阅读说明：本技术 一种氧化还原引发的分散聚合制备单分散聚合物微球的方法 (Method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization ) 是由 曾兆华 王梦真 黄永平 杨建文 袁佳宇 于 2019-09-03 设计创作，主要内容包括：本发明公开了一种氧化还原引发分散聚合制备单分散聚合物微球的制备方法,是在氮气氛围下,将聚合单体、链转移剂、稳定分散剂溶解在乙醇/水混合液中,在体系中分别加入氧化剂和还原剂引发聚合,聚合反应结束后得到稳定的悬浮乳状液,通过数次离心-洗涤后,去除少量未参与反应的单体及分散介质,得到粒径非常均匀的单分散聚合物微球。本发明相对于一般的分散聚合来说,其关键是在氧化还原引发自由基聚合体系中加入了链转移剂,避免了自由基聚合成核及增长过快导致的微球不均匀问题,实现了微球高产率和形貌的统一。同时,本发明氧化还原体系可快速制备单分散的聚合物微球,工艺简单,操作方便,适合工业化批量生产,具有较大的应用前景。(The invention discloses a method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization, which comprises the steps of dissolving a polymerization monomer, a chain transfer agent and a stable dispersant in an ethanol/water mixed solution under the nitrogen atmosphere, respectively adding an oxidant and a reducing agent into the system to initiate polymerization, obtaining a stable suspension emulsion after the polymerization reaction is finished, and removing a small amount of unreacted monomer and dispersion medium after centrifuging and washing for several times to obtain the monodisperse polymer microspheres with very uniform particle sizes. Compared with the common dispersion polymerization, the method has the key point that the chain transfer agent is added into the redox initiation free radical polymerization system, so that the problems of non-uniformity of the microspheres caused by the synthesis of nuclei and over-rapid growth of free radicals are solved, and the high yield and the uniform appearance of the microspheres are realized. Meanwhile, the redox system can be used for quickly preparing the monodisperse polymer microspheres, and has the advantages of simple process, convenient operation, suitability for industrial mass production and larger application prospect.)

1. A preparation method of monodisperse polymer microspheres by redox-initiated dispersion polymerization is characterized in that under the atmosphere of nitrogen, a polymerization monomer is dissolved in an ethanol/water reaction medium containing a chain transfer agent and a stable dispersant, an oxidant and a reducing agent are added for dispersion polymerization reaction, after the reaction is finished, centrifugal separation is carried out, and the polymer microspheres are obtained by cleaning with ethanol/water mixed solution.

2. The method according to claim 1, wherein the amount of the polymerized monomer is 5 to 20 wt% of the reaction system, the amount of the chain transfer agent is 0.05 to 5 wt% of the polymerized monomer, the amount of the stabilizing dispersant is 0.2 to 20 wt% of the polymerized monomer, and the amount of the redox initiator is 0.5 to 10 wt% of the polymerized monomer.

3. The method according to claim 1 or 2, wherein the redox initiator has an oxidizing agent to reducing agent molar ratio of 1: 0.5 to 1.5.

4. The method according to claim 1 or 2, wherein the redox initiation system comprises oil-soluble and water-soluble, the water-soluble oxidizing agent is hydrogen peroxide, persulfate or hydroperoxide, and the corresponding reducing agent is ferrous ion, ascorbic acid, sodium ascorbate, sodium sulfite or sodium bisulfite;

the oil-soluble oxidant is organic peroxide: cyclohexanone peroxide, methyl ethyl ketone peroxide or dibenzoyl peroxide, and the corresponding reducing agent is naphthenate or a tertiary amine compound: n, N-dimethylaniline, N-diethylaniline or a thiol.

5. The method according to claim 1 or 2, wherein the polymerizable monomer is vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, dibutyl maleate, dioctyl maleate, acrylamide, methacrylamide, acrylonitrile, methyl acrylate, ethyl acrylate, isobornyl acrylate, butyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, isobutyl acrylate, isodecyl acrylate, isooctyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, itaconic acrylate, itaconic acid, butyl acrylate, ethyl methacrylate, lauryl acrylate, methyl methacrylate, or lauryl methacrylate, One or more of isooctyl methacrylate, dimethylaminoethyl methacrylate or 2-hydroxypropyl methacrylate, or a copolymer of one or more of the foregoing monomers.

