CN105399881A - Preparation method of monodispersed polymer microsphere - Google Patents
Preparation method of monodispersed polymer microsphere Download PDFInfo
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- CN105399881A CN105399881A CN201510964513.9A CN201510964513A CN105399881A CN 105399881 A CN105399881 A CN 105399881A CN 201510964513 A CN201510964513 A CN 201510964513A CN 105399881 A CN105399881 A CN 105399881A
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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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
- C08F2/08—Organic solvent with the aid of dispersing agents for the polymer
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
Abstract
The present invention discloses a preparation method of monodispersed polymer microsphere, and belongs to the technical field of the preparation of polymers. The method of the invention comprises the steps of: adding an organic solvent, a stabilizer and water into a reaction vessel and heating with stirring; then adding a polymer monomer and an initiator, and conducting dispersion polymerization reaction; reacting for 1-4 h, and adding a polymerization inhibitor to the system; and after the reaction, preserving the prepared monodispersed polymer microspheres in a reagent bottle. According to the preparation method of the monodispersed polymer microspheres provided by the invention, the polymerization inhibitor is added timely in the growth period of polystyrene microspheres, so that the prepared monodispersed microspheres have the advantages of good monodispersion, small particle size variation and good reproducibility; and the method is applicable to the bulk preparation of monodispersed polystyrene microspheres.
Description
Technical field
The invention belongs to technical field of polymer preparation, particularly relate to a kind of preparation method of monodisperse polymer micro-sphere.
Background technology
Single dispersing, Large stone, specific surface is large, adsorptivity is strong, agglutination is large and have the specific physiques such as surface reaction ability because having to have the polymer microballoon of variable grain form and surface characteristic, therefore has extremely wide application prospect in fields such as standard metering, immune medical science, biotechnology, analytical chemistry, chemical industry and microelectronics.Along with the development of liquid crystal technology, the interval insulant that polymer microballoon is used as liquid-crystal display has a wide range of applications.But have strict requirement for the polymer microballoon being used as liquid-crystal display spacer: uniform particle diameter, particle diameter relative standard deviation requires below 4%, otherwise cannot keep the homogeneity of thickness of liquid crystal; Size is suitable, and the particle diameter of general conventional microballoon is all below 10 μm; High purity, pollutes liquid crystal to avoid microballoon; Higher compressive strength and the elasticity of compression; With the similar thermal expansion coefficient etc. of liquid crystal material.
Dispersion copolymerization method is a kind of precipitation polymerization process of specific type.Be dissolved in reaction medium by monomer, stablizer and initiator, be homogeneous system before reaction, the polymeric articles generated does not dissolve in reaction medium, thus is precipitated out.Dispersion copolymerization method is a kind of important method preparing micron order yardstick polymer microballoon, particularly prepare the important method of polystyrene (PS) microballoon, this is due under normal circumstances, and the monodispersity of polystyrene microsphere prepared by dispersion copolymerization method is better.But subject matter existing is at present obtained PS microspherulite diameter and the poor repeatability of relative standard deviation thereof, and is difficult to accurate control in preparation process.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of monodisperse polymer micro-sphere.
The technical scheme adopted is as follows:
A preparation method for monodisperse polymer micro-sphere, comprises the following steps:
(1) in reaction vessel, add monomer and the initiator of polymkeric substance, carry out dispersion polymerization;
(2), after reacting 1 ~ 4h, in reaction system, stopper is added.
Wherein,
Also step is comprised: organic solvent, stablizer and water join in reaction vessel by (0) before described step (1), and the stirring that heats up, be 66 ~ 70 DEG C to temperature.
Described organic solvent is ethanol; Described stablizer is Polyvinylpyrolidone (PVP).
Described step starts timing in (1) after the temperature in reaction vessel rises to 66 ~ 70 DEG C, adds monomer and the initiator of polymkeric substance after 0.5 ~ 1h in reaction vessel.
Monomer in described step (1) is vinylbenzene, and initiator is Diisopropyl azodicarboxylate.
Described step (2), after reaction 2 ~ 3h, adds stopper in reaction system.
Stopper in described step (2) is para benzoquinone or p-ten.-butylcatechol.
In described step (2), the mass ratio of stopper and monomer is 0.005% ~ 0.08%:1.
Also step is comprised: after (3) reaction 15 ~ 18h, obtained monodisperse polymer micro-sphere is saved to reagent bottle after described step (2).
Described monodisperse polymer micro-sphere is polystyrene microsphere.
