CN105399881A - Preparation method of monodispersed polymer microsphere - Google Patents

Preparation method of monodispersed polymer microsphere Download PDF

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Publication number
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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microspheres
preparation
reaction
prepared
particle size
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刘艳丽
李蕴翔
王晓东
慕建洲
李银
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Beijing Huoliyuan Technology Co Ltd
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Beijing Huoliyuan Technology Co Ltd
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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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

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

Preparation method of monodisperse polymer microspheres
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a preparation method of monodisperse polymer microspheres.
Background
The monodisperse polymer microsphere with large particle size and different particle forms and surface characteristics has special properties of large specific surface, strong adsorbability, large agglutination, surface reaction capability and the like, so the microsphere has extremely wide application prospect in the fields of standard measurement, immune medicine, bioengineering, analytical chemistry, chemical industry, microelectronics and the like. With the development of liquid crystal technology, the polymer microspheres have wide application prospects as spacing materials of liquid crystal displays. However, there are strict requirements for polymeric microspheres to be used as spacers for liquid crystal displays: the particle size is uniform, the relative standard deviation of the particle size is required to be below 4 percent, otherwise, the uniformity of the liquid crystal thickness cannot be maintained; the size is proper, and the particle size of the common microspheres is below 10 mu m; high purity to avoid the microsphere polluting liquid crystal; higher compressive strength and compression elasticity; and the coefficient of thermal expansion is similar to that of the liquid crystal material.
The dispersion polymerization process is a special type of precipitation polymerization process. The monomer, stabilizer and initiator are dissolved in the reaction medium, a homogeneous system is formed before the reaction, and the generated polymer product is not dissolved in the reaction medium and is precipitated. The dispersion polymerization method is an important method for preparing the polymer microspheres with micron-scale dimensions, in particular to an important method for preparing Polystyrene (PS) microspheres, because the monodispersity of the polystyrene microspheres prepared by the dispersion polymerization method is better under normal conditions. However, the main problems of the prior art are that the particle size of the prepared PS microspheres and the repeatability of the relative standard deviation thereof are poor, and the preparation process is difficult to control accurately.
Disclosure of Invention
In order to overcome the above-mentioned disadvantages of the prior art, the present invention is directed to a method for preparing monodisperse polymer microspheres.
The technical scheme is as follows:
a preparation method of monodisperse polymer microspheres comprises the following steps:
(1) adding monomers and an initiator of a polymer into a reaction vessel to carry out dispersion polymerization;
(2) and after reacting for 1-4 h, adding a polymerization inhibitor into the reaction system.
Wherein,
the step (1) is preceded by the steps of: (0) adding an organic solvent, a stabilizer and water into a reaction container, and heating and stirring until the temperature is 66-70 ℃.
The organic solvent is ethanol; the stabilizer is polyvinylpyrrolidone.
In the step (1), when the temperature in the reaction vessel rises to 66-70 ℃, timing is started, and the monomer and the initiator of the polymer are added into the reaction vessel after 0.5-1 h.
The monomer in the step (1) is styrene, and the initiator is azobisisobutyronitrile.
And (3) after the reaction for 2-3 hours, adding a polymerization inhibitor into the reaction system in the step (2).
The polymerization inhibitor in the step (2) is p-benzoquinone or p-tert-butylcatechol.
The mass ratio of the polymerization inhibitor to the monomer in the step (2) is 0.005-0.08%: 1.
the step (2) is followed by the steps of: (3) and after reacting for 15-18 h, storing the prepared monodisperse polymer microspheres into a reagent bottle.
The monodisperse polymer microspheres are polystyrene microspheres.
