CN114456321A - Polymer microsphere with core-shell structure and preparation method and application thereof - Google Patents

Polymer microsphere with core-shell structure and preparation method and application thereof Download PDF

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CN114456321A
CN114456321A CN202011132784.5A CN202011132784A CN114456321A CN 114456321 A CN114456321 A CN 114456321A CN 202011132784 A CN202011132784 A CN 202011132784A CN 114456321 A CN114456321 A CN 114456321A
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monomer
polymer
maleic anhydride
solvent
shell structure
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计文希
张韬毅
李娟�
许宁
姚雪容
陈婧
张龙贵
王蔼廉
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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    • C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
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    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract

The invention belongs to the technical field of high-molecular fluorescent materials, and discloses a polymer microsphere with a core-shell structure, and a preparation method and application thereof. The polymeric microspheres include a first polymeric shell structure and a second polymeric core structure; wherein the second polymer core structure is a copolymer of styrenic monomer A and maleic anhydride monomer. According to the invention, a polystyrene maleic anhydride chain segment is introduced into the microsphere, and the polystyrene maleic anhydride chain segment is an aggregated luminescent group, so that fluorescence and phosphorescence can be generated through electronic transition under the action of light.

Description

Polymer microsphere with core-shell structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of high-molecular fluorescent materials, in particular to a polymer microsphere with a core-shell structure, and a preparation method and application thereof.
Background
The polymer fluorescent material has good application prospect, and is a research hotspot in the field of material science in recent years. The application modes of the organic fluorescent polymer material mainly include three types: 1) fluorescent polymer microspheres; 2) a fluorescent polymer film; 3) fluorescent polymer plate. The polymer fluorescent microspheres are mainly studied. The preparation method of the polymer fluorescent microsphere mainly comprises an adsorption method, an embedding method, a chemical coupling method, a swelling method, a copolymerization method and the like.
For example, the high-quality quantum dots are prepared firstly, and then the fluorescent microspheres with the particle size of 1-10 microns can be obtained by coating the quantum dots in the polystyrene microspheres by adopting a dispersion polymerization method. However, quantum dots in the fluorescent microspheres prepared by the method are easy to leak, and can cause sample pollution when in use. The chemical coupling method is to bond dye molecules to the surface of the microsphere through chemical reaction, and is easily limited by the number of binding sites on the surface of the microsphere, and meanwhile, fluorescent dye molecules are easily interfered by the environment; the copolymerization method refers to a fluorescent microsphere prepared by polymerization reaction of a fluorescent substance with polymerizable functional groups and an organic monomer, the fluorescent groups are uniformly distributed and are not easy to leak, but the copolymerization method has the problem that a chain transfer reaction is easy to generate and a high-molecular-weight polymer is not easy to obtain. For example, vinylcarbazole, dansyl chloride allylamine and styrene are used as raw materials, and a dispersion polymerization method is adopted to prepare the fluorescent microsphere, however, the fluorescent microsphere has no functional group and is not easy to be combined with subsequent biology.
Disclosure of Invention
The invention aims to provide a polymer microsphere with a core-shell structure and a preparation method thereof. By adjusting the length of chain segments and the size of aggregates, the fluorescence intensity and the quantum yield of the microspheres can be adjusted within a certain range. The polymer microsphere product prepared by the invention has great application potential in the fields of biomedicine, electronic luminescent devices and the like.
A first aspect of the present invention provides a polymeric microsphere with a core-shell structure, the polymeric microsphere comprising a first polymeric shell structure and a second polymeric core structure; wherein the second polymer core structure is a copolymer of styrenic monomer A and maleic anhydride monomer.
