CN102464754A - Emulsifier-free acrylic ester emulsion polymerization method - Google Patents

Emulsifier-free acrylic ester emulsion polymerization method Download PDF

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CN102464754A
CN102464754A CN 201010535262 CN201010535262A CN102464754A CN 102464754 A CN102464754 A CN 102464754A CN 201010535262 CN201010535262 CN 201010535262 CN 201010535262 A CN201010535262 A CN 201010535262A CN 102464754 A CN102464754 A CN 102464754A
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emulsion
monomer
acrylate
acid
reaction
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CN 201010535262
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CN102464754B (en )
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廖德章
张志玮
胡继光
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展华化学工业股份有限公司
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Abstract

The invention relates to an emulsifier-free acrylic ester emulsion polymerization method. For a reaction system comprising 40-60 wt% of purified water, 2-9 wt% of a carboxylic acid monomer (A) with a polymerizable functional group of a carbon-carbon double bond and 40-50 wt% of a methyl acrylicylester monomer or an acrylic ester monomer ( B ), 0.2-2.0 wt% of an inorganic alkali liquid is adopted to adjust the pH value of the reaction to 9.0-13.0, 0.2-1.0 wt% of a peroxide initiator of a sulfate is adopted to carry out emulsion polymerization, and an organic amine compound is adopted to adjustthe pH value of the resulting aqueous resin emulsion to 7.0-9.5 at the terminal stage of the reaction. The prepared aqueous resin emulsion has characteristics of particle size of about 100-130 nm, uniform distribution, good appearance, low acid value of 3.5-6.5 mgKOH/g, specific gravity of about 1.07, excellent storage stability, good permeability and easy construction, wherein the specific gravity of the prepared aqueous resin emulsion is slightly larger than the specific gravity of the water. The dry coating film by the emulsion has characteristics of good water resistance, excellent tensile strength and excellent wear resistance.

Description

一种无乳化剂的丙烯酸酯乳液聚合方法 A non-acrylate emulsion polymerization process emulsifier

技术领域 FIELD

[0001] 本发明涉及水性丙烯酸酯乳液聚合方法,特别是涉及一种无乳化剂的丙烯酸酯乳液聚合方法,可提供环保无公害的水分散性丙烯酸酯乳液,其树脂乳液粒径小且分布均勻外观良好,比重稍大于水,低酸价,储藏安定性优越,渗透性良好容易施工。 [0001] The present invention relates to an aqueous acrylate emulsion polymerization method, emulsion polymerization of acrylates in particular, relates to a method of emulsifier-free, environmental pollution may provide water dispersible acrylic emulsion, its small particle size and a uniform distribution of the resin emulsion good appearance, specific gravity slightly greater than water, a low acid value, excellent storage stability, good permeability easy construction. 其干燥涂膜的耐水性佳,抗拉强度优良且耐磨耗性优越。 Its water resistance of the dried coating film, excellent in tensile strength and excellent abrasion resistance.

背景技术 Background technique

[0002] 传统上,丙烯酸酯乳液是以丙烯酸类单体于水溶液中,采用低分子量乳化剂经乳化聚合反应,对单体、水及/或溶剂、起始剂、乳化剂,在乳化剂的作用及机械搅拌下,使单体在水或其他溶剂中分散成乳状液进行自由基聚合而得。 [0002] Conventionally, acrylic emulsion is an acrylic monomer in an aqueous solution, emulsified low molecular weight emulsifier polymerization reaction, the monomers, water and / or solvent, initiator, emulsifier, the emulsifier and under the action of mechanical stirring, the monomer is dispersed in water or other solvent into the emulsion obtained by free radical polymerization. 但是如果需要制得聚合物固体时,则须破乳、洗涤、脱水、干燥等多步手续,生产成本高;且所得的聚合物产品中乳化剂等杂质不易除尽,而影响电气性能等,并不合适。 However, if required to give a polymer solids, breaking shall, washing, dehydration, drying multi-step procedures, high production costs; and the resulting polymer product and other impurities not easily divisible emulsifiers, affect the electrical properties, It is not appropriate.

[0003] 所得到的乳液在干燥时,乳化剂容易从聚合物内渗出,而污染丙烯酸酯乳液的表面而降低与其他材料间的接着强度,亦不适用。 [0003] The resulting emulsion upon drying, emulsifying readily exude from the polymer, and the acrylic emulsion surface contamination is reduced and the adhesive strength between the other materials, not applicable.

[0004] 为解决乳化剂参与乳化聚合反应所引起的问题,于专利文献1(日本特开2006-206907号)内,记载着使用聚乙二醇辛基苯基醚(polyethyleneglycol octyl phenyl ether)、聚乙二醇壬基苯基醚、聚乙二醇癸基苯基醚等非离子界面活性剂合成丙烯酸酯乳液,虽有助于防制环境污染,但此等环境荷尔蒙的化合物对人体有害,在使用上受限制。 [0004] To solve the problem of emulsification in the emulsion polymerization reaction is caused, in Patent Document (Japanese Patent Laid-Open No. 2006-206907) within 1 discloses the use of polyethylene glycol octylphenyl ether (polyethyleneglycol octyl phenyl ether), polyethylene glycol nonylphenyl ether, polyethylene glycol decyl phenyl ether nonionic surfactant synthetic acrylic emulsion, may help prevention and control of environmental pollution, but these compounds harmful environmental hormones, in the use of restricted.

[0005] 通常进行乳化聚合时,单体在水相中的溶解度较小,不易使液滴迁移至微胞(micelle),而需加入丙酮或异丙醇等有机溶剂予以助溶,也有人尝试加入共乳化剂并在高速搅拌下,使单体于水中被分散成微米级单体液滴供作主要的聚合场所。 When [0005] The emulsion polymerization is generally carried out, the solubility of the monomer in the aqueous phase is small, easy to make the droplets to migrate to the micelles (Micelle), and the like need to add organic solvent to be acetone or isopropanol to aid solubility, others try were added under high-speed stirring emulsifier and the monomer in water is dispersed as micron sized monomer droplets made for the main polymerization sites. 亦即所谓的细乳液聚合,以解决单体难溶的问题。 I.e. the so-called miniemulsion polymerization, in order to solve the problems of insoluble monomers.

[0006] 上述细乳液聚合法可较好的解决单体难溶的问题,有人采用油溶性的起始剂使单体直接在液滴中引发聚合,单体不需由液滴向微胞的迁移过程,可直接液滴成核,避免单体不溶解的问题。 [0006] The mini-emulsion polymerization method can preferably solve problems of insoluble monomers, was employed oil-soluble initiator directly to initiate polymerization of the monomer in the droplets of the monomer from the droplets need to micelles migration process, the droplet nucleation directly, avoiding problems insoluble monomers.

[0007] 有人采用由离子型表面活性剂及长链脂肪醇或长链烷烃组成的复合乳化剂,使单体在细乳液中形成稳定的纳米液滴(30〜500nm)。 [0007] Some compound emulsifier is an ionic surfactant and a long chain fatty alcohols or long-chain alkanes of the monomer to form a stable nanodroplets (30~500nm) in miniemulsion. 由于离子型表面活性剂及复合乳化剂产生的渗透压抵消单体的大小液滴间的压力差,降低不同尺寸液滴间的单体扩散,从而大大提高小液滴的稳定性,使细乳液获得足够的动力学稳定性。 Since the osmolarity ionic surfactant and emulsifier counteract the pressure generated between the difference in size of the droplets of the monomer, the monomer to reduce diffusion between the different size of the droplets, thereby greatly improving the stability of droplets of the miniemulsion sufficient kinetic stability. 使由水、油、表面活性剂及助剂, 能自发形成热力学稳定的乳状液。 So that the water, oil, surfactant and additives, can form spontaneously a thermodynamically stable emulsion.