The dispersion polymerization method is a special type of precipitation polymerization method, wherein before the reaction, monomers, an initiator and a stabilizer are dissolved in a reaction medium, after the reaction, the polymer is subjected to homogeneous nucleation, and when polymer chain links reach a certain length, the polymer is separated out from the reaction medium and is stably dispersed in a solute by virtue of the stabilizer. In the initial stage of the reaction, the difference between the solubility parameter of the reaction medium and the solubility parameter of the polymer is small, the critical value of the chain length of the polymer is large, the nucleation rate is low, the concentration of the polymer monomer is relatively high, and the generated polymer particles are swelled by the monomer with higher concentration, so that the particle size is increased. As the particle size increases, the polymerization rate begins to increase, the growth of oligomers increases, and the relative rate at which the polymer particles capture oligomers and monomers slows, resulting in the combination of oligomers and stabilizers to form new particles, i.e., secondary nucleation. The invention effectively prevents the secondary nucleation by adding the polymerization inhibitor in the period, ensures the stable polymerization growth of the monomer on the primary core, and generates the microspheres with relatively uniform and regular particle size.
The basic principle of the invention is that polymerization inhibitor is added in the dispersion polymerization process of preparing monodisperse polymer microsphere, and the polymerization inhibitor prevents the occurrence of secondary core in the growing period of monodisperse polymer microsphere, so that the particle size and relative standard deviation of the prepared microsphere are far lower than those of the general method.
It should be noted that benzoquinone is actually used as a polymerization inhibitor in the above system, so that other chemical agents that can be converted into benzoquinone in the system can perform polymerization inhibition, for example, p-tert-butylcatechol, and therefore all other agents that can be converted into benzoquinone in the present reaction are within the scope of the present invention.
The invention has the beneficial effects that:
according to the preparation method of the monodisperse polymer microspheres, the polymerization inhibitor is added in the growth period of the polystyrene microspheres at a proper time, so that the prepared PS microspheres have the advantages of good monodispersity, small particle size deviation and good repeatability, and are suitable for batch preparation of the monodisperse polystyrene microspheres.
The PS microspheres prepared by the method are superior to PS microspheres prepared by a general method in the aspects of particle size and repeatability of particle size deviation, and the particle size deviation can be controlled to be below 4%.
Drawings
FIG. 1 is a transmission electron micrograph of PS microspheres prepared according to example 1.
FIG. 2 is a transmission electron micrograph of the PS microspheres prepared in example 2.
FIG. 3 is an optical micrograph of PS microspheres prepared according to example 4 at 100 Xmagnification.
FIG. 4 is an optical micrograph of PS microspheres prepared according to example 6 at 400 Xmagnification.
FIG. 5 is an optical micrograph of PS microspheres prepared according to example 7 at 400 Xmagnification.
FIG. 6 is an optical micrograph of PS microspheres prepared according to example 8 at 400 Xmagnification.
Detailed Description
The invention will be further described with reference to specific embodiments and drawings which will make the invention more comprehensible and advantageous, but in no way limiting thereof.
The invention relates to a preparation method of monodisperse polymer microspheres, which comprises the following steps:
(0) adding ethanol, polyvinylpyrrolidone and water into a reaction container, and heating and stirring until the temperature is 66-70 ℃;
(1) adding styrene and azodiisobutyronitrile into the reaction vessel after timing for 0.5-1 h, and carrying out dispersion polymerization reaction;
(2) after reacting for 1-4 h, adding a polymerization inhibitor (p-benzoquinone or p-tert-butylcatechol) into the reaction system, wherein the mass ratio of the polymerization inhibitor to the monomer is 0.005-0.08%: 1;
(3) and after reacting for 15-18 h, storing the prepared polystyrene microspheres into a reagent bottle.
Example 1
A preparation method of monodisperse polymer microspheres comprises the following steps:
(0) adding 200mL of ethanol, 5.4g of polyvinylpyrrolidone and 160mL of water into a reaction vessel, and heating and stirring until the temperature is 66 ℃;
(1) timing for 1 hour, adding 187mL of styrene and 3.0g of azobisisobutyronitrile into the reaction vessel, and carrying out dispersion polymerization;
(2) after reacting for 1h, adding 0.01g of p-benzoquinone into the reaction system;
(3) after reacting for 15h, the prepared polystyrene microspheres are stored in a reagent bottle.
The transmission electron micrograph of the prepared polystyrene microsphere is shown in figure 1, and as can be seen from figure 1, the PS microsphere prepared by the method disclosed by the invention is in a regular spherical shape, the surface is smooth, no agglomeration exists among the microspheres, and the monodispersity of the PS microsphere is very good.