The second aspect of the present invention provides a method for preparing polymer microspheres, comprising the steps of:
in the presence of a first solvent, carrying out a first-stage polymerization reaction on a chain transfer agent, an initiator and a first free radical polymerization monomer; then directly adding a styrene monomer A and a maleic anhydride monomer to carry out second-stage polymerization reaction, or adding the styrene monomer A, the maleic anhydride monomer and a second solvent after separation and purification to carry out second-stage polymerization reaction to obtain polymer microspheres;
wherein, when direct addition of styrenic monomer A and maleic anhydride monomer is selected, the first solvent comprises a selective solvent and optionally a non-selective solvent; when a separation and purification process is selected, the first solvent comprises a selective solvent and/or a non-selective solvent;
the second solvent is a selective solvent.
In a third aspect of the present invention, there is provided a polymeric microsphere produced by the above-mentioned production method.
In a fourth aspect, the present invention provides the use of the above-described polymeric microspheres as a light conversion agent and/or toughening agent.
The technical scheme of the invention has the following beneficial effects:
(1) according to the invention, a polystyrene maleic anhydride chain segment is introduced into the microsphere, and the polystyrene maleic anhydride chain segment is an aggregated luminescent group and can generate fluorescence and phosphorescence under the action of light through electron transition; meanwhile, the core of the polymer microsphere is styrene maleic anhydride copolymer, and the polymer microsphere has the characteristics of heat resistance and the like.
(2) The polymer microsphere is a copolymer, has the characteristics of stable structure and size, and is adjustable in size from 10nm to 500 nm.
(3) The polymer microsphere of the invention has wide application, can be used as a light conversion agent or a toughening agent, and has great application potential in the fields of biomedicine, electronic luminescent devices, polymer processing aids and the like.
(4) Compared with the prior art, the preparation method has the characteristics of simple synthesis steps, easily obtained monomers, cheap raw materials and the like; furthermore, when the polymer microsphere is used as a light conversion agent, the polymer microsphere has good fluorescence effect and lower cost.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
FIG. 1 shows a schematic structural morphology of the polymeric microspheres of the present invention.
Description of reference numerals:
1. a second polymer core structure, 2, a first polymer shell structure.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The first aspect of the present invention provides a polymer microsphere with a core-shell structure, which comprises a first polymer shell structure and a second polymer core structure; wherein the second polymer core structure is a copolymer of styrenic monomer A and maleic anhydride monomer.
The polymer microsphere with the core-shell structure can generate 400-600nm fluorescence under the excitation of laser.
The structural morphology of the polymeric microspheres of the present invention can be shown in fig. 1.
According to the present invention, preferably, the degree of polymerization of the first polymer shell structure is 5 to 500, preferably 20 to 100.
According to the present invention, preferably, the first polymeric shell structure is a homopolymer or copolymer of a styrenic monomer B and/or an acrylate monomer; preferably polystyrene or polyacrylate.
In the present invention, the acrylate monomer is preferably acrylate and/or methacrylate.
In the present invention, the styrenic monomer B may be the same as or different from the styrenic monomer a, and the styrenic monomer B is preferably styrene and/or α -methylstyrene.
According to the invention, preferably, the styrene monomer A is a compound shown as a formula I;
Figure BDA0002735688950000041
wherein R is6Is substituted or unsubstitutedC of (A)6-C20The aryl group is at least one of halogen, alkyl and alkoxy, and the aryl group is phenyl, biphenyl, naphthyl or anthryl.
According to the present invention, preferably, the diameter of the polymeric microspheres is 10 to 500 nm.
The second aspect of the present invention provides a method for preparing the above-mentioned polymeric microspheres, comprising the steps of:
in the presence of a first solvent, carrying out a first-stage polymerization reaction on a chain transfer agent, an initiator and a first free radical polymerization monomer; then directly adding a styrene monomer A and a maleic anhydride monomer to carry out second-stage polymerization reaction, or adding the styrene monomer A, the maleic anhydride monomer and a second solvent after separation and purification to carry out second-stage polymerization reaction to obtain polymer microspheres;
wherein, when direct addition of styrenic monomer A and maleic anhydride monomer is selected, the first solvent comprises a selective solvent and optionally a non-selective solvent; when a separation and purification process is selected, the first solvent comprises a selective solvent and/or a non-selective solvent;
the second solvent is a selective solvent.
