The method has the advantage of simple operation. Compared to a conventional seed swelling method, the method provided by the invention is more practical, and has a potential application prospect.
Description
Technical field
The invention belongs to polymers function Microspheres Technique field, particularly a kind of cross-linking type monodisperse polymer functional microsphere and preparation method thereof.
Background technology
Polymer microballoon refers to diameter at nano level to micron order, and pattern is spherical or aspherical, and structure consists of the matrix material of single polymers or polymkeric substance.In the last few years, polymer microballoon was widely used in fields such as Solid-phase organic synthesis, compartment analysis, drug controlled release, biomedicine, paint additives, and therefore the microballoon of people to various materials and structures conducts extensive research and develop.Wherein multi-functional, high-performance, the Large stone polymer microsphere with different molecular weight, different structure, different surfaces characteristic and size uniformity have broad application prospects in a lot of fields.And cross-linking type mono-disperse polymer microspheres also have compared with common polymer microsphere spherical good, adsorptive power is strong, specific surface area is large, surface reaction ability is excellent, be easy to functionalization and the better advantageous property such as thermostability and solvent resistance.
In recent years, the technology of preparing of polymer microballoon progressively improves, and especially on inorganic/polymer composite microsphere novel preparation method, nano level microballoon and oversize microballoon, achieves breakthrough.In short, the preparation of polymer microballoon can be divided into polymkeric substance be raw material preparation method and take monomer as the preparation method of raw material.Be in the preparation method of raw material with polymkeric substance, the selection source of polymkeric substance can be all kinds of macromolecular materials of natural polymer and synthetic, its preparation method is generally first prepare oil/water (O/W), water/oil (W/O), water/oil/water (W/O/W) and oil/water/oil (O/W/O) emulsion, then selects diverse ways that drop is solidified according to the character of different polymkeric substance.Be that the micro-sphere method of preparing of raw material is mainly the methods such as letex polymerization, emulsifier-free emulsion polymerization, dispersion polymerization, precipitation polymerization, suspension polymerization, micro-emulsion polymerization, seeded emulsion polymerization and mini-emulsion polymerization with monomer.Compare other polymerization process, dispersion polymerization technology have that productive rate is high, the advantage such as polymkeric substance particle diameter is large, size uniformity, because of but the prefered method of preparation use Large stone monodisperse polymer micro-sphere.
The method of the monodisperse cross-linked polymerizing microballoons of current preparation is mainly divided into seed swelling polymerization, dispersion polymerization.Seed swelling polymerization prepares cross-linked polymer microsphere, and method steps is loaded down with trivial details, long reaction time, and the swelling conditional request of the first step is strict, therefore only rests on laboratory stage at present.And traditional dispersion polymerization is difficult to prepare high crosslinked polymer microballoon, this mainly because high-crosslinking-degree core not easily by monomer and linking agent swelling, thus the surface of the core that polyreaction is mainly occurred, the double bond on microsphere particles surface easily reacts to each other, thus causes being cross-linked between microballoon.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of cross-linking type monodisperse polymer functional microsphere.
Another object of the present invention is the preparation method providing a kind of above-mentioned cross-linking type monodisperse polymer functional microsphere.The semicontinuous dispersion polymerization processes that the inventive method drips after adopting crosslinkers monomers mixed solution, has that cross-linking density is high, uniform particle diameter, solvent resistance are good, simple operation and other advantages, and more conventional seed swelling method has more practicality.
Object of the present invention is realized by following proposal:
A kind of cross-linking type monodisperse polymer functional microsphere, is prepared by the method comprised the following steps:
After acrylic ester monomer, initiator, stablizer and alcohol solution being mixed, be divided into A, B two parts, wherein component A adds linking agent and mixes, after heated and stirred, the component A being added with linking agent is added drop-wise in B component, isothermal reaction, obtains cross-linking type monodisperse polymer functional microsphere.