[0008] 但是在聚合过程中,随着体系组成中的水、溶剂、乳化剂及助乳化剂或聚合反应温度的改变,可以使表面活性剂分子在溶液中,由于亲水、亲油基团而产生的微胞相互转变成油于水中0/W、水于油中W/0及双连续型(bicontinue)B. C三种类型的结构,而成平均粒径小、表面张力低、润湿性渗透性极强、稳定性更好的聚合物微乳液。 [0008] However, in the polymerization process, with the system consisting of water, solvents, emulsifiers or co-emulsifiers and the polymerization reaction temperature was changed to be a surfactant molecule in solution, due to the hydrophilic, lipophilic group the micelles resulting oil converted to each other in 0 / W, water in oil W / 0 and B. C three types of bicontinuous structure (bicontinue) in water, the average particle diameter is made small, low surface tension, Run highly permeable wet, better stability of the microemulsion polymer.

[0009] 于专利文献2(日本特开平7-331208号公报)内,指出在反应性乳化剂、与苯乙烯类及/或(甲基)丙烯酸烷基酯(B)与丙烯酸及/或甲基丙烯酸阴离子性单体(C)为主成分所构成的高分子乳化剂存在下,乳化赋黏剂树脂而得赋黏剂树脂乳液,与含有丙烯酸酯系聚合物乳液及/或黏着剂用乳胶而成的水性黏合剂组成物。 [0009] 2 (Japanese Unexamined Patent Publication No. 7-331208) in the Patent Literature, indicated in the reactive emulsifier, and styrenic and / or (meth) acrylic acid alkyl ester (B) with acrylic acid and / or A the presence of the polymeric emulsifier-based acrylic anionic monomer (C) composed of a main component, a resin obtained by emulsifying excipient excipient adhesion promoter adhesion promoter resin emulsion containing acrylate polymer emulsion and / or a latex adhesive from an aqueous binder composition.

[0010] 但前述反应性乳化剂(A)是指分子中有碳-碳双键具有亲水基及疏水基的界面活性剂的使用比例占构成单体成分高达10〜50wt%,且另需赋黏剂树脂参与反应。 [0010] However, the reactive emulsifier (A) refers to a molecule having a carbon - carbon double bond having a surfactant used in a proportion of hydrophilic group and hydrophobic group constituting monomer component accounts for up to 10~50wt%, and the other for an excipients reacted resin adhesion promoter.

[0011] 如何避免乳化剂参与反应引起的问题点,反应过程中完全不加乳化剂或仅加入微量乳化剂(其浓度小于临界微胞浓度CMC)的乳液聚合过程或是所得聚合物的一部分具有高分子乳化剂的特征,即为乳化聚合的时势所趋。 [0011] How to avoid problems caused by emulsification of the reaction, the reaction part of the process completely without addition of emulsifier or emulsifier only trace amounts (at a concentration less than the critical micelle concentration CMC) or emulsion polymerization process the resultant polymer having wherein the polymeric emulsifier, emulsion polymerization is the trend of the times. 此即为不加常规乳化剂的无皂乳液聚合, 可得表面洁净、单一分散的乳胶粒,同时避免乳化剂对环境的影响。 That is, for an emulsifier without conventional emulsion polymerization, clean surface can be obtained, monodisperse latex particles, while avoiding the environmental impact emulsifier.

[0012] 另外,于专利文献1内,指出合成丙烯酸酯乳液时,由使用水溶性增黏树脂而不使用乳化剂进行乳液聚合,可提高丙烯酸酯乳液的冻结安定性,且可于冻结后的解冻时可再使用,以一次的合成可使完全满足此等物性,虽有缩短工序阶段的效果。 [0012] Further, in Patent Document 1, when the indicated synthetic acrylic emulsion, a water-soluble tackifying resin without the use of emulsifiers for emulsion polymerization, a freezing acrylic emulsion stability, and can be frozen after reusable thawed to a synthesis can satisfy these properties, although the effect of shortening the process stages. 但是所采用的增黏树脂是水溶性,使所得的乳胶膜欠缺耐水性,并不适用于涂料方面。 However, the tackifying resins used are water soluble, the resulting lack of water resistance of the latex film, not suitable for coatings.

[0013] 欲解决耐水性的问题点,应自与乳胶膜中的电解质及其他低分子的含量有关的乳胶胶粒稳定性着手。 [0013] To solve the problem of water resistance, stability should proceed from latex rubber and latex membrane electrolyte content and other low molecular weight related. 而乳胶胶粒稳定性主要由表面活性寡聚物所决定,乳胶胶粒表面电荷密度愈大,则稳定性愈佳;胶粒表面稳定性尚取决于乳胶胶粒粒子表面的亲水性,亲水性愈大,则稳定性愈佳;此乃因乳胶胶粒的极性导致粒子表面与水相界面相互作用而降低界面的GilDbs自由能,使能提高乳化液胶粒粒子的稳定性所致。 Latex rubber and stability is mainly determined by the surface active oligomer, rubber latex surface charge density greater, the more the stability is good; colloidal stability of the surface is still dependent on a hydrophilic surface of latex rubber particles, pro aqueous larger, the more the stability is good; This is due to the polarity of the latex particles and causes the surface of the micelle aqueous phase interface decreases GilDbs interaction free energy that can improve the stability of emulsion particles due micelles .

[0014] 因此在避免采用非离子界面活性剂产生的污染及共乳化剂解决单体难溶的问题, 及进行不加常规乳化剂的无皂乳液聚合,并提高乳化聚合时小液滴的稳定性及由表面活性寡聚物提高乳胶胶粒的稳定性,而得表面洁净、单一分散的乳胶粒,同时避免乳化剂对环境的影响,即为本发明亟待解决的课题。 [0014] Therefore, in avoiding contamination and were employed nonionic surfactant emulsifiers to produce insoluble monomer solution to the problem, and performed without the conventional free emulsion polymerization emulsifier, emulsion polymerization and to improve the stability of droplets property and improving the surface active oligomer rubber latex stability, clean surface is obtained, monodisperse latex particles, while avoiding the influence of the emulsifier on the environment, the present invention is the problem to be solved.

发明内容 SUMMARY

[0015] 本发明的目的在于提供一种无乳化剂的丙烯酸酯乳液聚合方法,以合成出平均粒径均勻、润湿性渗透性极强、稳定性更好的聚合物微乳液。 [0015] The object of the present invention to provide an acrylate emulsifier-free emulsion polymerization method, an average particle size uniform, highly permeable wetting, better stability of the microemulsion polymer synthesized.