In the invention, the styrene monomer A and the maleic anhydride monomer are directly added, and can be respectively added; or the styrene monomer A, the maleic anhydride monomer and the selective solvent are uniformly mixed to obtain a monomer mixed solution, and then the monomer mixed solution is added.
The preparation method of the invention is not limited to initiating polymerization reaction by using an initiator, and can also initiate polymerization reaction under the condition of heating or ultraviolet illumination; the polymerization is preferably initiated using an initiator.
The invention uses a polymerization-induced self-assembly method, takes polystyrene maleic anhydride copolymer as a core, and carries out polymerization in a non-benign solvent to obtain the polystyrene maleic anhydride core microsphere.
The polymerization-induced self-assembly (PISA) combines the CRP method and the self-assembly property of the block polymer, can prepare the nanometer microsphere with a core-shell structure by a one-step method, has the characteristics of rich applicable monomers, high solid content (the concentration of the nanometer microsphere is more than 20 percent) and the like, can industrially produce nanometer materials on a large scale, can obtain non-spherical nanometer structures, can be used as polymer processing aids, photoelectric materials and the like, and can bring anisotropy to the materials by the non-spherical structures. The technology of 'living'/controlled radial polymerization, LRP/CRP, is a new polymerization means, has the advantages of both anionic polymerization method and free radical polymerization method, realizes the controlled polymerization of free radical polymerization, is an upgrading technology of the free radical polymerization method, can realize the control of sequence, composition, distribution and the like on the molecular level, and improves the properties of the material to the greatest extent, thereby achieving the purpose of high performance.
In 1982, Ostu proposed the concept of "iniferter" as the first real "living" radical polymerization. After this, the CRP method has become a rapidly growing field in polymer chemistry research. Over thirty years, polymer chemists have developed a variety of CRP methods, including stable free radical polymerization (NMP), Atom Transfer Radical Polymerization (ATRP), and reversible addition fragmentation chain transfer polymerization (RAFT), among others. In the preparation method of the present invention, the radical living polymerization reaction can be specifically carried out by an ATRP polymerization method (atom transfer radical polymerization) or NMP (nitroxide radical polymerization) polymerization method, or by a RAFT (reversible addition-fragmentation chain transfer radical polymerization) polymerization method. In addition to the choice of free radical initiator, the living radical polymerization reaction may be carried out with other reaction aids depending on the particular implementation. For example, when the present invention employs an ATRP polymerization method to prepare a block copolymer, the reaction also requires the use of a catalyst, i.e., the reaction is carried out in the presence of an initiator and a catalyst; when the present invention employs a RAFT polymerisation process to prepare a block copolymer, the reaction also requires the use of a RAFT agent (CTA, chain transfer agent), i.e. the reaction is carried out in the presence of an initiator and a RAFT agent. In the preparation method of the present invention, the living radical polymerization is preferably performed by a RAFT polymerization method.
