CN104031210A - Method for preparing quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion - Google Patents

Method for preparing quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion Download PDF

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CN104031210A
CN104031210A CN 201410283783 CN201410283783A CN104031210A CN 104031210 A CN104031210 A CN 104031210A CN 201410283783 CN201410283783 CN 201410283783 CN 201410283783 A CN201410283783 A CN 201410283783A CN 104031210 A CN104031210 A CN 104031210A
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quaternary ammonium
surface
modified
ammonium salt
emulsion
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CN 201410283783
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CN104031210B (en )
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谷岩
闫丰文
袁国卿
郭存悦
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中国科学院化学研究所
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Abstract

The invention relates to a method for preparing a quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion. The quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion is prepared by introducing a hydrophilic functional monomer and changing the feeding ratio of styrene to water, so as to achieve effective control on the monodisperse polystyrene microsphere. The method comprises the following steps: by taking styrene as a main monomer, dimethyl diallyl ammonium chloride as a functional monomer, methyl methacrylate as a third monomer, potassium peroxodisulfate or ammonium persulfate as an initiator and water as a reaction medium, preparing the polystyrene microsphere with quaternary ammonium salt gathered on the surface by adopting a soap-free emulsion polymerization method in a semi-continuous manner. No surfactant, organic solvent or inorganic salt is added in the preparation process; the method is simple in preparation technology and low in cost; the particle size of the obtained quaternary ammonium salt surface-modified monodisperse polystyrene microsphere can be flexibly controlled between 150nm and 600nm by regulating the dosage ratio of the initiator to the three monomers.

Description

季铵盐表面改性的单分散聚苯乙烯微球乳液的制备方法 The method of preparing a quaternary ammonium salt surface-modified polystyrene microspheres monodisperse emulsion

技术领域 FIELD

[0001] 本发明涉及高分子材料合成领域,特别涉及季铵盐表面改性的单分散聚苯乙烯微球乳液的制备方法。 [0001] The present invention relates to the field of synthetic polymer materials, particularly relates to a method of surface-modified quaternary ammonium salts of monodisperse polystyrene latex microspheres.

背景技术 Background technique

[0002] 表面功能化的聚合物微球由于可以广泛应用于许多领域,如生物化学和生物医学、药物学、色谱柱填料及临床检验等,目前已受到越来越多的关注。 [0002] surface-functionalized polymer microspheres due can be widely used in many fields, such as biochemistry and biomedicine, pharmacology, column packing and clinical inspection, has attracted more and more attention. 至今,已有含不同功能基团的聚合物微球见诸报道,包括羧基(Song JS,Leonid C,Mitchell A, MonodisperseMicrometer-Size Carboxy1-Funct1nalized Polystyrene Particles Obtained byTwo-Stage Dispers1n Polymerizat1n, Macromolecules, 2006, 39:5729-5737)> 氨基(王伟财,张琦,张兵波等,氨基化单分散超顺磁荧光PGMA多功能微球制备,科学通报,2007,52:2477 ~2481)、羟基(CN200810239501.X)、溴取代基(CN200910070904.0)等。 To date, the polymeric microspheres containing different functional groups been reported, including a carboxyl group (Song JS, Leonid C, Mitchell A, MonodisperseMicrometer-Size Carboxy1-Funct1nalized Polystyrene Particles Obtained byTwo-Stage Dispers1n Polymerizat1n, Macromolecules, 2006, 39 : 5729-5737)> amino (Wang Choi, Zhang Qi, Zhang Bingbo the like, amides monodisperse superparamagnetic microspheres prepared multifunctional PGMA fluorescence, Chinese Science Bulletin, 2007,52: 2477 - 2481), hydroxy (CN200810239501.X ), bromo substituent (CN200910070904.0) and so on. 这些表面功能化的聚合物微球可以用于固定和检测生物大分子,比如抗体和酶等蛋白质。 These surface functionalized polymeric microspheres can be used for fixing and detection of biological macromolecules, proteins such as antibodies and enzymes.