[0016] 为实现上述目的,本发明提供的无乳化剂的丙烯酸酯乳液聚合方法,包括下述工序: [0016] To achieve the above object, the present invention provides an emulsifier-free acrylate emulsion polymerization process, comprising the steps of:

[0017] 1)制备由纯水40〜60wt%、具碳-碳双键可聚合官能基的羧酸单体A2〜9wt%、 和甲基丙烯酸烷酯或丙烯酸烷酯单体B 40〜50wt%为主成分而成的反应系; [0017] 1) Preparation of pure water 40~60wt%, having a carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group A2~9wt%, and alkyl methacrylates or alkyl acrylates monomer B 40~50wt % of a main component from the reaction system;

[0018] 2)以0. 2〜2衬%的无机碱液调整反应在pH9. 0〜13. 0的范围内; [0018] 2) 0.5% of an inorganic alkaline 2~2 liner within the scope of the reaction was adjusted to pH9 0~13 0.;

[0019] 3)保持该反应于温度70〜95°C且以转速150〜300rpm搅拌30分钟,采用0. 2〜 1. Owt %的过硫酸钠,过硫酸钾,过硫酸铵而成的群体选出的一种或一种以上作为起始剂予以起始化,进行乳化聚合; [0019] 3) The reaction was kept stirred at a temperature and a rotation speed of 70~95 ° C 150~300rpm 30 min using 0. 2~ 1. Owt% of sodium persulfate, potassium persulfate, ammonium persulfate groups formed selected from one or more of starting to be used as an initiator, emulsion polymerization;

[0020] 4)于反应末期以由氨水、三甲胺、单乙醇胺、二甲基乙醇胺、二甲基乙醇胺、2-胺基-2-甲基丙醇而成的群体中选出一种或一种以上的有机胺类调整所得到的水性树脂乳化液的PH值于7. 0〜9. 5的范围内,得到粒径100〜130nm均一且分布极窄小的水性压克力聚合体。 [0020] 4) at the end of the reaction to ammonia, trimethylamine, monoethanolamine, dimethyl ethanolamine, dimethylethanolamine, 2-amino-2-methyl-propanol obtained by selecting one or a group PH aqueous resin emulsion or more organic amines adjustment value obtained in the range of 0 ~ 9 7. 5, and to give a uniform particle size distribution is very narrow 100~130nm aqueous acrylic polymer.

[0021] 所述的聚合方法,其中具述碳-碳双键可聚合官能基的羧酸单体A是由丙烯酸、甲基丙烯酸、依康酸和巴豆酸群体选出的一种或一种以上[0022] 所述的聚合方法,其中甲基丙烯酸烷酯或丙烯酸烷酯单体B是甲基丙烯酸甲酯、 甲基丙烯酸乙基酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸第三丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸第三丁酯、丙烯酸2-乙己酯、甲基丙烯酸2-乙己酯、甲基丙烯酸月桂酯、丙烯腈、丙烯腈群体选出的一种或一种以上。 [0021] The polymerization method, wherein said having a carbon - carbon double bond of a carboxylic acid monomer A polymerizable functional group is acrylic acid, methacrylic acid, itaconic acid and crotonic acid or one group selected from above [0022] the polymerization method, wherein the alkyl methacrylates or alkyl acrylates B monomer is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, third, butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, acrylonitrile, acrylonitrile groups selected from one or more.

[0023] 所述的聚合方法,其中无机碱液是由氢氧化钠、氢氧化钾、磷酸三钠群体选出的一种或一种以上。 [0023] The polymerization method, wherein the inorganic alkali is sodium hydroxide, potassium hydroxide, an aqueous trisodium phosphate or one or more groups selected.

[0024] 由本发明方法乳化聚合制备而得表面具有较大亲水性及较佳稳定性的乳胶胶粒粒子,合成出平均粒径均勻、润湿性渗透性极强、稳定性更好的聚合物微乳液。 [0024] by the method of the present invention is obtained by emulsion polymerization has a greater surface hydrophilic colloid and latex particles better stability, the average particle diameter of the synthetic uniform, highly permeable wetting, better polymerization stability It was microemulsion.

附图说明 BRIEF DESCRIPTION

[0025] 图1为与本发明有关的一种无乳化剂的丙烯酸酯乳液的聚合方法,由其中实施例1〜5所得的乳液聚合物的微球粒径分布曲线而直接得出微球粒径的分布情况。 [0025] FIG. 1 is a process for the polymerization emulsifier-free emulsion acrylate related to the present invention, the particle size distribution curve of the microspheres in the emulsion polymer obtained in Example 1 ~ 5 by the embodiment wherein the microspheres obtained directly diameter distribution.

[0026] 图2为与本发明有关的一种无乳化剂的丙烯酸酯乳液的聚合方法,由其中实施例1 所得的乳液聚合物利用METTLER-TOLEDO Differentialscanning calorimeters (DSC)所测得的Tg点。 The polymerization process [0026] Figure 2 is relevant to the present invention, one kind of emulsifier-free acrylate emulsion, wherein the emulsion polymer obtained in Example 1 using the METTLER-TOLEDO Differentialscanning calorimeters (DSC) Tg measured point embodiment.

[0027] 附图标号说明: [0027] Reference numerals:

[0028] 纵坐标:体积(<% ); [0028] ordinate: volume (<%);

[0029] 横坐标:粒径(μ m)。 [0029] Abscissa: particle diameter (μ m).

具体实施方式 detailed description

[0030] 本发明对由纯水40〜60wt%、具碳-碳双键可聚合官能基的羧酸单体A2〜 9wt%、及甲基丙烯酸烷酯或丙烯酸烷酯单体B 40〜50wt%为主成分而成的反应,不采用有机溶剂或助溶剂或两性溶剂,先以无机碱液0. 2〜2. 调整反应在适当的pH值范围(以pH 9. 0〜13. 0为宜,其中又以11. 0〜13. 0为较宜)下加入起始剂予以起始化进行无乳化剂的乳化聚合反应,于反应末段添加适量PH调整剂的有机胺类以调整pH于7. 0〜 9. 5的范围内(以8. 0〜9. 0为宜),可制成粒径100〜130nm分布均勻且极窄的聚合体乳液,以至完成本发明。 [0030] The present invention is made of water 40~60wt%, having a carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group A2~ 9wt%, or alkyl methacrylates and alkyl acrylates monomer B 40~50wt % obtained by reacting the main component, an organic solvent or without using the amphoteric solvent or co-solvent, an inorganic alkali to 2~2 0.5. adjusted in an appropriate range pH (to pH 9. 0~13. 0 to should, among 0~13 11. 0 is more appropriate) be added at the start of the initiator emulsifier-free emulsion polymerization, a suitable amount pH adjusting agent include organic amines in the last paragraph of the reaction to adjust the pH 7. 0~ in the range of 9.5 (at 8. 0 ~ 9. preferably 0), may be an emulsion polymer with a particle size distribution of 100~130nm uniform and extremely narrow, leading to completion of the present invention. 可提供环保无公害的水分散性丙烯酸酯乳液,其树脂乳液粒径小且分布均勻外观良好,比重稍大于水,低酸价,储藏安定性优越,渗透性佳容易施工。 It provides environmental pollution of the water-dispersible acrylic emulsion of small particle size and a distribution of the resin emulsion which good uniform appearance, slightly larger than the specific gravity of water, a low acid value, excellent storage stability, good permeability easy construction. 其干燥涂膜的耐水性佳,抗拉强度优良且耐磨耗性优越。 Its water resistance of the dried coating film, excellent in tensile strength and excellent abrasion resistance.