According to the present invention, preferably, the first radical polymerization monomer is a styrene monomer B and/or an acrylate monomer;
the styrene monomer A is preferably a compound shown as a formula I;
Figure BDA0002735688950000061
wherein R is6Is substituted or unsubstituted C6-C20Aryl, wherein the substituent is at least one of halogen, alkyl and alkoxy, and the aryl is phenyl, biphenyl, naphthyl or anthryl;
the chain transfer agent (RAFT agent) used in the present invention is not limited as long as it can regulate the styrene-based polymer or the acrylic polymer. From the aspect of easy availability of raw materials, the chain transfer agent is at least one of isopropyl phenyl bisthiobenzoate (CDB), benzyl bisthiobenzoate, S- (thiobenzoyl) acetic acid and ester thereof, dithiocarboxylic ester and trithiobenzyl carbonate;
in the production method of the present invention, the molar ratio of the chain transfer agent to the total amount of the first radical polymerization monomer used is preferably 1: 5 to 100, more preferably 1: 10-100 parts of;
the initiator is at least one of Benzoyl Peroxide (BPO), Azobisisobutyronitrile (AIBN) and potassium persulfate; preferably azobisisobutyronitrile;
in the present invention, the amount of the initiator is not particularly limited as long as the living radical polymerization reaction can be smoothly performed. Preferably, the molar ratio of the initiator to the total amount of the first free-radical polymerization monomer used is 1: 100-: 200-;
the non-selective solvent and the amount thereof used in the present invention are not particularly limited as long as they can sufficiently dissolve the reaction raw materials and the polymer and do not participate in the reaction. Typically, the non-selective solvent may be at least one of dioxane, acetone, and tetrahydrofuran.
The selective solvent is aromatic hydrocarbon and/or chloralkane, preferably at least one of toluene, xylene, trimethylbenzene, chloroform, dichloromethane and tetrachloroethane;
the polymerization conditions of the present invention are not particularly limited as long as the core-shell structure polymer microspheres of the present invention can be successfully synthesized. Preferably, the temperature of the first stage polymerization and the second stage polymerization are each independently from 0 ℃ to 150 ℃, preferably from 40 ℃ to 90 ℃; the time of the first stage polymerization reaction and the second stage polymerization reaction is 0.5 to 18 hours, preferably 3 to 12 hours;
the molar ratio of the total dosage of the chain transfer agent, the initiator and the first free radical polymerization monomer is 1: 0.1-0.5: 5-500;
the molar ratio of the styrene monomer A to the maleic anhydride monomer is (1-10): 1, preferably (1.0-1.2): 1.
according to the present invention, preferably, the preparation method further comprises: adding a multifunctional monomer at the beginning or during the second-stage polymerization reaction;
in the present invention, the addition of the polyfunctional monomer at the beginning of the second-stage polymerization reaction means that the polyfunctional monomer is added together with the styrenic monomer A and the maleic anhydride monomer; the multifunctional group monomer added during the second-stage polymerization reaction means that it may be added at any time period after the second-stage polymerization reaction is carried out, preferably at a time when the conversion of the monomer participating in the second polymerization reaction is not less than 80%;
the multifunctional monomer is preferably divinylbenzene.
In the invention, the polymer microspheres are crosslinked and stabilized by adding the multifunctional monomer, so that the polymer microspheres with a stable microsphere structure are obtained.
In the present invention, when the second-stage polymerization reaction is carried out, the molar ratio of the polyfunctional monomer to the styrene-based monomer a is 1: 10-1000, preferably 1: 10-100.
Preferably, in the preparation method of the present invention, in order to improve the efficiency of the polymerization reaction and reduce the generation of by-products, the method further comprises: prior to the polymerization reaction, the system was deoxygenated. In the present invention, the method for removing oxygen is not particularly limited, and may be a method for removing oxygen that is conventional in the art, for example, removing oxygen by charging nitrogen gas into the system for 20 to 50 min.
In the preparation method of the present invention, in order to reduce the preparation cost of the polymer microsphere copolymer having a core-shell structure, in one embodiment, the method may further include: after the polymerization reaction is completed, unreacted monomers possibly present in the reaction solution are recovered. The specific recovery process can be performed by methods conventional in the art, and those skilled in the art are aware of this and will not be described herein.
In a third aspect of the present invention, there is provided a polymeric microsphere produced by the above-mentioned production method.
In a fourth aspect, the present invention provides the use of the above-described polymeric microspheres as a light conversion agent and/or toughening agent.
When the polymer microsphere is applied as a light conversion agent or a toughening agent, the addition amount of the polymer microsphere is 0.05-3 wt% based on the weight of the added carrier.