[0003] 在聚合物微球的表面引入不同的基团,如亲水性的羟基或羧基,可以改善聚合物微球的稳定性甚至生物相容性;利用表面基团可以把无机半导体微粒和功能有机分子以及生物分子引入聚合物微球中,赋予聚合物微球特殊的性能,使其广泛应用于涂料、光电功能材料和生物医用材料等领域。 [0003] The introduction of groups at the surface of different polymeric microspheres, such as hydrophilic hydroxyl or carboxyl groups, the stability can be improved even biocompatible polymeric microspheres; surface groups can use the inorganic semiconductor fine particles and functional organic molecules and biological molecules incorporated in polymeric microspheres, polymeric microspheres to impart special properties, it is widely used in the coatings art, photoelectric functional materials, and biomedical materials. 其中,表面带有阳离子的聚合物微球在絮凝剂、胶粘剂、水性涂料等方面已经得到了广泛的应用。 Wherein the polymeric microspheres in the surface with a cationic coagulant, adhesive, aqueous coating, etc. have been widely used. 通常阳离子聚合物微球可以根据不同的需要利用常规乳液聚合、核壳乳液聚合等方法来合成。 Typically the cationic polymeric microspheres may be synthesized using conventional emulsion polymerization, core-shell emulsion polymerization and other methods according to different needs. 亲水性和疏水性单体进行的无皂乳液聚合,因其能在聚合物微球表面引入不同的功能基团且表面洁净而备受关注,也是合成阳离子聚合物微球的理想方法。 Free emulsion polymerization of hydrophilic and hydrophobic monomer, because of its surface can be introduced in the microsphere polymers having different functional groups and the surface clean and concern, but also over a cationic synthetic polymeric microspheres.

[0004] 各种功能纳米粒子因为具有巨大的潜在应用价值,已成为研究的热点。 [0004] various functions because nanoparticles have great potential applications, it has become a hot research. 在纳米粒子的表面引入季铵盐也是一种重要的功能化方式,具有广泛的应用前景。 Introducing a quaternary ammonium salt is also an important feature of the embodiment the surface of the nanoparticles, having a wide application prospect. 由于在金属纳米粒子或者半导体纳米粒子的表面引入季铵盐较为容易,因此这些研究大部分仅限于金属纳米粒子或者半导体纳米粒子,而对于聚合物纳米粒子的表面季铵盐化的研究相对较少。 Since the introduction of quaternary ammonium easier on the surface of the metal nanoparticles or semiconductor nanoparticles, so most of these studies are limited to metal nanoparticles or semiconductor nanoparticles, while the relatively small particles to the surface of the polymer nanoparticles quaternized Research .

[0005] 陈鑫等提出将苯乙烯、4,4' - 二甲基丙烯酰氧基-2,2' - 二苯基丙烷、2,2' - 二(2-甲基丙脒)二盐酸盐和功能单体乙烯苄基三甲基铵氯化物以一定比例混合,通过乳液聚合方式在75°C的水浴中反应24小时,制备稳定的表面富集季铵盐的交联聚苯乙烯微球乳液(陈鑫.表面富集季铵盐的交联聚苯乙烯微球合成与表征及其溶胀行为研究.高分子学报,2003,2:293~297)。 [0005] Xin Chen put forward styrene, 4,4 '- methacryloyloxy-2,2' - diphenyl propane, 2,2 '- bis (2-methyl propionamidine) dihydrochloride acid functional monomers and vinyl benzyl trimethylammonium chloride in a certain proportion, the reaction in a water bath at 75 ° C in 24 hours by emulsion polymerization, a quaternary ammonium salt enriched preparation of stable surface crosslinked polystyrene microsphere emulsion (Chen Xin crosslinked polystyrene microspheres and the swelling behavior synthesis and Characterization of a quaternary ammonium salt surface enrichment Polymers Research, 2003,2: 293 ~ 297). 此种方法虽然所制备的微球粒径较为均匀,但是由于生产成本较高,而且乳化剂大量残留对产物性能和环境都易造成不利影响,致其应用受到极大限制,尤其是在生物、医药领域。 Although the size of the microspheres prepared by this method are more uniform, but because of higher production costs, and a large amount of residual emulsifier on their properties and are prone to adversely affect the environment, their use is extremely limited induced, especially in biological, the field of medicine.