As measured from the microspheres in fig. 1, the average particle size of the PS microspheres prepared in this example is: d is 2.93 μm, and the particle size deviation is: cv＝2.71％。
Example 2
A preparation method of monodisperse polymer microspheres comprises the following steps:
(0) adding 200mL of ethanol, 5.4g of polyvinylpyrrolidone and 160mL of water into a reaction vessel, and heating and stirring until the temperature is 69 ℃;
(1) timing for 0.5h, adding 187mL of styrene and 3.0g of azobisisobutyronitrile into the reaction vessel, and carrying out dispersion polymerization;
(2) after reacting for 2h, adding 0.12g of p-tert-butylcatechol into the reaction system;
(3) after reacting for 18h, the prepared polystyrene microspheres are stored in a reagent bottle.
The transmission electron micrograph of the prepared polystyrene microsphere is shown in FIG. 2, and as can be seen from FIG. 2, the PS microsphere prepared by the method of the invention is in a regular spherical shape, the surface is smooth, no agglomeration exists among the microspheres, and the monodispersity of the PS microsphere is very good.
As measured from the microspheres in fig. 2, the average particle size of the PS microspheres prepared in this example is: d is 2.91 μm, and the particle size deviation is: cv＝2.64％。
Example 3
A preparation method of monodisperse polymer microspheres comprises the following steps:
(0) adding 200mL of ethanol, 5.4g of polyvinylpyrrolidone and 160mL of water into a reaction vessel, and heating and stirring until the temperature is 67 ℃;
(1) timing for 40min, adding 187mL of styrene and 3.0g of azobisisobutyronitrile into the reaction vessel, and carrying out dispersion polymerization;
(2) after reacting for 3 hours, adding 0.06g of p-benzoquinone into the reaction system;
(3) after reacting for 16h, the prepared polystyrene microspheres are stored in a reagent bottle.
The average particle size of the polystyrene microspheres prepared above is measured as follows: d is 2.85 μm, and the particle size deviation is: cv＝2.07％。
Example 4
A preparation method of monodisperse polymer microspheres comprises the following steps:
(0) adding 200mL of ethanol, 5.4g of polyvinylpyrrolidone and 160mL of water into a reaction vessel, and heating and stirring until the temperature is 70 ℃;
(1) timing for 50min, adding 187mL of styrene and 3.0g of azobisisobutyronitrile into the reaction vessel, and carrying out dispersion polymerization;
(2) after reacting for 4 hours, adding 0.08g of p-tert-butylcatechol into the reaction system;
(3) after reacting for 17h, the prepared polystyrene microspheres are stored in a reagent bottle.
An optical microscope photograph (magnification is 100X) of the prepared polystyrene microspheres is shown in FIG. 3, and as can be seen from FIG. 3, the PS microspheres prepared by the method of the present invention are arranged into an ordered array, which shows that the particle sizes of the prepared PS microspheres have high uniformity and small relative standard deviation.
The PS microspheres prepared in this example were measured to have an average particle size of: d is 2.88 μm, and the particle size deviation is: cv＝2.36％。
Example 5
A preparation method of monodisperse polymer microspheres comprises the following steps:
(0) adding 200mL of ethanol, 5.4g of polyvinylpyrrolidone and 160mL of water into a reaction vessel, and heating and stirring until the temperature is 68 ℃;
(1) timing for 1 hour, adding 187mL of styrene and 3.0g of azobisisobutyronitrile into the reaction vessel, and carrying out dispersion polymerization;
(2) after reacting for 4h, adding 0.12g of p-benzoquinone into the reaction system;
(3) after reacting for 16h, the prepared polystyrene microspheres are stored in a reagent bottle.
The average particle size of the polystyrene microspheres prepared above is measured as follows: d is 2.97 μm, and the particle size deviation is: cv＝2.53％。
Example 6
A preparation method of monodisperse polymer microspheres comprises the following steps:
(0) adding 200mL of ethanol, 5.4g of polyvinylpyrrolidone and 160mL of water into a reaction vessel, and heating and stirring until the temperature is 66 ℃;
(1) timing for 0.5h, adding 187mL of styrene and 3.0g of azobisisobutyronitrile into the reaction vessel, and carrying out dispersion polymerization;
(2) after reacting for 3 hours, adding 0.04g of p-tert-butylcatechol into the reaction system;
(3) after reacting for 18h, the prepared polystyrene microspheres are stored in a reagent bottle.