[0031] 本发明于乳液聚合时,使用具碳-碳双键可聚合官能基的羧酸单体于水内,以无机碱类溶解丙烯酸单体使碳-碳双键可聚合官能基的羧酸单体溶解而成碱性水溶液使在聚合物分子链(亲油)的端基上形成亲水性的离子基团,以硫酸盐类的过氧化物作为起始剂,在微球表面形成带电层可使乳液稳定。 [0031] When the emulsion polymerization in the present invention, having a carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group in the water to dissolve inorganic bases acrylic monomer of the carbon - carbon double bond polymerizable functional carboxylic groups an alkaline aqueous solution obtained by dissolving the acid monomers forming the hydrophilic ionic groups on the polymer chains (lipophilic) end groups to sulfates peroxide as initiator, formed on the surface of the microspheres charging layer can stabilize the emulsion.

[0032] 通常乳化方法中所采的丙烯酸单体在水相中的溶解度太小,不易由单体液滴向微胞迁移,如采用传统的乳液聚合方法,欲得到稳定的丙烯酸酯乳液比较困难,需采工业上常加入的有机溶剂(例如丙酮或者异丙醇等)的方式予以增溶。 [0032] The acrylic monomer is generally adopted as the method of emulsification in the aqueous phase, the solubility is too small to easily migrate from the monomer droplet micelles, such as the use of conventional emulsion polymerization process, to be obtained a stable emulsion is difficult acrylate, mining industry often required the addition of an organic solvent (e.g. acetone or isopropanol) in a manner to be solubilized. 而本发明在考虑所得的水性丙烯酸酯乳液的涂膜性能时,即不采用有机溶剂。 In considering the present invention the film properties resulting aqueous acrylic emulsion, i.e., without using an organic solvent.

[0033] 本发明所采用的起始剂,虽然可采用常规的苯甲酰过氧化物(BPO)、偶氮异丁腈(AIBN)、过硫酸钠、过硫酸铵、过硫酸钾、过氧化氢的过氧化物而成的群体选出的一种或一种以上作为起始剂予以起始化。 [0033] The initiator used in the present invention, although using conventional benzoyl peroxide (the BPO), azobisisobutyronitrile (AIBN), sodium persulfate, ammonium persulfate, potassium persulfate, peroxide hydrogen peroxide groups selected from one or more of starting to be used as an initiator. 但是于本发明宜为采用硫酸盐过氧化物,例如可举出过硫酸钠(以下简称为Na2S2O8)、过硫酸钾(以下简称为Kj2O8)、过硫酸铵(以下简称为(NH4)2S2O8)。 However, in the present invention is suitable for the introduction of peroxide sulphates, for example, include sodium persulfate (hereinafter abbreviated as on Na2S2O8), potassium persulfate (hereinafter abbreviated as Kj2O8), ammonium persulfate (hereinafter abbreviated as (NH4) 2S2O8).

[0034] 单体分子在水中由起始剂引发聚合,链增长速度比较快,当生成的聚合物分子量达到某一临界值时,即从水相中析出,形成初始乳胶粒子。 [0034] monomer molecule in water initiated by a polymerization initiator, chain faster, when the molecular weight of the resulting polymer reaches a critical value, i.e., precipitate from the aqueous phase, forming the initial latex particles. 由于这些粒子表面电荷密度比较低,粒子之间静电排斥力不足而使粒子稳定,即可相互聚集,直至生成稳定的乳胶粒子,在聚合物分子链(亲油)及其末端基上的离子基(亲水),生成的酯类具有阴离子乳化剂的特性-含亲水亲油基,而达到无乳化剂的乳化效果,使聚合而得的聚合物酯类具有阴离子乳化剂的特性,而达到无乳化剂进行乳液聚合的乳化效果。 Since the surface charge density of these particles is relatively low, insufficient electrostatic repulsion between the particles are stable particles can agglomerate with each other until a stable latex particles generated in the polymer chains (lipophilic) groups and ionic groups on the ends (hydrophilic), the resulting ester has a characteristic of anionic emulsifiers - having a hydrophilic lipophilic groups, to achieve the effect of emulsifier-free emulsion, the polymer obtained by the polymerization has a characteristic ester anionic emulsifiers, to achieve emulsifier-free emulsion polymerization effect emulsification.

[0035] 本发明由加入无机碱,使参与乳化聚合反应的单体产生极性基团而于微球表面形成带电层,可使乳液稳定使所得的乳胶胶粒粒子表面具有亲水基,以取代传统乳化剂。 [0035] The present invention is by the addition of an inorganic base, emulsion polymerization of the monomers involved in generating the polar group is formed on a charged microsphere surface layer, the surface of the latex emulsion stabilizers make the micelle particles obtained having a hydrophilic group to replace traditional emulsifier.

[0036] 在反应过程中完全不加乳化剂,使(甲基)丙烯酸烷基酯(B),与具碳-碳双键可聚合官能基的羧酸单体(A)为主成分进行乳化聚合,使所得聚合物的一部分具有高分子乳化剂的特征,于反应末段选用有机胺类调整所得水性树脂乳化液的PH值于pH 7. 0〜9. 5 的范围内,且所得的水性树脂乳化液的酸价低至3. 5〜6. 5mgK0H/g。 [0036] During the reaction completely without emulsifier, (meth) acrylate (B), and having a carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group (A) as a main component was emulsified polymerization, characterized in that the polymeric emulsifier having a portion of the resulting polymer, the reaction in the last paragraph of organic amines selected adjustment resulting aqueous resin emulsion PH value in the range of pH 7. 0~9. 5, and the resulting aqueous acid resin emulsion lowest to 3. 5~6. 5mgK0H / g. 又进行无乳化剂的乳化聚合时,使在亲油的聚合物分子链的末端基上形成亲水性的离子基团,在所得的乳胶胶粒的微球表面形成带电层可使乳液稳定。 When another emulsifier-free emulsion polymerization, a hydrophilic ionic groups in the molecular chain terminal group oleophilic polymer, stable emulsions can form a charged layer on the surface of the microspheres of the resulting latex micelles.

[0037] 本发明所采用的无机碱,虽然可采用由氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、氢化钙、氢化钠、氢化钾、磷酸三钠而成的群体选出的一种或一种以上,但是宜为氢氧化钠、氢氧化钾、磷酸三钠中的一种或一种以上。 [0037] The inorganic base used in the present invention, although may be employed with sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium hydride, sodium hydride, potassium hydride, trisodium phosphate group selected from out one or more, but is suitably sodium hydroxide, potassium hydroxide, trisodium phosphate, one or more than one. 此种无机碱可使与其反应的具碳-碳双键可聚合官能基的羧酸单体在宽广的PH范围有高度的亲水性及阴离子特性,使在亲油的聚合物分子链的末端基上形成亲水性的离子基团,以致所得的乳胶胶粒的微球表面形成带电层,而得稳定的乳液。 Such can react with an inorganic base having a carbon - carbon double bond polymerizable functional group acid monomer in a wide range of PH highly hydrophilic and anionic character, so that at the end of the polymer chains of the lipophilic forming on a substrate a hydrophilic ionic groups, so that the surface of the resulting latex microspheres micelle form a charged layer to give a stable emulsion.