[0006]近年来,也有关于聚苯乙烯季铵盐化的专利(CN201110449023.7),此方法是将十六烷基三甲基溴化铵和过硫酸钾或过硫酸铵加入到苯乙烯、无水乙醇和去离子水的混合液中引发聚合反应,该方法简单易行,但是由于聚苯乙烯链段与季铵盐改性剂之间并未真正形成化学键,材料稳定性较低,应用受限。 [0006] In recent years, there are patents on quaternary ammonium salt of polystyrene (CN201110449023.7), this method is cetyl trimethyl ammonium bromide and potassium persulfate or ammonium persulfate is added to styrene, ethanol and deionized water mixture to initiate the polymerization reaction, the method is simple, but since the polystyrene segments between the modifying agent and a quaternary ammonium salt not really form a chemical bond, lower stability of the material application limited. [0007] 因此,若能以常规的无皂乳液聚合代替上述的聚合方法来制备季铵盐改性聚苯乙烯微球,在聚苯乙烯链段与含不饱和键的季铵盐改性剂之间引入化学键合的第三单体,则有望克服上述不足,获得性能稳定的表面功能化聚苯乙烯无皂乳液。 [0007] Thus, if quaternary ammonium salt is prepared in a conventional polystyrene microspheres in place of the above-described soap-free emulsion polymerization method, the quaternary ammonium salts and polystyrene segments modifier containing an unsaturated bond surface functionalized chemically bonded introduced between the third monomer, it is expected to overcome the above disadvantages, stable performance polystyrene soap-free emulsion.

发明内容 SUMMARY

[0008] 本发明的目的之一是针对苯乙烯与二甲基二烯丙基氯化铵两种单体接枝困难的缺陷,在聚合过程中引入第三单体作为桥联段,同时采用二次投料和半连续的聚合方法,改变引发阶段和聚合阶段的反应温度,控制反应平稳地进行,从而提供一种直接在水相中聚合的季铵盐表面改性的单分散聚苯乙烯微球乳液的制备方法。 [0008] One object of the present invention is directed to styrene and difficult dimethyl diallyl ammonium chloride graft defects two monomers, the third monomer is incorporated as a bridging segment during the polymerization, while using secondary material and semi-continuous polymerization process, changing the reaction temperature and the initiation of the polymerization stage to control the reaction proceeds smoothly, thereby providing a direct monodisperse polystyrene microspheres in the aqueous phase polymerization of the surface-modified quaternary ammonium salts preparing an emulsion of the ball.

[0009] 本发明的目的之二是针对季铵盐改性聚苯乙烯微球表面存在多余稳定剂的缺陷,通过改变苯乙烯、水、功能单体的比例,从而提供一种在不添加任何表面活性剂、无机盐和有机溶剂的情况下,制备得到的能够稳定存放的季铵盐表面改性的聚苯乙烯微球乳液。 [0009] The object of the present invention is directed to two defects in excess of a quaternary ammonium salt stabilizer modified polystyrene microsphere surface, by changing the styrene, water, the proportion of functional monomer, thereby providing a without the addition of any a case where a surfactant, an inorganic salt and an organic solvent, surface-modified quaternary ammonium salts can be prepared in shelf-stable emulsions of polystyrene microspheres.