6. The production method according to claim 1 or 2, characterized in that the stabilizing dispersant is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid type macro-molecule RAFT agent, cellulose derivative, polyethylene glycol type macro-molecule RAFT agent, or polyacrylamide type macro-molecule RAFT agent.

7. The method of claim 1 or 2, wherein the chain transfer agent is one of S, S ' -bis (2-methyl-2-propanoyl) trithiocarbonate, S-dodecyl-S ' - (2-methyl-2-propanoyl) trithiocarbonate, S-ethyl-S ' - (2-dimethyl-2-propanoyl) trithiocarbonate, or dibenzyl trithiocarbonate (DBTTC).

8. The preparation method according to claim 1, wherein the weight ratio of ethanol to water in the ethanol/water reaction medium is 20:80 to 80: 20.

9. Polymer microspheres obtainable by a process according to any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of monodisperse polymer microspheres, in particular to a method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization.

Background

Monodisperse polymeric microspheres, particularly functional polymeric microspheres, are increasingly used in various fields, such as biomedicine, ink coating, chromatographic separation, electronic materials, etc., and have become hot spots for research in the field of high molecular materials. At present, the methods for preparing the polymer microspheres mainly include emulsion polymerization, precipitation polymerization, dispersion polymerization, seed polymerization, and the like. The dispersion polymerization is a common method for preparing micron-sized polymer microspheres, and compared with other preparation methods, the method has the remarkable characteristics of simple process, wide applicable monomer range, wide particle size range of the obtained microspheres, good monodispersity and the like. In these preparation methods, the initiation modes of the polymerization reaction mainly include thermal initiation, photo initiation, radiation initiation, microwave-induced initiation, macromolecule initiation, etc., wherein the thermal initiation and the photo initiation are two response modes which are the most deeply studied and widely applied at present.

The preparation of the polymer microspheres by thermal initiation dispersion polymerization is usually carried out at a moderate temperature of 40-100 ℃, and commonly, common thermal initiators such as azobisisobutyronitrile, diacyl peroxide, persulfate, benzoyl peroxide and the like need to be added into a system. However, this method is slow in polymerization process, requires a long reaction time, often requires 24 hours to achieve a conversion rate of 90% or more, and cannot synthesize temperature-sensitive polymer microspheres.

The free radical polymerization initiated by the photoinitiator is a very rapid polymerization method, and the biggest advantages of the method are that the initiation speed is high, the efficiency is high, and heating is not needed. Under the irradiation of ultraviolet light or visible light, the photoinitiator can be rapidly cracked and then generate free radicals, and then rapidly initiate polymerization. Photo-initiated dispersion polymerization the microspheres prepared had relatively poor particle size uniformity due to the too fast reaction (J.Polym.Sci.part A: Polym.Chem.,2008, 46(4): 1329-. Monodisperse polymer microspheres (Macromolecules,2012,45(21): 8790-8795) can be obtained by controlling the nucleation process by means of controlled polymerization, for example by adding an appropriate amount of a reversible addition-fragmentation chain transfer agent, namely a RAFT agent. However, the problem of light penetration limits the scale of polymerization and the polymerization system is very sensitive to the presence of photosensitive substances (e.g., dyes, noble metal nanoparticles, etc.). Furthermore, the polymerization process requires the maintenance of light and is not a completely energy-efficient process. Therefore, the development of a novel initiation system with mild reaction conditions can provide a new method for preparing monodisperse polymer microspheres.