[0038] 于本发明中,于水中的具碳-碳双键可聚合官能基的羧酸单体,例如可举出丙烯酸、甲基丙烯酸、巴豆酸(顺丁烯酸)等单羧酸、或马林酸、马林酸酐、富马酸、伊康酸、黏康酸(2,4-己二烯二酸)等二羧酸类的羧酸,以硫酸盐的过氧化物作为起始剂,以无机碱使M 酸单体溶解而得高分子的亲水性树脂,所得聚合物的一部分具有高分子乳化剂的特征,可取代常规的界面活性剂,在反应过程中完全不加乳化剂使靈酸单体于水内进行无乳化剂的乳化聚合,使在聚合物分子链的亲油的末端基上形成亲水性的离子基团而在微球表面形成带电层使乳液稳定。 [0038] In the present invention, in water having a carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group, and examples thereof include acrylic acid, methacrylic acid, crotonic acid (cis-crotonic acid), and other monocarboxylic acids, Malic or, Marin anhydride, fumaric acid, itaconic acid, muconic acid (2,4 hexadiene acid) dicarboxylic acids other carboxylic acids, as a starting peroxide sulphate agent, an inorganic base to an acid monomer M obtained by dissolving a hydrophilic polymer resin, wherein a portion of the resulting polymer having a high molecular emulsifier can replace conventional surfactant, during the reaction without completely emulsified Ling agent to an acid monomer emulsifier-free emulsion polymerization in water, forming a hydrophilic ionic groups in the end group of the lipophilic chain of the polymer molecule to form a charged layer on the surface of the microspheres stabilize the emulsion.

[0039] 至于本发明所用具碳-碳双键可聚合官能基的羧酸单体(A),占反应的使用比例是指2〜9wt%,其使用比例若未满2wt%时,则所得该共聚物的乳化性降低,较易起泡,又超过9wt %时,则该共聚物的疏水性变成过大,而乳化性变差。 [0039] As the device of the present invention is a carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group (A), the proportion of reactive means 2~9wt%, if the ratio is less than when using 2wt%, the resulting when the copolymer emulsion is lowered, foaming easily, and more than 9wt%, the copolymer becomes too large hydrophobicity, and the emulsifiability deteriorates. 单体B的使用比例是指40〜 50wt %,其使用比例若未满40wt %时,则所得该共聚物的乳化性降低又超过50wt %时,则该共聚物的亲水性变成过大,所得的树脂乳液的性能降低,尤其耐水性降低。 Monomer B is used in a proportion refers 40~ 50wt%, if the amount thereof is less than 40wt%, the emulsification of the resulting copolymer is reduced and exceeds 50wt%, the hydrophilicity of the copolymer becomes too large , properties of the resulting resin emulsion is decreased, in particular the water resistance is lowered.

[0040] 于本发明所采用的无机碱,可使与其反应的具碳-碳双键可聚合官能基的羧酸单体在宽广的PH范围有高度的亲水性及阴离子特性,使在亲油的聚合物分子链的末端基上形成亲水性的离子基团,以致所得的乳胶胶粒的微球表面形成带电层,而得稳定的乳液,具有优越的乳化性能,其酸价虽未予特别的限定,但以经中和时的共聚物固形份的酸价通常以设成在3. 5〜6. 5mg KOH/g左右为宜。 [0040] The inorganic base employed in the present invention, can react with the carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group in a wide range of PH highly hydrophilic and anionic character, so that in the parent is formed on the end of the molecular chain of the polymer oils hydrophilic ionic groups, so that the surface of the resulting latex microspheres micelle form a charged layer to give a stable emulsion having excellent emulsifying properties, although not acid value I particularly limited, but the solid parts of the copolymer acid neutralized by monovalent generally set to at 3. 5~6. 5mg KOH / g or so is appropriate.

[0041] 至于本发明所用的压克力单体,由考虑所得的水性丙烯酸酯乳液的黏着性、该乳化液的黏度或安定性等予以决定,需将各该玻璃转移温度(Tg)设定于特定范围内。 [0041] As the acrylic monomer used in the present invention, by a consideration of the adhesive aqueous acrylic emulsion obtained, the emulsion viscosity stability or the like to be determined, each of the glass transition temperature (Tg) required to set within a specific range. 压克力单体成分的Tg设定于-20〜20°C,宜为-5〜10°C。 Tg acrylic monomer component is set at -20~20 ° C, is suitably -5~10 ° C.

[0042] 水性丙烯酸酯乳液的固形分以设定成40〜50%为宜,可容易抑制制造水性乳化液时的黏度,且可使凝集强度提高。 [0042] The aqueous acrylic emulsion to set to a solid content of 40~50%, more preferably be easy to suppress the viscosity of the aqueous emulsion during production, and can improve the strength of the agglutination. 且所得的水性丙烯酸酯乳液的形态,并不含有机溶剂。 And form an aqueous acrylic emulsion obtained, not containing organic solvents.

[0043] 适用于本发明方法的压克力单体,虽未予特别限制,其中具碳-碳双键可聚合官能基的羧酸A单体,例如可举出由丙烯酸(acrylic acid ;以下简称为AAc)、甲基丙烯酸(methacrylic acid ;以下简称为MAAc)、富马酸(fumaric acid)、依康酸(itaconic acid ; 以下简称为ITA)及巴豆酸(crotonicacid ;以下简称为CTA)而成的群体选出的一种或一种以上。 [0043] The method of the present invention suitable acrylic monomers, although not been particularly limits having a carbon - carbon double bond polymerizable carboxylic acid monomer having a functional group A includes, for example from acrylic acid (acrylic acid; hereinafter abbreviated as AAc), methacrylic acid (methacrylic acid; hereinafter abbreviated as MAAc), fumaric acid (fumaric acid), itaconic acid (itaconic acid; hereinafter referred to as ITA) and crotonic acid (crotonicacid; hereinafter referred to as CTA) and into one or more groups selected.

[0044] 至于甲基丙烯酸烷酯或丙烯酸烷酯单体B,例如可举出由甲基丙烯酸甲酯(methyl methacrylate ;以下简称为MMA)、甲基丙烯酸乙基酯(ethylmethacrylate ;EMA)、甲基丙烯酸正丁酉旨(η-butyl methacrylate ;n_BMA)、甲基丙;! [0044] As for the alkyl methacrylate or alkyl acrylate monomers B, from for example, include methyl methacrylate (methyl methacrylate; hereinafter abbreviated as MMA), ethyl methacrylate (ethylmethacrylate; EMA), A Ding purpose yl acrylate, n (η-butyl methacrylate; n_BMA), methyl propyl;! ;希酸异丁酉旨(i—butyl methacrylate ; i-BMA)、甲基丙烯酸第三丁酯(t-butyl methacrylate ; t-BMA)、丙烯酸甲酯(methyl acrylate ;MA)、丙;I;希酸乙酉旨(ethyl acrylate ;EA)、丙;I;希酸正丁酉旨(n_butyl acrylate ; 以下简称为n-BA)、丙烯酸异丁酯(i-butyl acrylate ;以下简称为i_BA)、丙烯酸第三丁酯(t-butyl acrylate ;t_BA)、丙烯酸2-乙己酯Q-ethyl hexyl scrylate ;以下简称为2-EHA)、甲基丙烯酸2-乙己酯Q-ethyl hexyl methylacrylate ;2_EHMA)、甲基丙烯酸月桂酯(lauric methyl acrylate ;LMA);丙烯腈(acrylnitrile ;AN)、丙烯腈(methyl acrylnitrile ;MAN)而成的群体选出的一种或一种以上。 ; Ding purpose Greek isobutyl (i-butyl methacrylate; i-BMA), tertiary butyl methacrylate (t-butyl methacrylate; t-BMA), methyl acrylate (methyl acrylate; MA), propyl; the I; Xi acid yiyou purpose (ethyl acrylate; EA), propyl; the I; n Ding purpose Greek acid (n_butyl acrylate; hereinafter referred to as n-BA), isobutyl methacrylate (i-butyl acrylate; hereinafter abbreviated as i_BA), the third acrylic butyl (t-butyl acrylate; t_BA), acrylate, 2-ethylhexyl acrylate Q-ethyl hexyl scrylate; hereinafter referred to as 2-EHA), methyl acrylate, 2-ethylhexyl acrylate Q-ethyl hexyl methylacrylate; 2_EHMA), lauryl methacrylate, ester (lauric methyl acrylate; LMA); acrylonitrile (acrylnitrile; AN), acrylonitrile (methyl acrylnitrile; MAN) one kind selected from a group of one or more. 且视必要时,亦可合并使用醋酸乙烯酯、苯乙烯等丙烯酸酯系单体以外的单体。 When and as necessary, a monomer other than vinyl acetate, styrene, acrylate monomers may also be used in combination.