[0010] 为实现本发明的目的,本发明采用二甲基二烯丙基氯化铵作为功能单体,在稳定乳液聚合的同时提供所需官能团,并最终得到稳定的季铵盐改性聚苯乙烯微球乳液。 [0010] To achieve the object of the present invention, the present invention is dimethyldiallylammonium chloride employed as the functional monomer in a stable emulsion to provide the desired functional groups, and ultimately a stable modified poly quaternary ammonium salt styrene microsphere emulsion. 为保证功能单体能够化学键合在聚苯乙烯微球表面,本发明添加一定量的第三单体甲基丙烯酸甲酯,利用其偶联作用,将疏水的单体苯乙烯与亲水的功能单体桥联在一起,通过半连续聚合法,在缩短聚合诱导期的同时,保证反应过程中乳液稳定。 To ensure functional monomers can be chemically bonded to the surface of polystyrene microspheres, the present invention is added an amount of a third monomer of methyl methacrylate, with its coupling effect, the hydrophobic monomers styrene and hydrophilic functionality monomer bridged together by semi-continuous polymerization, the polymerization induction period shortened while ensuring a stable emulsion during the reaction.

[0011] 本发明的季铵盐表面改性的单分散聚苯乙烯微球乳液的制备方法:将苯乙烯与水按1:12~1:7的质量比混合搅拌均匀,按所述的苯乙烯质量的3%~8%向上述搅拌均匀的混合液中加入第三单体甲基丙烯酸甲酯;在惰性气氛下,按所述的苯乙烯质量的 [0011] Preparation of surface-modified quaternary ammonium salt of the present invention, monodisperse polystyrene latex microspheres: styrene with water at 1: 12 to 1: 7 mass ratio of uniform mixing, according to the benzene 3% to 8% by mass of the ethylene-methyl methacrylate third monomer was added to the stirred homogeneous mixture; under an inert atmosphere, according to the mass of styrene

0.5%~6%再加入过硫酸钾或过硫酸铵;在温度为77~85°C下反应10~50分钟后,按所述的苯乙烯质量的0.93~2.0倍,加入二甲基二烯丙基氯化铵水溶液(优选二甲基二烯丙基氯化铵水溶液的质量分数为30%~60% );然后在温度为70°C~75°C下反应8~24小时,停止加热并在搅拌下冷却到室温,得到表面富集季铵盐的季铵盐表面改性的单分散聚苯乙烯微球乳液。 0.5% to 6% was further added potassium persulfate or ammonium persulfate; 10 to 50 minutes the reaction at a temperature of 77 ~ 85 ° C, the styrene by the mass of 0.93 to 2.0 times, diene was added dimethyl propyl ammonium chloride solution (mass fraction is preferably an aqueous solution of diallyl dimethyl ammonium chloride 30% to 60%); followed by reaction at a temperature of 70 ° C ~ 75 ° C for 8 to 24 hours, heating was stopped and cooled with stirring to room temperature to obtain surface-modified quaternary ammonium salt of a quaternary ammonium salt surface enrichment of monodisperse polystyrene microsphere emulsion.

[0012] 本发明在制备过程中接枝功能单体,引入甲基丙烯酸甲酯作为第三单体将疏水的单体苯乙烯与亲水的二甲基二烯丙基氯化铵功能单体桥联在一起;制备过程中采用半连续法,反应一段时间后,再加入功能单体二甲基二烯丙基氯化铵;制备过程中不添加任何表面活性剂、有机溶剂和无机盐,确保季铵盐表面改性的单分散聚苯乙烯微球乳液的表面洁净,且在单分散聚苯乙烯微球表面无其它干扰杂质的情况下,保证单分散聚苯乙烯微球具有良好的粒度均一性。 [0012] The present invention is in the preparation of graft functional monomer, methyl methacrylate as the introduction of the styrene monomer and the third monomer hydrophilic hydrophobic functional dimethyl diallyl ammonium chloride monomers bridged together; preparation process using semi-continuous process, after a period of reaction, added functional monomer dimethyldiallylammonium chloride; without adding any surfactant, organic solvent and an inorganic salt during preparation, ensuring a quaternary ammonium salt surface modified surface of monodisperse polystyrene microsphere emulsion clean, and the surface of monodisperse polystyrene microspheres no other interfering impurities, to ensure monodisperse polystyrene microspheres having a good particle size uniformity.