The invention is further illustrated by the following examples:
the number average molecular weight (Mn) and the molecular weight distribution index (PDI) thereof are determined by Gel Permeation Chromatography (GPC), and are specifically determined by Shimadzu LC-20AD type gel permeation chromatograph, tetrahydrofuran is used as a mobile phase, narrow-distribution polystyrene is used as a standard sample, and the flow rate of the mobile phase is 1.0 mL/min.
Example 1
In this example, a RAFT polymerization method was used to prepare a core-shell polymer microsphere copolymer.
The first stage is as follows: dissolving benzyl dithiobenzoate and AIBN in 50mL of methylbenzene in a polymerization bottle, adding 5.2g of styrene monomer, blowing nitrogen for 30 minutes, and heating in an oil bath at 80 ℃ for 10 hours to react to obtain a first polymer shell structure; wherein the feeding ratio of reactants is as follows: benzyl bisthiobenzoate, AIBN and styrene (St) in a molar ratio of 1: 0.2: 40;
and a second stage: 50ml of toluene mixed solution of styrene and maleic anhydride was added to the first-stage reaction system, wherein the molar ratio of styrene to maleic anhydride was 50: 50, continuously reacting for 10 hours to obtain polymer microspheres; wherein the molar ratio of maleic anhydride to styrene in the first stage is 1: 2;
and finally, precipitating the reaction product in diethyl ether, and then drying in vacuum to obtain the fluorescent core-shell polymer microsphere marked as A1. The product A1 was measured to be 25nm in size with a maximum excitation at 494nm at 365nm excitation. The degree of polymerization of the first polymer shell structure is 40, and the molecular weight distribution index of the first polymer shell structure is 1.05.
Example 2
In this example, a RAFT polymerization method was used to prepare a core-shell polymer microsphere copolymer.
The first stage is as follows: dissolving benzyl dithiobenzoate and AIBN in 50mLCHCl3 in a polymerization bottle, adding 5.2g of styrene monomer, blowing nitrogen for 30 minutes, and heating in an oil bath at 60 ℃ for 10 hours to react to obtain a first polymer shell structure; wherein the feeding ratio of reactants is as follows: benzyl dithiobenzoate, AIBN and St in a molar ratio of 1: 0.2: 100, respectively;
and a second stage: 50ml of toluene mixed solution of 2-vinylnaphthalene and maleic anhydride is added into the first-stage reaction system, wherein the molar ratio of the 2-vinylnaphthalene to the maleic anhydride is 50: 50, continuously reacting for 10 hours to obtain polymer microspheres; wherein the molar ratio of maleic anhydride to styrene in the first stage is 1: 2;
and finally, precipitating the reaction product in diethyl ether, and then drying in vacuum to obtain the fluorescent core-shell polymer microsphere marked as A2. The product A2 was measured to be 52nm in size with a maximum excitation at 493nm under 365nm excitation. The degree of polymerization of the first polymer shell structure is 100, and the molecular weight distribution index of the first polymer shell structure is 1.10.
Example 3
In this example, a RAFT polymerization method was used to prepare a core-shell polymer microsphere copolymer.
The first stage is as follows: dissolving benzyl dithiobenzoate and AIBN in 50mLCHCl3 in a polymerization bottle, adding 1.1g of butyl acrylate monomer, blowing nitrogen for 30 minutes, and heating in an oil bath at 60 ℃ for 10 hours to react to obtain a first polymer shell structure; wherein the feeding ratio of reactants is as follows: benzyl dithiobenzoate, AIBN and butyl acrylate in a molar ratio of 1: 0.2: 5;
and a second stage: adding a toluene mixed solution of divinylbenzene, methylstyrene and maleic anhydride to the first-stage reaction system, wherein the molar ratio of divinylbenzene, methylstyrene and maleic anhydride is 1: 50: 50, continuously reacting for 10 hours to obtain polymer microspheres; wherein the molar ratio of maleic anhydride to butyl acrylate in the first stage is 10: 1;
and finally, precipitating the reaction product in diethyl ether, and then drying in vacuum to obtain the fluorescent core-shell polymer microsphere marked as A3. The product A3 was determined to be 67nm in size with a maximum excitation at 474nm at 365nm excitation. The degree of polymerization of the first polymer shell structure is 5, and the molecular weight distribution index of the first polymer shell structure is 1.25.