[0045] 由本发明方法而得的压克力树脂乳化液,其储藏安定性良好,与传统方式而得者比较时,由于其在耐热性、黏着强度、凝集强度、涂布性方面良好。 [0045] The method of the acrylic resin emulsion obtained according to the present invention, which is excellent storage stability, when compared to those obtained by conventional manner, because of its heat resistance, adhesive strength, agglutination strength, good coatability. 且因该树脂乳化液中并不含有机溶剂,对使用作涂料者而言,在安全卫生方面是较宜的。 And because the resin emulsion not containing organic solvents, for use as coatings are concerned, in terms of safety and health is the more appropriate. 尤其最适宜使用在要求耐热性、黏着强度、凝集强度较高的制品中残留溶剂的标准严格的建材。 Most particularly suitable for use in heat resistance, adhesive strength, cohesive strength of the article in a higher residual solvent strict standards of building materials.

[0046] 本发明方法中单体分子在水中由起始剂引发聚合,所以链增长速度比较快,当生成的聚合物分子量达到某一临界值时,即从水相中析出,形成初始乳胶粒子。 [0046] The method of the present invention, the monomer molecule in water initiated by a polymerization initiator, the chain growth faster, when the molecular weight of the resulting polymer reaches a critical value, i.e., precipitate from the aqueous phase, forming the initial latex particles . 由于这些粒子表面电荷密度比较低,粒子之间静电排斥力不足而使粒子稳定,即可相互聚集,直至生成稳定的乳胶粒子在亲油的聚合物分子链的末端基上形成亲水的离子基团,其生成的酯类具有阴离子乳化剂的特性,而达到无乳化剂的乳化效果,使聚合而得的聚合物酯类具有阴离子乳化剂的特性,而达到无乳化剂进行乳液聚合的乳化效果。 Since the surface charge density of these particles is relatively low, the electrostatic repulsion between the particles is less than the stable particles can agglomerate with each other, until the particles form a stable emulsion of forming a hydrophilic ionic group on a molecular chain terminal group oleophilic polymer group, which generates esters having a characteristic of anionic emulsifiers, the emulsifier-free emulsion to achieve the effect, a polymer obtained by the polymerization has a characteristic ester anionic emulsifiers, emulsification to achieve the effect of emulsifier-free emulsion polymerization .

[0047] 本发明方法中所采用作pH调整剂的有机胺类,可列举有:氨水(ammonia;以下简称为NH4OH)、三甲胺(trimethyl amine ;以下简称为TMA)、二乙基胺(Diethylamine ; DEA)、三乙基胺(triethylamine ;TEA)、单乙醇胺(monoethanolamine,;以下简称为ΜΕΤΑ)、 二乙醇胺diethanolamine ;DETA)、二甲基乙醇胺(dimethyl ethanolamine ;以下简称为DMEA)、二乙基乙醇胺(dimethyl ethanolamine ;DEEA)、异丙基乙醇胺(isopropyl ethanolamine,;以下简称为IPEA)、2_ 月安基一2-甲基丙醇(2-amino-2-methyl propanol, AMP)、2_ 二甲月安■ 甲■ M 酉享(2-dimethylamino-2-methyl propanol ;DMAMP) 、0¾ if木(morpholine, MOR)、η- (η-methyl morpholine ;NMR)、η ^¾¾¾! (morpholine ; PH adjusting agent as an organic amine [0047] The method of the present invention is employed, there can be enumerated: aqueous ammonia (Ammonia; hereinafter abbreviated as NH40H), trimethylamine (trimethyl amine; hereinafter abbreviated as TMA), diethylamine (Diethylamine ; DEA), triethylamine (triethylamine; TEA), monoethanolamine (monoethanolamine ,; hereinafter abbreviated as ΜΕΤΑ), diethanolamine diethanolamine; DETA), dimethylethanolamine (dimethyl ethanolamine; hereinafter abbreviated as DMEA), diethyl ethanolamine (dimethyl ethanolamine; DEEA), isopropyl ethanolamine (isopropyl ethanolamine ,; hereinafter abbreviated as IPEA), 2_ month Kay a methyl propanol (2-amino-2-methyl propanol, AMP), 2_ dimethyl An month ■ ■ A unitary sharing M (2-dimethylamino-2-methyl propanol; DMAMP), 0¾ if wood (morpholine, MOR), η- (η-methyl morpholine; NMR), η ^ ¾¾¾ (morpholine!;

NEM)等。 NEM) and so on. 其中较宜使用的为氨水、三甲胺、二甲基乙醇胺、2-胺基-2-甲基丙醇等。 Which is more appropriate to use ammonia, trimethylamine, dimethylethanolamine, 2-amino-2-methyl propanol.

[0048] 由本发明方法乳化聚合制备而得表面具有较大的亲水性及较佳的稳定性的乳胶胶粒粒子,合成出平均粒径小、表面张力低、润湿性渗透性极强、稳定性更好的聚合物乳液。 [0048] The emulsion polymerization prepared by the process of the present invention is obtained by having a greater surface hydrophilic colloidal particles and better stability of the latex, synthesized small average particle size, low surface tension, wettability highly permeable, better stability of the polymer emulsion.

[0049] 本发明有关的一种无乳化剂的丙烯酸酯乳液的聚合方法,是于反应槽内加入由对由纯水40〜60wt %及具碳-碳双键可聚合官能基的羧酸单体(A) 2〜9wt %、甲基丙烯酸烷酯或丙烯酸烷酯单体(B)40〜50wt%而成的反应,先以无机碱液0. 2〜2. 调整反应在pH值9.0〜13.0的范围内,接着采用由硫酸盐的过氧化物起始剂0.2〜1.0衬%,进行乳化聚合,于反应末段以有机胺化合物调整所得的水性树脂乳化液的PH值于7. 0〜9. 5的范围内。 [0049] The polymerization process relating acrylate emulsifier-free emulsions according to the invention, is added to the reaction vessel by the pure water 40~60wt% and having a carbon - carbon double bond polymerizable functional carboxylic groups single (B) 40~50wt% reactant obtained by (a) 2~9wt%, methacrylic acid alkyl ester or acrylic acid alkyl ester monomer, an inorganic alkali to 0.5 2~2. the reaction adjust the pH 9.0~ in the range of 13.0, followed by the use of a peroxide initiator liner sulfate 0.2~1.0%, emulsion polymerization, adjusting the PH value of the resulting aqueous resin emulsion is an organic amine compound in the reaction in the last paragraph 7. 0~ within a range of 9.5. 制得的水性树脂乳化液,粒径约100〜130nm且分布均勻外观良好,低酸价3. 5〜 6. 5mgK0H/g,其比重约为1. 07稍大于水,储藏安定性优越,渗透性佳容易施工。 The resulting aqueous resin emulsion, and particle size distribution of from about 100~130nm good uniform appearance, low acid value 3. 5~ 6. 5mgK0H / g, which is slightly larger than the specific gravity of about 1.07 in water, excellent storage stability, penetration best of easy construction. 其干燥涂膜的耐水性佳,抗拉强度优良且耐磨耗性优越。 Its water resistance of the dried coating film, excellent in tensile strength and excellent abrasion resistance.