In recent years, with the research on the mechanism of free radical initiation, the polymerization reaction initiated by the generation of free radicals by redox reaction has been drawing more and more attention, and is applied to the research on the preparation of polymer materials. Among them, the use of redox initiation in polymerization-induced self-assembly has been reported most. Compared with the common initiation system, the redox initiation system has low activation energy and short induction period, and can quickly generate a large amount of free radicals at low temperature, so that the polymerization reaction can be carried out at low temperature. Different oxidants and different reductants can form various redox initiation systems, and the polymerization speed can be regulated and controlled by adjusting the concentration and the proportion of the oxidants and the reductants, so that the reaction can realize higher conversion rate in a shorter time. When it is desired to obtain as much polymer as possible (to improve the yield), it is common practice in the art to increase the amount of initiator used in the reaction system; however, in the redox initiation system, when the amount of the redox initiator exceeds 4%, nucleation and growth are too fast, resulting in non-uniformity of microspheres, and uniformity of the yield and morphology of the microspheres cannot be realized.

Disclosure of Invention

The invention aims to overcome the defects and technical defects of a preparation method of polymer microspheres in the prior art and provide a method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization. A redox initiation system is adopted to initiate dispersion polymerization, and the monodisperse polymer microspheres are rapidly prepared at room temperature. Compared with the photo-initiated dispersion polymerization, the method has the key points that a redox initiation system is used, the method has the characteristics of rapidness, no need of heating and the like, and the problem of light blockage of the photo-initiation system is avoided; compared with the common dispersion polymerization, the method has the key point that a chain transfer agent is added into a redox initiation free radical polymerization system, so that the problems of non-uniformity of microspheres caused by synthesis nuclei and over-rapid growth of free radicals are avoided.

The invention also aims to provide the monodisperse polymer microsphere prepared by the method.

The above purpose of the invention is realized by the following technical scheme:

a method for preparing polymer microspheres by redox-initiated dispersion polymerization comprises the steps of dissolving a polymerization monomer, a chain transfer agent and a stable dispersing agent in an ethanol/water reaction medium in a nitrogen atmosphere, adding an oxidant and a reducing agent to initiate polymerization reaction to obtain a stable emulsion, centrifugally separating, and cleaning with an ethanol/water mixed solution to obtain the monodisperse polymer microspheres.

The invention introduces a redox initiation system into dispersion polymerization, adopts the redox initiation system to initiate dispersion polymerization, and quickly prepares the monodisperse polymer microspheres at room temperature. Compared with photoinitiated dispersion polymerization, the method has the characteristics of rapidness, no need of heating and the like, and avoids the problem of light blockage of a photoinitiated system. Compared with the common dispersion polymerization, the key point of the invention is that the chain transfer agent is added into the redox initiation free radical polymerization system at the same time, so that the problems of non-uniformity of free radical synthesis core and microsphere caused by over-rapid growth are avoided. When the redox introduction amount is increased, the productivity of the polymer microspheres can be improved, and the morphology of the polymer microspheres can be ensured.

Preferably, the amount of the polymerized monomer is 5 to 20 wt% (e.g., 5 to 10 wt%, 10 to 15 wt%, 15 to 20 wt%) of the reaction system, the amount of the chain transfer agent is 0.05 to 5 wt% (e.g., 0.05 to 0.1 wt%, 0.1 to 0.5 wt%, 0.5 to 1 wt%, 1 to 2 wt%, 2 to 5 wt%) of the polymerized monomer, the amount of the stabilizing dispersant is 0.2 to 20 wt% (e.g., 0.2 to 1 wt%, 1 to 2 wt%, 2 to 5 wt%, 5 to 10 wt%, 10 to 15 wt%, 15 to 20 wt%) of the polymerized monomer, and the amount of the redox initiator is 0.5 to 10 wt% (e.g., 1 to 10 wt%, 2 to 10 wt%, 4 to 10 wt%) of the polymerized monomer.

Preferably, the redox initiator has a molar ratio of oxidant to reductant of 1: 0.5 to 1.5.

Preferably, the polymeric monomer is vinyl acetate, styrene, acrylic acid, methacrylic acid, itaconic acid, dibutyl maleate, dioctyl maleate, acrylamide, methacrylamide, acrylonitrile, methyl acrylate, ethyl acrylate, isobornyl acrylate, butyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, isobutyl acrylate, isodecyl acrylate, isooctyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, isooctyl methacrylate, itaconic methacrylate, dibutyl maleate, butyl acrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, butyl methacrylate, lauryl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, One or more of dimethylaminoethyl methacrylate or 2-hydroxypropyl methacrylate, or a copolymer of one or more of the foregoing monomers.