[0013] 本发明的制备方法得到的季铵盐表面改性的单分散聚苯乙烯微球乳液的特点在于:季铵盐表面改性的单分散聚苯乙烯微球乳液中不含任何表面活性剂、有机溶剂和无机盐,且组成单分散聚苯乙烯微球乳液的季铵盐表面改性的聚苯乙烯微球的单分散性好,单分散聚苯乙烯微球的表面富集大量的季铵盐,单分散聚苯乙烯微球的粒径范围为150nm~600nmo [0013] Characteristics of monodisperse polystyrene latex microspheres prepared surface-modified quaternary ammonium salts of the present invention is obtained by a method comprising: monodisperse polystyrene microsphere emulsion surface-modified quaternary ammonium salts free of any surfactant , organic solvents and inorganic salts, and the composition of the surface-modified quaternary ammonium salts monodisperse polystyrene microspheres emulsion monodisperse polystyrene microspheres good monodisperse polystyrene microspheres of large surface concentration quaternary ammonium salts, monodisperse polystyrene microspheres particle size range of 150nm ~ 600nmo

[0014] 本发明通过引入亲水性功能单体,并改变苯乙烯与水的投料比例制备季铵盐表面改性的单分散聚苯乙烯微球乳液,可在一定范围内实现对单分散聚苯乙烯微球的有效控制。 [0014] The present invention is by introducing a hydrophilic functional monomer, and changing the feed ratio of the surface-modified styrene quaternary ammonium salt prepared aqueous monodisperse polystyrene microspheres emulsion Monodisperse Poly can be realized within a predetermined range styrene effective control microspheres. 本发明以苯乙烯为主要单体,二甲基二烯丙基氯化铵为功能单体,甲基丙烯酸甲酯为第三单体,过硫酸钾或过硫酸铵为引发剂,水为反应媒介,通过半连续方式采用无皂乳液聚合方法,制备表面富集季铵盐的聚苯乙烯微球。 The present invention is styrene as the main monomer, dimethyldiallylammonium chloride as the functional monomer, a third monomer is methyl methacrylate, potassium persulfate or ammonium persulfate as the initiator, the reaction water media, soap-free emulsion polymerization process by semi-continuous manner, a surface concentration of the quaternary ammonium salt of polystyrene microspheres. 该方法对机械搅拌速度的均匀性要求相对较低,无需表面活性剂,制备工艺简单,成本低,所得季铵盐表面改性的单分散聚苯乙烯微球的粒径可以通过调节引发剂的用量和三种单体之间的比例,在150nm~600nm之间灵活调控。 This method requires relatively low uniformity of mechanical stirring speed, without a surfactant, the preparation process is simple, low cost, the resulting quaternary ammonium salt of monodispersed polystyrene microspheres may be surface modified by adjusting the initiator and the ratio between the amounts of the three monomers, flexible regulation between 150nm ~ 600nm. 季铵盐表面改性的单分散聚苯乙烯微球可作为聚合物模板、胶粘剂基体或无机物载体材料,在构建光子晶体、无机/有机纳米复合材料和微米/纳米空心球方面具有重要的应用价值。 Surface-modified quaternary ammonium salts of monodisperse polystyrene microspheres can be used as a template polymer, an adhesive support material or inorganic matrix, having important applications in building a photonic crystal, an inorganic / organic nano composites and micro / nano hollow spheres value.