Above-mentioned dispersion copolymerization method is a kind of precipitation polymerization process of specific type, before reaction starts, monomer, initiator and stablizer are dissolved in reaction medium, after reaction starts, polymkeric substance homogeneous nucleation, just can separate out from reaction medium after polymkeric substance chain link reaches certain length, and stably be dispersed in solute by means of stablizer.Initial reaction stage, the difference of the solubility parameters of reaction medium and the solubility parameters of polymkeric substance is little, and the chain length threshold value of polymkeric substance is large, nucleation rate is low, and the relative concentration of polymer monomer is higher, the polymer particle of generation is by the higher monomer swell of concentration, and then particle diameter increases.Along with the increase of particle diameter, polymerization rate starts to accelerate, and the growth of oligopolymer is accelerated, and the speed of relative movement that polymer beads catches oligopolymer and monomer slows down, and causes oligopolymer and stablizer to combine and generates new particle, i.e. secondary nucleation.The appearance of the particle that secondary nucleation causes, have impact on the consistence of the grain diameter that whole dispersion polymerization produces, the present invention is by the phase adds stopper at this moment, realize the effective prevention to secondary nucleation, guarantee monomer stably aggregation growth in a core, thus generate the microballoon with relatively uniform and neat particle diameter.
Ultimate principle of the present invention is by adding stopper in the dispersion polymerization process preparing monodisperse polymer micro-sphere, stoped the appearance of secondary core in monodisperse polymer micro-sphere vegetative period by stopper, thus make the particle diameter of the microballoon obtained and relative standard deviation far below general method.
It should be noted that; in above-mentioned system, actual performance inhibition is benzoquinones; so other chemical reagent that can be transformed into benzoquinones in system can play inhibition; such as p-ten.-butylcatechol, therefore other all reagent that can be transformed into benzoquinones are in the present reaction all in protection scope of the present invention.
Beneficial effect of the present invention:
The preparation method of monodisperse polymer micro-sphere provided by the invention, add stopper by the vegetative period at polystyrene microsphere in good time, make the PS microballoon of preparation have the advantage that monodispersity is good, particle diameter deviation is little, reproducible, be applicable to the batch preparation of monodisperse polystyrene microsphere.
The PS microballoon prepared of the inventive method particle diameter and particle diameter deviation repeated in be better than the obtained PS microballoon of general method, and particle diameter deviation can control below 4%.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of PS microballoon prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of PS microballoon prepared by embodiment 2.
Fig. 3 is the optical microscope photograph of PS microballoon prepared by embodiment 4, and magnification is 100X.
Fig. 4 is the optical microscope photograph of PS microballoon prepared by embodiment 6, and magnification is 400X.
Fig. 5 is the optical microscope photograph of PS microballoon prepared by embodiment 7, and magnification is 400X.
Fig. 6 is the optical microscope photograph of PS microballoon prepared by embodiment 8, and magnification is 400X.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention will be further described, can make content of the present invention and advantage more clear, but not limit the present invention in any way.
The preparation method of a kind of monodisperse polymer micro-sphere of the present invention, comprises the following steps:
(0) ethanol, Polyvinylpyrolidone (PVP) and water are joined in reaction vessel, and the stirring that heats up, be 66 ~ 70 DEG C to temperature;
(1) in reaction vessel, add vinylbenzene and Diisopropyl azodicarboxylate after timing 0.5 ~ 1h, carry out dispersion polymerization;
(2), after reacting 1 ~ 4h, in reaction system, add stopper (para benzoquinone or p-ten.-butylcatechol), the mass ratio of stopper and monomer is 0.005% ~ 0.08%:1;
(3), after reacting 15 ~ 18h, obtained polystyrene microsphere is saved to reagent bottle.
Embodiment 1
A preparation method for monodisperse polymer micro-sphere, comprises the following steps:
(0) 200mL ethanol, 5.4g Polyvinylpyrolidone (PVP) and 160mL water are joined in reaction vessel, and the stirring that heats up, be 66 DEG C to temperature;
(1) in reaction vessel, add 187mL vinylbenzene and 3.0g Diisopropyl azodicarboxylate after timing 1h, carry out dispersion polymerization;
(2), after reacting 1h, in reaction system, 0.01g para benzoquinone is added;
(3), after reacting 15h, obtained polystyrene microsphere is saved to reagent bottle.
As shown in Figure 1, as seen from Figure 1, PS microballoon prepared by the inventive method presents just spherical the transmission electron microscope photo of the polystyrene microsphere of above-mentioned preparation, smooth surface, soilless sticking between microballoon, and the monodispersity of PS microballoon is very good.
Carry out measurement to the microballoon in Fig. 1 can obtain, the median size of PS microballoon prepared by the present embodiment is: d=2.93 μm, particle diameter deviation is: C
v=2.71%.