Preferably, the stabilizing dispersant is one of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylic acid type macro-molecule RAFT agent (PAA-TTC), cellulose derivative, polyethylene glycol type macro-molecule RAFT agent (mPEGA-TTC), polyacrylamide type macro-molecule RAFT agent (PDMA-TTC), but not limited thereto, and in principle, stabilizing dispersants for dispersion polymerization may be used in the present invention.

More preferably, the stabilizing dispersant is polyacrylic acid type macro-molecule RAFT agent (PAA-TTC) with a structural formula shown as the following formula (I):

preferably, the preparation method of the macro RAFT agent PAA-TTC is to use DDMAT as a micro RAFT agent to carry out solution polymerization of acrylic monomer RAFT, and synthesize the macro RAFT agent PAA-TTC.

Preferably, the chain transfer agent is a small molecule RAFT agent: one of S, S ' -bis (2-methyl-2-propionyloxy) trithiocarbonate (BDMAT), S-dodecyl-S ' - (2-methyl-2-propionyloxy) trithiocarbonate (DDMAT), S-ethyl-S ' - (2-dimethyl-2-propionyloxy) trithiocarbonate (EDMAT), or dibenzyl trithiocarbonate (DBTTC).

More preferably, the chain transfer agent (i.e., small molecule RAFT agent) is S-dodecyl-S' - (2-methyl-2-propanoyl) trithiocarbonate (DDMAT) having the formula (II):

preferably, the redox initiation system includes oil-soluble and water-soluble, the water-soluble oxidizing agent is hydrogen peroxide, persulfate, hydroperoxide, etc., and the corresponding reducing agent is ferrous ion, ascorbic acid, sodium ascorbate, sodium sulfite, sodium bisulfite, etc. The oil-soluble oxidizing agent is an organic peroxide, such as cyclohexanone peroxide, methyl ethyl ketone peroxide, dibenzoyl peroxide, etc., and the reducing agent is naphthenate (cobalt, manganese, vanadium, iron, etc.) or a tertiary amine compound, such as N, N-dimethylaniline, N-diethylaniline, mercaptan, etc.

Preferably, the redox initiation system is hydrogen peroxide and ferrous sulfate.

Preferably, the reaction time is 0.5-5 h; the centrifugation is 10000 r/min for 3-5 min.

In addition, the polymer microspheres prepared by the method and the application thereof are also within the protection scope of the invention.

Compared with the prior art, the invention has the following beneficial effects:

the invention provides a method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization, which utilizes single electron transfer between an oxidant and a reducing agent to cause redox reaction to generate free radicals, thereby not only reducing the decomposition activation energy of peroxide and initiating monomer polymerization under the condition of lower temperature (such as zero temperature to room temperature), but also increasing the decomposition rate of the peroxide so as to increase the polymerization rate; the dispersion polymerization initiated by redox has fast reaction speed which can reach 73% in half an hour, and the method does not need illumination, has simple operation and is suitable for batch production of factories; more importantly, the chain transfer agent is added into the redox initiation free radical polymerization system, so that the problems of non-uniformity of the microspheres caused by the synthesis of nuclei and over-rapid growth of free radicals are solved, and the high yield and the uniform appearance of the microspheres are realized.

Drawings

FIG. 1 is a Scanning Electron Micrograph (SEM) of the polymeric microspheres prepared in example 2.

FIG. 2 is a Scanning Electron Micrograph (SEM) of the polymeric microspheres prepared in example 3.

FIG. 3 is a Scanning Electron Micrograph (SEM) of polymeric microspheres prepared according to example 4.

FIG. 4 is a Scanning Electron Micrograph (SEM) of polymeric microspheres prepared according to example 5.

FIG. 5 is a Scanning Electron Micrograph (SEM) of polymeric microspheres prepared according to example 6.

FIG. 6 is a Scanning Electron Micrograph (SEM) of polymeric microspheres prepared according to example 7.

FIG. 7 is a Scanning Electron Micrograph (SEM) of the polymeric microspheres prepared in comparative example 1.

Detailed Description

The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available.