An optical microscope photograph (magnification is 400X) of the polystyrene microspheres prepared in the above way is shown in FIG. 4, and as can be seen more intuitively from FIG. 4, the PS microspheres prepared by the method of the present invention are orderly arranged, and the monodispersity of the microspheres is very good, and the deviation of the particle size is very small.
The PS microspheres prepared in this example were measured to have an average particle size of: d is 2.90 μm, and the particle size deviation is: cv＝2.22％。
Example 7 (comparative example 1)
The reaction procedure was the same as in example 1 except that p-benzoquinone was not added in step (2).
An optical microscope photograph (magnification is 400X) of the prepared polystyrene microsphere is shown in fig. 5, and as can be seen from fig. 5, the prepared PS microsphere has poor monodispersity, obviously non-uniform particle size, large particle size deviation, and a large number of microspheres are difficult to arrange into an ordered array.
The PS microspheres prepared in this example were measured to have an average particle size of: d is 3.47 μm, and the particle size deviation is: cv＝7.52％。
Example 8 (comparative example 2)
The procedure was as in example 2 except that no p-tert-butylcatechol was added in step (2).
An optical microscope photograph (magnification is 400X) of the prepared polystyrene microspheres is shown in fig. 6, and as can be seen from fig. 6, the prepared PS microspheres have poor monodispersity, obviously non-uniform particle size and large particle size deviation, and a large number of microspheres are difficult to arrange into an ordered array.
The PS microspheres prepared in this example were measured to have an average particle size of: d is 3.39 μm, and the particle size deviation is: cv＝8.76％。
The above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the foregoing embodiments illustrate the present invention in detail, those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (10)

1. A preparation method of monodisperse polymer microspheres is characterized by comprising the following steps:
(1) adding monomers and an initiator of a polymer into a reaction vessel to carry out dispersion polymerization;
(2) and after reacting for 1-4 h, adding a polymerization inhibitor into the reaction system.
2. The method for preparing monodisperse polymer microspheres according to claim 1, wherein step (1) is preceded by the steps of: (0) adding an organic solvent, a stabilizer and water into a reaction container, and heating and stirring until the temperature is 66-70 ℃.
3. The method of claim 2, wherein the organic solvent is ethanol; the stabilizer is polyvinylpyrrolidone.
4. The method for preparing monodisperse polymer microspheres according to claim 1, wherein in step (1), when the temperature in the reaction vessel is increased to 66-70 ℃ and the time is started, the monomers of the polymer and the initiator are added into the reaction vessel after 0.5-1 h.
5. The method for preparing monodisperse polymer microspheres according to claim 1, wherein the monomer in step (1) is styrene, and the initiator is azobisisobutyronitrile.
6. The preparation method of monodisperse polymer microspheres according to claim 1, wherein polymerization inhibitor is added into the reaction system after the reaction in step (2) is carried out for 2-3 hours.
7. The method for preparing monodisperse polymer microspheres according to claim 1, wherein the polymerization inhibitor in step (2) is p-benzoquinone or p-tert-butylcatechol.
8. The method for preparing monodisperse polymer microspheres according to claim 1, wherein the mass ratio of polymerization inhibitor to monomer in step (2) is 0.005-0.08%: 1.
9. the method of claim 1, further comprising the step of, after the step (2): (3) and after reacting for 15-18 h, storing the prepared monodisperse polymer microspheres into a reagent bottle.
10. The method of claim 9, wherein the monodisperse polymeric microspheres are polystyrene microspheres.
CN201510964513.9A 2015-12-21 2015-12-21 Preparation method of monodispersed polymer microsphere Pending CN105399881A (en)

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Publication number Priority date Publication date Assignee Title
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CN1663970A (en) * 2005-03-02 2005-09-07 东南大学 Method for preparing mono dispersed functionalized polymer microsphere
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