Embodiment 2
A preparation method for monodisperse polymer micro-sphere, comprises the following steps:
(0) 200mL ethanol, 5.4g Polyvinylpyrolidone (PVP) and 160mL water are joined in reaction vessel, and the stirring that heats up, be 69 DEG C to temperature;
(1) in reaction vessel, add 187mL vinylbenzene and 3.0g Diisopropyl azodicarboxylate after timing 0.5h, carry out dispersion polymerization;
(2), after reacting 2h, in reaction system, 0.12g p-ten.-butylcatechol is added;
(3), after reacting 18h, obtained polystyrene microsphere is saved to reagent bottle.
As shown in Figure 2, as seen from Figure 2, PS microballoon prepared by the inventive method presents just spherical the transmission electron microscope photo of the polystyrene microsphere of above-mentioned preparation, smooth surface, soilless sticking between microballoon, and the monodispersity of PS microballoon is very good.
Carry out measurement to the microballoon in Fig. 2 can obtain, the median size of PS microballoon prepared by the present embodiment is: d=2.91 μm, particle diameter deviation is: C
v=2.64%.
Embodiment 3
A preparation method for monodisperse polymer micro-sphere, comprises the following steps:
(0) 200mL ethanol, 5.4g Polyvinylpyrolidone (PVP) and 160mL water are joined in reaction vessel, and the stirring that heats up, be 67 DEG C to temperature;
(1) in reaction vessel, add 187mL vinylbenzene and 3.0g Diisopropyl azodicarboxylate after timing 40min, carry out dispersion polymerization;
(2), after reacting 3h, in reaction system, 0.06g para benzoquinone is added;
(3), after reacting 16h, obtained polystyrene microsphere is saved to reagent bottle.
Through measuring, the median size of the polystyrene microsphere of above-mentioned preparation is: d=2.85 μm, and particle diameter deviation is: C
v=2.07%.
Embodiment 4
A preparation method for monodisperse polymer micro-sphere, comprises the following steps:
(0) 200mL ethanol, 5.4g Polyvinylpyrolidone (PVP) and 160mL water are joined in reaction vessel, and the stirring that heats up, be 70 DEG C to temperature;
(1) in reaction vessel, add 187mL vinylbenzene and 3.0g Diisopropyl azodicarboxylate after timing 50min, carry out dispersion polymerization;
(2), after reacting 4h, in reaction system, 0.08g p-ten.-butylcatechol is added;
(3), after reacting 17h, obtained polystyrene microsphere is saved to reagent bottle.
The optical microscope photograph (magnification is 100X) of the polystyrene microsphere of above-mentioned preparation as shown in Figure 3, as seen from Figure 3, PS arrangement of microspheres prepared by the inventive method becomes oldered array, and show that the PS microspherulite diameter obtained has very high consistence, relative standard deviation is little.
Through measuring, the median size of PS microballoon prepared by the present embodiment is: d=2.88 μm, particle diameter deviation is: C
v=2.36%.
Embodiment 5
A preparation method for monodisperse polymer micro-sphere, comprises the following steps:
(0) 200mL ethanol, 5.4g Polyvinylpyrolidone (PVP) and 160mL water are joined in reaction vessel, and the stirring that heats up, be 68 DEG C to temperature;
(1) in reaction vessel, add 187mL vinylbenzene and 3.0g Diisopropyl azodicarboxylate after timing 1h, carry out dispersion polymerization;
(2), after reacting 4h, in reaction system, 0.12g para benzoquinone is added;
(3), after reacting 16h, obtained polystyrene microsphere is saved to reagent bottle.
Through measuring, the median size of the polystyrene microsphere of above-mentioned preparation is: d=2.97 μm, and particle diameter deviation is: C
v=2.53%.
Embodiment 6
A preparation method for monodisperse polymer micro-sphere, comprises the following steps:
(0) 200mL ethanol, 5.4g Polyvinylpyrolidone (PVP) and 160mL water are joined in reaction vessel, and the stirring that heats up, be 66 DEG C to temperature;
(1) in reaction vessel, add 187mL vinylbenzene and 3.0g Diisopropyl azodicarboxylate after timing 0.5h, carry out dispersion polymerization;
(2), after reacting 3h, in reaction system, 0.04g p-ten.-butylcatechol is added;
(3), after reacting 18h, obtained polystyrene microsphere is saved to reagent bottle.
The optical microscope photograph (magnification is 400X) of the polystyrene microsphere of above-mentioned preparation as shown in Figure 4, from Fig. 4 more intuitively, PS arrangement of microspheres prepared by the inventive method is orderly, and the monodispersity of microballoon is very good, and particle diameter deviation is very little.