The mass ratio of acrylic ester monomer used, linking agent, initiator, stablizer and alcohol solution is 100:(5 ~ 20): (0.3 ~ 3): (0.5 ~ 30): (500 ~ 1000).
Described heated and stirred preferred stirring reaction for some time, be preferably 1.5 ~ 2h.
The condition optimization of described isothermal reaction is 70 ~ 80 DEG C, reaction 10 ~ 24h.
The amount of described component A and B component is preferably equal.
Described acrylic ester monomer can be methacrylate-based monomer.
Preferably, described acrylic ester monomer is the mixture of methyl methacrylate monomer and glycidyl methacrylate monomer.
Preferred, in described acrylic ester monomer, the content of methyl methacrylate is 50 ~ 100wt%.
Described linking agent can be at least one in ethylene glycol dimethacrylate, 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, 1,4 butanediol diacrylate and Vinylstyrene.
Described initiator is oil-soluble initiator.
Preferably, described initiator is at least one in azo-initiator and organic peroxy class initiator, as at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and dibenzoyl peroxide.
Described stablizer is amphipathic nature polyalcohol, as at least one in Polyvinylpyrolidone (PVP) (PVP), hydroxypropylcellulose (HPC), polyacrylic acid (PAA) and polyoxyethylene glycol.
Preferably, described stablizer is Polyvinylpyrolidone (PVP).
Preferred, described stablizer is weight-average molecular weight is 40000 Polyvinylpyrolidone (PVP)s (PVP-K30).
Described alcohol solution can be the mixing solutions of a kind of and water in ethanol, methyl alcohol and Virahol.
Preferably, described alcohol solution is methanol aqueous solution.
More preferably, in described methanol aqueous solution, the mass ratio of first alcohol and water is 7:3 ~ 1:1.
After above-mentioned isothermal reaction, obtain white emulsion, preferably centrifuge washing is carried out to it, room temperature dries, obtain dried cross-linking type monodisperse polymer functional microsphere.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) semicontinuous method that drips after using crosslinkers monomers mixed solution of the present invention, dispersion polymerization obtains the Monodispersed polymeric microparticle of high-crosslinking-degree;
(2) the present invention adopts the glycidyl methacrylate monomer copolymerization of band epoxide function base, polymer microballoon is had certain functional;
(3) to be polymerized than General Decentralized the crosslinked microsphere degree of crosslinking obtained high for the crosslinked Monodispersed polymeric microparticle that obtains of the present invention, has better solvent resistant characteristic, have potential application prospect.
Accompanying drawing explanation
Fig. 1 is the polymer microballoon scanning electron microscope (SEM) photograph of embodiment 4.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Use in the following example is that reagent all can be bought and obtains.
Embodiment 1: a kind of preparation of cross-linking type monodisperse polymer functional microsphere
100 mass parts acrylic ester monomers (50 parts of MMA, 50 parts of GMA), 0.3 mass parts initiator (dibenzoyl peroxide), 0.5 mass parts stablizer (Polyvinylpyrolidone (PVP)), 500 mass parts alcohol solutions (methyl alcohol: quality is than 7:3) are divided into two equal portions a, b after mixing in proportion.Wherein a component directly adds in four-hole boiling flask, and b component adds 5 mass parts linking agents (ethylene glycol dimethacrylate) and mixes and be placed in constant pressure funnel.In flask, b mixed solution is dripped after logical nitrogen 70 DEG C stirs 1.5h.Continue reaction 10.5h, obtain white emulsion, repeatedly centrifuge washing, room temperature is dried and is obtained described cross-linking type monodisperse polymer functional microsphere.