[0050] 首先秤取蒸镏水(先加入占参与聚合反应的反应物的40〜60wt%的蒸镏水),开始以转速约150〜300RPM搅拌,维持于70〜95°C后,加入具碳-碳双键可聚合官能基的羧酸单体及无机碱液、于20〜30分钟到达设定温度后加入起始剂,开始缓慢滴加丙烯酸烷酯或甲基丙烯酸烷酯单体并于2. 0〜4. 5小时完成滴加,并保持温度及转速下继续反应约2〜3小时。 [0050] First weighed distilled water (added to account for 40~60wt% of the reactants involved in the polymerization reaction distilled water), begins at a rotational speed of about 150~300RPM stirring maintained after 70~95 ° C, is added with carbon - carbon double bond polymerizable functional group of carboxylic acid monomer and an inorganic alkali at 20 to 30 minutes after reaching the set temperature initiator was added, slowly dropwise alkyl acrylates or alkyl methacrylates monomers and 2. 0~4 to 5 hours to complete the dropwise addition, the reaction was continued and maintained for about 2 to 3 hours at a temperature and speed. 关闭加热器但继续搅拌使其自然降温。 Turn off the heater but continued to mix and natural cooling. 下降至40°C后,以水稀释pH调整剂的有机胺类后,缓慢加入约15分钟,使pH值达到8. 0〜9. 0,结束聚合反应。 Then decreased to 40 ° C, diluted with water and the pH adjusting agent is an organic amine, was slowly added for about 15 minutes, the pH value reached 8. 0 ~ 9. 0, the end of the polymerization reaction. 所得的水性丙烯酸酯乳液的平均粒径小(微球粒径d为100〜130nm)。 The resulting aqueous emulsion of acrylic ester small average particle size (diameter d of microspheres 100~130nm).

[0051] 由本发明方法乳化聚合制备而得表面具有较大的亲水性及较佳的稳定性的乳胶胶粒粒子,合成出平均粒径均勻、润湿性渗透性极强、稳定性更好的聚合物微乳液。 [0051] by the method of the present invention is obtained by emulsion polymerization of a hydrophilic surface having a large latex and preferred colloidal particle stability, and a uniform average particle diameter of the synthetic, highly permeable wetting, better stability polymeric microemulsion.

[0052] 探究本发明方法何以可达成无乳化剂进行乳液聚合,大致可归因于为有效的合成粒径均勻的聚合物粒子,通常适用异相系聚合反应。 [0052] The method of the present invention is to explore how polymerization can be achieved without an emulsifier, is generally attributable to the effective diameter of the synthetic polymer particles uniform, generally apply different phase polymerization system. 异相是聚合有采用水作为溶剂的乳化聚合或采用有机液体作为溶剂的分散聚合。 It has different phase polymerization using water as a solvent or emulsion polymerization using an organic liquid as a dispersion in the polymerization solvent. 任一种情形因均是大量添加皂类或高分子安定剂等分散剂,有合成后的后处理问题或杂质残留于生成物的问题。 Either case by adding a large amount of soaps are the polymer stabilizer or a dispersing agent, post-processing problems or impurities remaining in the synthesized product in question. 各自的合成法亦有他法难以替代的特征,发挥该特征的开发即属必需的。 He also their synthesis method is difficult alternative features, i.e., exhibit the features as are necessary to develop. 避免乳化剂的参与反应引起的问题点,本发明于反应过程中完全不加乳化剂,对由纯水40〜60wt%及具碳-碳双键可聚合官能基的羧酸单体(A) 2〜9wt%、甲基丙烯酸烷酯或丙烯酸烷酯单体(B) 40〜50wt%而成的反应系,先以无机碱液0. 2〜2wt%调整反应在pH值9. 0〜13. 0的范围内使具有高分子乳化剂的特征,接着采用由硫酸盐的过氧化物起始剂,进行乳化聚合,于反应末段以有机胺化合物调整所得的水性树脂乳化液的PH值于7. 0〜9. 5的范围内。 Participation in the reactions to avoid problems caused by an emulsifier, in the present invention is added during the reaction is completely emulsifiers, 40~60wt% of water and having a carbon - carbon double bond acid monomer polymerizable functional group (A) 2~9wt%, the reaction system alkyl methacrylates or acrylic acid alkyl ester monomer (B) 40~50wt% formed, the first inorganic alkali 0. 2~2wt% adjusted at pH 9. the reaction 0~13 . characterized in that the emulsifier is a polymer having in the range of 0, followed by the use of a peroxide initiator sulfate, emulsion polymerization, PH adjusted in the last paragraph of the reaction of an organic amine compound resulting aqueous resin emulsion to a value 7. the range of 0 ~ 9. 5. 而得表面洁净、单一分散的乳胶粒,同时避免乳化剂对环境的影响。 To give a clean surface, monodisperse latex particles, while avoiding the environmental impact emulsifier.

[0053] 近年高涨的环境问题或自医疗生物技术关系的应用或各种机能性材料的开发的观点而言,正予期待着环境友善型工艺的开发或高纯度聚合物粒子的合成法的开发。 [0053] In recent years, rising from the viewpoint of environmental problems or technical application or development of the relationship between the various functional bio-medical materials, the positive to look forward to the development of environment-friendly type of synthesis process of development or high-purity polymer particles .

[0054] 粒径均勻的所谓单分散性的粒子合成方面,有无乳化剂的乳化聚合,此聚合法以水为溶剂,亦兼具不添加皂类的清净工艺作为特征。 Particle synthesis [0054] The so-called uniform particle size monodisperse, with or without an emulsifier emulsion polymerization, the polymerization method using water as a solvent, without adding both clean process also soaps as a feature. 因此聚合成为单纯,于最简单的情形即为由单体/起始剂/水所构成的。 Thus the polymerization becomes simple, in the simplest case is the monomer / initiator / water is formed. 通常粒子合成法的最大一个问题,常在于可予控制的粒径的范围,随着本发明方法的无乳化剂聚合方法的可得粒径100〜130nm且分布均勻的乳液,粒径可予控制的范围亦被期待扩展着。 The maximum particle synthesis method is generally a problem is often that the range of particle size can be controlled, as emulsifier-free polymerization method can be obtained according to the method of the invention the particle size distribution and a uniform emulsion 100~130nm, the particle size can be controlled the range was also looking forward to the expansion. [0055] 无乳化剂聚合长久以来即被试图应用于无公害型的黏接剂、黏合剂、油墨工业等的应用。 [0055] The emulsifier-free polymerization i.e. long application seeks to apply pollution type bonding agent, adhesives, inks and other industries. 又清净的界面的单分散性粒子系正被采用作胶体研究的模型粒子或电子显微镜等的校正用的标准粒子。 And pure monodisperse particles being based interface standard model particle or particle such as an electron microscope the correction as colloidal study. 惟其可适用的粒径的领域在次微米以下。 Only in the applicable art sub-micron or less in particle size. 超过此粒径的粒子的合成是较困难的。 Synthesis than this particle diameter is more difficult. 另一方面,微米级的单分散性粒子近年来随着其用途的扩大,其用途可被举出有液晶间隔件、导电性粒子、医疗检查担体、分析用填充剂、复印机调色剂等高附加价值制品。 On the other hand, monodisperse micron particles in recent years with the expansion of its use, its use may be mentioned a liquid crystal spacer, the conductive particles, the medical examination supporter, analysis filler, high copier toner, value-added products. 本发明方法的以无乳化剂的乳化聚合,亦可合成纳米级的单分散粒子,所得的水性丙烯酸酯乳液的平均粒径小(微球粒径d为100〜130nm),乃被期待应用于上述领域。 The method of the present invention to emulsifier-free emulsion polymerization, also single synthetic nano-dispersed particles, the resulting aqueous acrylic ester emulsion small average particle size (diameter d of microspheres 100~130nm), is expected to be applied is the these areas.