Through measuring, the median size of PS microballoon prepared by the present embodiment is: d=2.90 μm, particle diameter deviation is: C
v=2.22%.
Embodiment 7 (comparative example 1)
Reaction process is identical with embodiment 1, just in step (2), does not add para benzoquinone.
The optical microscope photograph (magnification is 400X) of the polystyrene microsphere of above-mentioned preparation as shown in Figure 5, as seen from Figure 5, the monodispersity of obtained PS microballoon is poor, and particle diameter exists obvious disunity, particle diameter deviation is comparatively large, and a large amount of microballoon is difficult to line up oldered array.
Through measuring, the median size of PS microballoon prepared by the present embodiment is: d=3.47 μm, particle diameter deviation is: C
v=7.52%.
Embodiment 8 (comparative example 2)
Reaction process is identical with embodiment 2, just in step (2), does not add p-ten.-butylcatechol.
The optical microscope photograph (magnification is 400X) of the polystyrene microsphere of above-mentioned preparation as shown in Figure 6, as seen from Figure 6, the monodispersity of obtained PS microballoon is poor, and particle diameter exists obvious disunity, particle diameter deviation is comparatively large, and a large amount of microballoon is difficult to line up oldered array.
Through measuring, the median size of PS microballoon prepared by the present embodiment is: d=3.39 μm, particle diameter deviation is: C
v=8.76%.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited.Although previous embodiment is to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of technical solution of the present invention.
Claims (10)
1. a preparation method for monodisperse polymer micro-sphere, is characterized in that, comprises the following steps:
(1) in reaction vessel, add monomer and the initiator of polymkeric substance, carry out dispersion polymerization;
(2), after reacting 1 ~ 4h, in reaction system, stopper is added.
2. the preparation method of monodisperse polymer micro-sphere according to claim 1, it is characterized in that, also step is comprised: organic solvent, stablizer and water join in reaction vessel by (0) before described step (1), and the stirring that heats up, be 66 ~ 70 DEG C to temperature.
3. the preparation method of monodisperse polymer micro-sphere according to claim 2, is characterized in that, described organic solvent is ethanol; Described stablizer is Polyvinylpyrolidone (PVP).
4. the preparation method of monodisperse polymer micro-sphere according to claim 1, it is characterized in that, described step starts timing in (1) after the temperature in reaction vessel rises to 66 ~ 70 DEG C, adds monomer and the initiator of polymkeric substance after 0.5 ~ 1h in reaction vessel.
5. the preparation method of monodisperse polymer micro-sphere according to claim 1, is characterized in that, the monomer in described step (1) is vinylbenzene, and initiator is Diisopropyl azodicarboxylate.
6. the preparation method of monodisperse polymer micro-sphere according to claim 1, is characterized in that, described step (2), after reaction 2 ~ 3h, adds stopper in reaction system.
7. the preparation method of monodisperse polymer micro-sphere according to claim 1, is characterized in that, the stopper in described step (2) is para benzoquinone or p-ten.-butylcatechol.
8. the preparation method of monodisperse polymer micro-sphere according to claim 1, is characterized in that, in described step (2), the mass ratio of stopper and monomer is 0.005% ~ 0.08%:1.
9. the preparation method of monodisperse polymer micro-sphere according to claim 1, is characterized in that, also comprises step after described step (2): after (3) reaction 15 ~ 18h, obtained monodisperse polymer micro-sphere is saved to reagent bottle.
10. the preparation method of monodisperse polymer micro-sphere according to claim 9, is characterized in that, described monodisperse polymer micro-sphere is polystyrene microsphere.
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| CN103159878A (en) * | 2013-04-03 | 2013-06-19 | 湖南科技大学 | Simple method for preparing monodisperse cationic polystyrene microspheres |
| WO2014120172A1 (en) * | 2013-01-31 | 2014-08-07 | Empire Technology Development Llc | Light weight structural materials |
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|---|---|---|---|---|
| CN1587286A (en) * | 2004-07-08 | 2005-03-02 | 清华大学 | Radiation dispersion polymerization process of phenylethylene micro ball |
| CN1663970A (en) * | 2005-03-02 | 2005-09-07 | 东南大学 | Method for preparing mono dispersed functionalized polymer microsphere |
| CN1876688A (en) * | 2006-05-22 | 2006-12-13 | 深圳华明科技有限公司 | Method for preparing mono dispersed micrograde polymer microsphere |
| CN102649826A (en) * | 2011-02-25 | 2012-08-29 | 常州均益新材料科技有限公司 | Preparation method of particle diameter controllable monodisperse polystyrene microspheres |
| WO2014120172A1 (en) * | 2013-01-31 | 2014-08-07 | Empire Technology Development Llc | Light weight structural materials |
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