Embodiment 2: a kind of preparation of cross-linking type monodisperse polymer functional microsphere
100 mass parts acrylic ester monomers (55 parts of MMA, 45 parts of GMA), 0.5 mass parts initiator (Diisopropyl azodicarboxylate), 5 mass parts stablizers (Polyvinylpyrolidone (PVP)), 600 mass parts alcohol solutions (methyl alcohol: quality is than 13:7) are divided into two equal portions a, b after mixing in proportion.Wherein a component directly adds in four-hole boiling flask, and b component adds 10 mass parts linking agents (ethylene glycol dimethacrylate) and mixes and be placed in constant pressure funnel.In flask, drip b mixed solution after logical nitrogen 70 DEG C stirs 2h, continue reaction 10h, obtain white emulsion, repeatedly centrifuge washing, room temperature is dried and is obtained described cross-linking type monodisperse polymer functional microsphere.
Embodiment 3: a kind of preparation of cross-linking type monodisperse polymer functional microsphere
100 mass parts acrylic ester monomers (60 parts of MMA, 40 parts of GMA), 1.2 mass parts initiators (Diisopropyl azodicarboxylate), 10 mass parts stablizers (Polyvinylpyrolidone (PVP)), 650 mass parts alcohol solutions (methyl alcohol: quality is than 1:1) are divided into two equal portions a, b after mixing in proportion.Wherein a component directly adds in four-hole boiling flask, and b component adds 12 mass parts linking agents (ethylene glycol dimethacrylate) and mixes and be placed in constant pressure funnel.In flask, drip b mixed solution after logical nitrogen 70 DEG C stirs 2h, continue reaction 10h, obtain white emulsion, repeatedly centrifuge washing, room temperature is dried and is obtained described cross-linking type monodisperse polymer functional microsphere.
Embodiment 4: a kind of preparation of cross-linking type monodisperse polymer functional microsphere
100 mass parts acrylic ester monomers (70 parts of MMA, 30 parts of GMA), 2 mass parts initiators (Diisopropyl azodicarboxylate), 20 mass parts stablizers (Polyvinylpyrolidone (PVP)), 800 mass parts alcohol solutions (methyl alcohol: quality is than 7:3) are divided into two equal portions a, b after mixing in proportion.Wherein a component directly adds in four-hole boiling flask, and b component adds 15 mass parts linking agents (ethylene glycol dimethacrylate) and mixes and be placed in constant pressure funnel.In flask, drip b mixed solution after logical nitrogen 70 DEG C stirs 2h, continue reaction 10h, obtain white emulsion, repeatedly centrifuge washing, room temperature is dried and is obtained described cross-linking type monodisperse polymer functional microsphere, carries out electron-microscope scanning, the results are shown in Figure 1 to it.
Embodiment 5: a kind of preparation of cross-linking type monodisperse polymer functional microsphere
100 mass parts acrylic ester monomers (90 parts of MMA, 10 parts of GMA), 3 mass parts initiators (Diisopropyl azodicarboxylate), 30 mass parts stablizers (Polyvinylpyrolidone (PVP)), 1000 mass parts alcohol solutions (methyl alcohol: quality is than 7:3) are divided into two equal portions a, b after mixing in proportion.Wherein a component directly adds in four-hole boiling flask, and b component adds 20 mass parts linking agents (ethylene glycol dimethacrylate) and mixes and be placed in constant pressure funnel.In flask, drip b mixed solution after logical nitrogen 70 DEG C stirs 2h, continue reaction 10h, obtain white emulsion, repeatedly centrifuge washing, room temperature is dried and is obtained described cross-linking type monodisperse polymer functional microsphere.
Embodiment 6: the Performance Detection of cross-linking type monodisperse polymer functional microsphere
Measure embodiment 1 ~ 5 and prepare the solvability of gained cross-linking type monodisperse polymer functional microsphere in different solvents, get 0.1g sample respectively and put into 30mL different solvents, the result of variations of observing emulsion color after half hour is as shown in table 1 below.
Control group is obtained by single stage method, method is as follows: 100 mass parts acrylic ester monomers (70 parts of MMA, 30 parts of GMA), 2 mass parts initiators (Diisopropyl azodicarboxylate), 20 mass parts stablizers (Polyvinylpyrolidone (PVP)), 800 mass parts alcohol solutions are directly added in four-hole boiling flask, logical nitrogen gas stirring for some time is placed on 70 DEG C of heating in water bath for reaction 12h, obtain white emulsion, centrifuge washing repeatedly, room temperature is dried, and obtains uncrosslinked monodisperse polymer functional microsphere.