Example 4
In this example, a RAFT polymerization method was used to prepare a core-shell polymer microsphere copolymer.
The first stage is as follows: dissolving benzyl dithiobenzoate and AIBN in 50mLCHCl 3/toluene (50/50) in a polymerization bottle, adding 5.0g of butyl acrylate monomer, blowing nitrogen for 30 minutes, and heating in an oil bath at 60 ℃ for reaction for 10 hours to obtain a first polymer shell structure; wherein the feeding ratio of reactants is as follows: benzyl dithiobenzoate, AIBN and butyl acrylate in a molar ratio of 1: 0.2: 40;
and a second stage: 50ml of a toluene mixed solution of 4-bromostyrene and maleic anhydride is added into the first-stage reaction system, wherein the molar ratio of the 4-bromostyrene to the maleic anhydride is 50: 50, continuously reacting for 10 hours to obtain polymer microspheres; wherein the molar ratio of maleic anhydride to butyl acrylate in the first stage is 1: 1;
and finally, precipitating the reaction product in diethyl ether, and then drying in vacuum to obtain the fluorescent core-shell polymer microsphere marked as A4. The product A4 was measured to be 50nm in size with a maximum excitation at 442nm at 365nm excitation. The degree of polymerization of the first polymer shell structure is 40, and the molecular weight distribution index of the first polymer shell structure is 1.30.
Example 5
In this example, a RAFT polymerization method was used to prepare a core-shell polymer microsphere copolymer.
The first stage is as follows: dissolving benzyl dithiobenzoate and AIBN in 50mLCHCl 3/toluene (50/50) in a polymerization bottle, adding 6.4g of butyl acrylate monomer, blowing nitrogen for 30 minutes, and heating in an oil bath at 60 ℃ for reaction for 10 hours to obtain a first polymer shell structure; wherein the feeding ratio of reactants is as follows: benzyl dithiobenzoate, AIBN and butyl acrylate in a molar ratio of 1: 0.2: 40;
and a second stage: 30ml of a toluene mixed solution of divinylbenzene, styrene and maleic anhydride was added to the first-stage reaction system, wherein the molar ratio of divinylbenzene, styrene and maleic anhydride was 1: 50: 50, continuously reacting for 10 hours to obtain polymer microspheres; wherein the molar ratio of maleic anhydride to butyl acrylate in the first stage is 1: 1;
and finally, precipitating the reaction product in diethyl ether, and then drying in vacuum to obtain the fluorescent core-shell polymer microsphere marked as A5. The product A5 was measured to be 50nm in size with a maximum excitation at 479nm at 365nm excitation. The degree of polymerization of the first polymer shell structure is 40, and the molecular weight distribution index of the first polymer shell structure is 1.10.
Test example
Respectively using the polymer microspheres A1-A5 as light conversion agents for processing and modifying polystyrene, wherein the adding amount of the polymer microspheres is 2 wt% based on the total weight of the polystyrene, so as to obtain modified polystyrene microspheres B1-B5 with a fluorescent effect; the specific test data are shown in table 1, wherein B0 is a common polystyrene microsphere without adding a light conversion agent.
TABLE 1
Numbering Glass transition temperature (. degree. C.) HDT(℃) Light transmittance Fluorescence emission (nm)
B0 104 63 92 Is free of
B1 108 70 91 494
B2 110 68 93 493
B3 120 74 92 474
B4 109 78 90 442
B5 114 80 93 479
In Table 1, HDT represents the heat distortion temperature.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. A polymer microsphere with a core-shell structure is characterized in that the polymer microsphere comprises a first polymer shell structure and a second polymer core structure; wherein the second polymer core structure is a copolymer of styrenic monomer A and maleic anhydride monomer.