[0015] 本发明与现有聚苯乙烯微球乳液的合成方法相比,具有以下优点: [0015] The method of the present invention as compared with prior synthetic latex of polystyrene microspheres having the following advantages:

[0016] (I)与传统乳液聚合制备乳液相比,本发明不需要加入任何表面活性剂,制备得到的单分散聚苯乙烯微球乳液的表面洁净,粒度均匀性好,且表面进行季铵盐改性。 [0016] (I) as compared to conventional emulsions prepared by emulsion polymerization, the present invention does not require addition of any surfactant, prepared surface of monodisperse polystyrene microsphere emulsion clean, particle size uniformity, and a quaternary ammonium surface modified salts.

[0017] (2)与分散聚合制备乳液相比,本发明不需要加入分散剂和有机溶剂,单分散聚苯乙烯微球乳液的表面洁净。 [0017] (2) dispersing the surface compared to the emulsion polymerization, the present invention does not require addition of a dispersant and an organic solvent, an emulsion of monodisperse polystyrene microspheres clean.

[0018] (3)本发明的制备方法的反应速度快,乳液稳定性好。 Preparation of the reaction rate [0018] (3) The method of the present invention is fast, good emulsion stability.

[0019] (4)本发明的制备方法可以明显缩短反应周期,提高苯乙烯单体的转化率。 [0019] (4) The production method of the present invention can significantly shorten the reaction period, increase the conversion of styrene monomer.

[0020] (5)组成本发明的制备方法得到的单分散聚苯乙烯微球乳液中的单分散聚苯乙烯微球的粒径均匀,呈明显单分散。 Monodisperse polystyrene microspheres monodisperse polystyrene microsphere emulsion [0020] (5) The method of preparing the composition of the present invention obtained in uniformity, showed a monodisperse.

具体实施方式 detailed description

[0021] 以下结合具体实施例对本发明作进一步的说明。 [0021] The following embodiments in conjunction with specific embodiments of the present invention will be further described. 应理解,这些实施例仅用于说明本发明而非限制本发明的保护范围。 It should be understood that these embodiments are illustrative only and the invention without limiting the scope of the present invention. 实施例中采用的实施条件可以根据具体要求作进一步的调整,未注明的实施条件通常为常规实验中的条件。 Conditions employed in the embodiment may further embodiment tailored to the specific requirements, conditions are generally not specified embodiment of a conventional test conditions.

[0022] 实施例1 [0022] Example 1

[0023] 在反应器中加入5.0g苯乙烯和60.0g蒸懼水,搅拌混合均匀,在搅拌下加入0.15g甲基丙烯酸甲酯,通入氮气排空,加入0.30g过硫酸钾;在温度为85°C下反应50分钟后,加入10.0g质量分数为60%的二甲基二烯丙基氯化铵水溶液,然后在温度为75°C下继续反应8小时;停止加热并在搅拌下冷却到室温,得到季铵盐表面改性的单分散聚苯乙烯微球乳液。 [0023] 5.0g of styrene and 60.0g fear distilled water in a reactor, mixing evenly, 0.15g of methyl methacrylate were added with stirring, nitrogen gas evacuation, 0.30g of potassium persulfate was added; the temperature after reaction at 85 ° C 50 minutes, 10.0g of 60% of the mass fraction of dimethyl diallyl ammonium chloride aqueous solution, and then the reaction was continued at a temperature of 75 ° C for 8 hours; under stirring and heating was stopped It cooled to room temperature to obtain a surface-modified quaternary ammonium salts of monodisperse polystyrene microsphere emulsion. 构成季铵盐表面改性的单分散聚苯乙烯微球乳液中的单分散聚苯乙烯微球的粒径为150nmo Monodisperse polystyrene microspheres monodisperse polystyrene microsphere emulsion constituting the quaternary ammonium salt in the surface-modified particle diameter 150nmo