The solvability of table 1 cross-linking type monodisperse polymer functional microsphere
| Tetrahydrofuran (THF) | Acetone | Toluene | Dimethylbenzene | Hexanaphthene | |
| Control group | Transparent | Transparent | Transparent | Transparent | Transparent |
| Embodiment 1 | Shallow milky white | Shallow milky white | Shallow milky white | Shallow milky white | Shallow milky white |
| Embodiment 2 | Oyster white | Oyster white | Oyster white | Oyster white | Oyster white |
| Embodiment 3 | Oyster white | Oyster white | Oyster white | Oyster white | Oyster white |
| Embodiment 4 | Oyster white | Oyster white | Oyster white | Oyster white | Oyster white |
| Embodiment 5 | Oyster white | Oyster white | Oyster white | Oyster white | Oyster white |
As can be seen from table 1 result, cross-linking type monodisperse polymer functional microsphere of the present invention has good solvent resistance.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a cross-linking type monodisperse polymer functional microsphere, is characterized in that the method by comprising the following steps prepares:
After acrylic ester monomer, initiator, stablizer and alcohol solution being mixed, be divided into A, B two parts, wherein component A adds linking agent and mixes, after heated and stirred, the component A being added with linking agent is added drop-wise in B component, isothermal reaction, obtains cross-linking type monodisperse polymer functional microsphere.
2. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: the mass ratio of acrylic ester monomer used, linking agent, initiator, stablizer and alcohol solution is 100:(5 ~ 20): (0.3 ~ 3): (0.5 ~ 30): (500 ~ 1000).
3. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: the condition of described isothermal reaction is 70 ~ 80 DEG C, reaction 10 ~ 24h.
4. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: described acrylic ester monomer is the mixture of methyl methacrylate monomer and glycidyl methacrylate monomer.
5. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: in described acrylic ester monomer, and the content of methyl methacrylate is 50 ~ 100wt%.
6. cross-linking type monodisperse polymer functional microsphere according to claim 1, it is characterized in that: described linking agent is ethylene glycol dimethacrylate, 1, at least one in 6-hexanediyl ester, tripropylene glycol diacrylate, 1,4 butanediol diacrylate and Vinylstyrene.
7. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: described initiator is at least one in azo-initiator and organic peroxy class initiator.
8. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: described stablizer is amphipathic nature polyalcohol.
9. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: described alcohol solution is the mixing solutions of a kind of and water in ethanol, methyl alcohol and Virahol.
10. cross-linking type monodisperse polymer functional microsphere according to claim 1, is characterized in that: described initiator is at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and dibenzoyl peroxide; Described stablizer is at least one in Polyvinylpyrolidone (PVP), hydroxypropylcellulose, polyacrylic acid and polyoxyethylene glycol; Described alcohol solution is methanol aqueous solution.
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| CN105462336A (en) * | 2015-11-25 | 2016-04-06 | 厦门大学 | Preparation method of nanopolyaniline-containing compound anti-corrosion coating auxiliary agent |
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| CN101168582A (en) * | 2007-10-17 | 2008-04-30 | 北京理工大学 | Method for preparing high cross-linking monodisperse polymer micro-sphere |
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
| 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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| CN101168582A (en) * | 2007-10-17 | 2008-04-30 | 北京理工大学 | Method for preparing high cross-linking monodisperse polymer micro-sphere |
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105462336A (en) * | 2015-11-25 | 2016-04-06 | 厦门大学 | Preparation method of nanopolyaniline-containing compound anti-corrosion coating auxiliary agent |
| CN105462336B (en) * | 2015-11-25 | 2018-11-13 | 厦门大学 | A kind of preparation method of the composite anticorrosion coating auxiliary agent containing nano polyaniline |
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Application publication date: 20151028 |