2. The polymeric microspheres of claim 1, wherein the degree of polymerization of the first polymeric shell structure is between 5 and 500, preferably between 20 and 100.
3. The polymeric microspheres of claim 1, wherein the first polymeric shell structure is a homopolymer or copolymer of a styrenic monomer B and/or an acrylate monomer; preferably polystyrene or polyacrylate.
4. The polymeric microspheres of claim 1, wherein said styrenic monomer a is a compound of formula i;
Figure FDA0002735688940000011
wherein R is6Is substituted or unsubstituted C6-C20The aryl group is at least one of halogen, alkyl and alkoxy, and the aryl group is phenyl, biphenyl, naphthyl or anthryl.
5. The polymeric microspheres of claim 1, wherein said polymeric microspheres have a diameter of 10-500 nm.
6. A preparation method of polymer microspheres is characterized by comprising the following steps:
in the presence of a first solvent, carrying out a first-stage polymerization reaction on a chain transfer agent, an initiator and a first free radical polymerization monomer; then directly adding a styrene monomer A and a maleic anhydride monomer to carry out second-stage polymerization reaction, or adding the styrene monomer A, the maleic anhydride monomer and a second solvent after separation and purification to carry out second-stage polymerization reaction to obtain polymer microspheres;
wherein, when direct addition of styrenic monomer A and maleic anhydride monomer is selected, the first solvent comprises a selective solvent and optionally a non-selective solvent; when a separation and purification process is selected, the first solvent comprises a selective solvent and/or a non-selective solvent;
the second solvent is a selective solvent.
7. The production method according to claim 6, wherein the first radical polymerization monomer is a styrene monomer B and/or an acrylate monomer;
the styrene monomer A is preferably a compound shown as a formula I;
Figure FDA0002735688940000021
wherein R is6Is substituted or unsubstituted C6-C20Aryl, the substituent is at least one of halogen, alkyl and alkoxyWherein aryl is phenyl, biphenyl, naphthyl or anthryl;
the acrylate monomer is preferably acrylate and/or methacrylate;
the chain transfer agent is at least one of isopropyl phenyl bisthiobenzoate, benzyl bisthiobenzoate, S- (thiobenzoyl) acetic acid and ester thereof, dithiocarboxylic ester and trithiobenzyl carbonate;
the initiator is at least one of benzoyl peroxide, azobisisobutyronitrile and potassium persulfate; preferably azobisisobutyronitrile;
the nonselective solvent is at least one of dioxane, acetone and tetrahydrofuran.
The selective solvent is aromatic hydrocarbon and/or chloralkane, preferably at least one of toluene, xylene, trimethylbenzene, chloroform, dichloromethane and tetrachloroethane;
the temperature of the first stage polymerization reaction and the second stage polymerization reaction is 0-150 ℃ independently, preferably 40-90 ℃; the time of the first stage polymerization reaction and the second stage polymerization reaction is 0.5 to 18 hours, preferably 3 to 12 hours;
the molar ratio of the total dosage of the chain transfer agent, the initiator and the first free radical polymerization monomer is 1: 0.1-0.5: 5-500;
the molar ratio of the styrene monomer A to the maleic anhydride monomer is (1-10): 1, preferably (1.0-1.2): 1.
8. the preparation method according to claim 6, further comprising: adding a multifunctional monomer at the beginning or during the second-stage polymerization reaction;
the multifunctional monomer is preferably divinylbenzene.
9. Polymer microspheres produced by the production process according to any one of claims 6 to 8.
10. Use of the polymeric microspheres of any of claims 1-5, 9 as a light conversion agent and/or toughening agent.
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