[0024] 实施例2 [0024] Example 2

[0025] 在反应器中加入6.0g苯乙烯和57.0g蒸懼水,搅拌混合均匀,在搅拌下加入0.3g甲基丙烯酸甲酯,通入氮气排空,加入0.20g过硫酸钾;在温度为82°C下反应30分钟后,加入8.0g质量分数为60%的二甲基二烯丙基氯化铵水溶液,然后在温度为75°C下继续反应12小时;停止加热并在搅拌下冷却到室温,得到季铵盐表面改性的单分散聚苯乙烯微球乳液。 [0025] 6.0g of styrene and 57.0g distilled added fear of water in a reactor, mixing evenly, 0.3g of methyl methacrylate was added under stirring, nitrogen gas evacuation, 0.20g of potassium persulfate was added; the temperature after reaction at 82 ° C 30 minutes, 8.0g of an aqueous solution of mass fraction of 60% dimethyl diallyl ammonium chloride, and the reaction was continued at a temperature of 75 ° C for 12 hours; the heating was stopped and stirring under It cooled to room temperature to obtain a surface-modified quaternary ammonium salts of monodisperse polystyrene microsphere emulsion. 构成季铵盐表面改性的单分散聚苯乙烯微球乳液中的单分散聚苯乙烯微球的粒径为220nm。 Monodisperse polystyrene microspheres monodispersed polystyrene microspheres in the emulsion constituting the surface-modified quaternary ammonium salt is 220nm.

[0026]实施例3 [0026] Example 3

[0027] 在反应器中加入7.0g苯乙烯和54.0g蒸懼水,搅拌混合均匀,在搅拌下加入0.4g甲基丙烯酸甲酯,通入氮气排空,加入0.035g过硫酸钾;在温度为80°C下反应30分钟后,加入7.5g质量分数为60%的二甲基二烯丙基氯化铵水溶液,然后在温度为73°C下继续反应18小时;停止加热并在搅拌下冷却到室温,得到季铵盐表面改性的单分散聚苯乙烯微球乳液。 [0027] 7.0g of styrene and 54.0g distilled added fear of water in a reactor, mixing evenly, 0.4g of methyl methacrylate was added under stirring, nitrogen gas evacuation, was added 0.035g of potassium persulfate; temperature after reaction at 80 ° C 30 minutes, 7.5g of an aqueous solution of mass fraction of 60% dimethyl diallyl ammonium chloride, and the reaction was continued for 18 hours at a temperature of 73 ° C; under stirring and heating was stopped It cooled to room temperature to obtain a surface-modified quaternary ammonium salts of monodisperse polystyrene microsphere emulsion. 构成季铵盐表面改性的单分散聚苯乙烯微球乳液中的单分散聚苯乙烯微球的粒径为450nmo Monodisperse polystyrene microspheres monodisperse polystyrene microsphere emulsion constituting the quaternary ammonium salt in the surface-modified particle diameter 450nmo

[0028] 实施例4 [0028] Example 4

[0029] 在反应器中加入7.5g苯乙烯和52.5g蒸懼水,搅拌混合均匀,在搅拌下加入0.60g甲基丙烯酸甲酯,通入氮气排空,加入0.15g过硫酸铵;在温度为77°C下反应10分钟后,加入7.0g质量分数为30%的二甲基二烯丙基氯化铵水溶液,然后在温度为70°C下继续反应24小时;停止加热并在搅拌下冷却到室温,得到季铵盐表面改性的单分散聚苯乙烯微球乳液。 [0029] 7.5g of styrene and 52.5g distilled added fear of water in a reactor, mixing evenly, 0.60g of methyl methacrylate were added with stirring, nitrogen gas evacuation, 0.15g ammonium persulfate was added; the temperature after reaction at 77 ° C 10 min, mass fraction of 30% 7.0g of dimethyl diallyl ammonium chloride aqueous solution, and then the reaction was continued at a temperature of 70 ° C for 24 hours; the heating was stopped and stirring under It cooled to room temperature to obtain a surface-modified quaternary ammonium salts of monodisperse polystyrene microsphere emulsion. 构成季铵盐表面改性的单分散聚苯乙烯微球乳液中的单分散聚苯乙烯微球的粒径为600nmo Monodisperse polystyrene microspheres monodisperse polystyrene microsphere emulsion constituting the quaternary ammonium salt in the surface-modified particle diameter 600nmo

[0030] 上述实施例只是为了说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所做的等效变换和修饰,都应涵盖在本发明的保护范围之内。 [0030] The above-described embodiments are illustrative only technical concept and features of the invention, its object is to allow those skilled in the art to understand the present invention and accordingly embodiment, and thus does not limit the scope of the present invention, where the modified equivalent transformation and spirit of the invention made, shall fall within the scope of the present invention.

Claims (5)

  1. 1.一种季铵盐表面改性的单分散聚苯乙烯微球乳液的制备方法,其特征是:将苯乙烯与水按1:12~1:7的质量比混合搅拌均匀,按所述的苯乙烯质量的3%~8%向上述搅拌均匀的混合液中加入甲基丙烯酸甲酯;在惰性气氛下,按所述的苯乙烯质量的0.5%~6%再加入过硫酸钾或过硫酸铵•'在温度为77~85°C下反应10~50分钟后,按所述的苯乙烯质量的0.93~2.0倍,加入二甲基二烯丙基氯化铵水溶液;然后在温度为70°C~75°C下反应8~24小时,停止加热并在搅拌下冷却到室温,得到季铵盐表面改性的单分散聚苯乙烯微球乳液。 Preparation of monodisperse polystyrene microspheres emulsion 1. A surface-modified quaternary ammonium salt, wherein: styrene with water at 1: 12 to 1: 7 mass ratio of uniform mixing, the press styrene 3% to 8 mass% of methyl methacrylate was added to the stirred homogeneous mixture; under an inert atmosphere, 0.5% to 6% by mass of the styrene was further added potassium persulfate or ammonium sulfate • 'reaction at a temperature of 77 ~ 85 ° C 10 ~ 50 minutes later, by mass of the styrene is 0.93 to 2.0 times, was added an aqueous solution of dimethyl diallyl ammonium chloride; then at a temperature of the reaction at 70 ° C ~ 75 ° C 8 ~ 24 hours, the heating was stopped and the stirring was cooled to room temperature to obtain a quaternary ammonium salt surface-modified polystyrene microspheres monodisperse emulsion.
  2. 2.根据权利要求1所述的制备方法,其特征是:所述的二甲基二烯丙基氯化铵水溶液的质量分数为30%~60%。 2. The production method according to claim 1, wherein: the mass fraction of dimethyl diallyl ammonium chloride aqueous solution of 30% to 60%.
  3. 3.根据权利要求1所述的制备方法,其特征是:所述的单分散聚苯乙烯微球的粒径范围为150nm ~600nm。 3. The production method according to claim 1, characterized in that: said monodisperse polystyrene microspheres in a particle size range of 150nm ~ 600nm.
  4. 4.一种季铵盐表面改性的单分散聚苯乙烯微球乳液,其特征是:由权利要求1或2的制备方法得到。 A quaternary ammonium salt surface-modified polystyrene microspheres monodisperse emulsion, wherein: production method 1 or 2 obtained by the claims.
  5. 5.根据权利要求4所述的季铵盐表面改性的单分散聚苯乙烯微球乳液,其特征是:组成乳液的季铵盐表面改性的单分散聚苯乙烯微球的粒径范围为150nm~600nm。 Monodisperse polystyrene microsphere emulsion according to claim 4, wherein the surface-modified quaternary ammonium salt, which is characterized in that: monodisperse polystyrene microspheres in a particle size range of the surface-modified quaternary ammonium salt of the composition of the emulsion It is 150nm ~ 600nm.
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