[0056] 试验方法 [0056] Test Method

[0057] 乳液物性: [0057] Emulsion properties:

[0058] 1、平均粒径d、粒径分布和标准偏差(sd).分散系数D。 [0058] 1, the average particle diameter d, the particle size distribution and the standard deviation (sd). Dispersion coefficient D.

[0059] 对所得的乳液聚合物,用MANERN公司制造的MASTERSUER-2000依激光绕射法而得微球粒径分布曲线,测出平均粒径d、粒径分布及标准偏差(sd).分散系数D按下式计算: D = sd/d.由所得的乳液聚合物的微球粒径分布曲线可以直接得出微球粒径的分布情况。 [0059] The resulting polymer emulsion, manufactured by MANERN MASTERSUER-2000 method by laser diffraction particle size distribution curve obtained by the microspheres, the measured average particle diameter d, the particle size distribution and standard deviation (sd). Dispersion coefficient D is calculated as follows: D = sd / d by a microsphere particle size distribution curve of the resulting emulsion polymer may be directly obtained the particle size distribution of the microspheres.

[0060] 2、玻璃转移温度Tg (°C ) [0060] 2, the glass transition temperature Tg (° C)

[0061] 利用METTLER-T0LED0仪器公司制造的示差扫瞄热量计(Differential scanning calorimeters ;DSC)所测得的Tg 点。 [0061] using a differential scanning calorimeter (Differential scanning calorimeters; DSC) METTLER-T0LED0 Instruments manufactured the measured Tg point.

[0062] 3、酸价 [0062] 3, acid value

[0063] 取用制得的乳化液,依日本工业规格(JIS)K5601第2部第1节规定的方法予以试验。 [0063] The resulting emulsion access, according to Japanese Industrial Standards (JIS) K5601 be test method specified in Section 1, Part 2.

[0064] 4、比重 [0064] 4, the proportion of

[0065] 取用制得的乳化液,依日本工业规格(JIS)K7232规定的方法制备试样并予试验。 [0065] access to the emulsion obtained, samples were prepared according to the method of Japanese Industrial Standards (JIS) K7232 and to a predetermined test.

[0066] 5、pH 值 [0066] 5, pH value

[0067] 取用制得的乳化液,依日本工业规格(JIS)K0400第12部第10节规定的方法制备试样并予试验。 [0067] access to the emulsion obtained, samples were prepared according to the method specified in Section 12 10 K0400 of the Japanese Industrial Standards (JIS), and to test.

[0068] 6、储存安定性 [0068] 6, storage stability

[0069] 取用制得的乳化液,依日本工业规格(JIS) K5600第2部第7节规定的方法制备试样并予试验。 [0069] access to the emulsion obtained, samples were prepared according to the method of Japanese Industrial Standards (JIS) K5600 predetermined second section 2 and 7 to the test.

[0070] 7、冻结安定性 [0070] 7, freeze stability

[0071] 取用制得的乳化液,依日本下业规格(JIS) K5600第2部第6节规定的方法制备试样并予试验。 [0071] access to the emulsion obtained, samples were prepared according to the method described in Japanese industry specification (JIS) K5600 specified in Section I and Part 2 of 6 trials.

[0072] 乳液涂膜物性: [0072] Emulsion coating properties:

[0073] 1、抗拉强度 [0073] 1, the tensile strength

[0074] 取用制得的乳化液,依日本工业规格(JIS)K6251规定的方法制备试样并予试验。 [0074] The resulting emulsion was drawn, by a predetermined method of preparing a sample Japanese Industrial Standards (JIS) K6251 and I test.

[0075] 2、撕裂强度 [0075] 2, tear strength

[0076] 取用制得的乳化液,依日本工业规格(JIS)K6252规定的方法制备试样并予试验。 [0076] access to the emulsion obtained, samples were prepared according to the method of Japanese Industrial Standards (JIS) K6252 and to a predetermined test.

[0077] 3、伸长率 [0077] 3, elongation

[0078] 取用制得的乳化液,依日本工业规格(JIS)K6251规定的方法制备试样并予试验。 [0078] The resulting emulsion was drawn, by a predetermined method of preparing a sample Japanese Industrial Standards (JIS) K6251 and I test.

[0079] 4、涂膜的硬度 [0079] 4, the hardness of coating film

[0080] 取用制得的乳化液,依日本工业规格(JIS)K6253规定的方法制备试样并予试验。 [0080] access to the emulsion obtained, samples were prepared according to the method of Japanese Industrial Standards (JIS) K6253 and to a predetermined test.

9[0081] 5、三日吸水率 9 [0081] 5, three days water absorption

[0082] 取用制得的乳化液,依日本工业规格(JIS)K7112规定的方法制备试样并予试验。 [0082] access to the emulsion obtained, samples were prepared according to the method of Japanese Industrial Standards (JIS) K7112 and to a predetermined test.

[0083] 乳液作业性: [0083] Emulsion workability:

[0084] 取用制得的乳化液,依日本工业规格(JIS)A1181规定的方法,观察其与骨材(CA-400)的混合性、密着性、重涂性,◎代表其结果为优良,而X代表其结果为劣。 [0084] The resulting emulsion was drawn, by the method specified in Japanese Industrial Standards A1181 (JIS), with mixed with aggregate (CA-400), the adhesion resistance, recoatability, representative of a result excellent ◎ and X represents the result was bad.

[0085] 至于电解质安定性,则依日本工业规格(JIS) K6935第2节规定的方法予以试验。 [0085] As the electrolyte stability, the test shall be in accordance with the Japanese Industrial Standards (JIS) K6935 method specified in Section 2.

[0086] 以下列实例予以详细说明与本发明有关的一种无乳化剂的丙烯酸酯乳液的聚合方法,唯并不意味本发明仅局限于此等实例所揭示的内容。 [0086] In the following examples to be described in detail polymerization method related to the present invention is a non-emulsifier acrylate emulsion, does not mean that the present invention is the only limited to the disclosed example of such content.

[0087] 关于实施例1〜5 [0087] Example 1 ~ 5 on

[0088] 实施例1〜3所采用的羧酸单体均为具碳-碳双键可聚合官能基的单羧酸,但采用不同的无机碱。 [0088] Example ~ 3 as carboxylic acid monomers are used in embodiments having a carbon - carbon double bond polymerizable monocarboxylic acid functional groups, but with a different inorganic bases.

[0089] 实施例4〜5则采用具碳-碳双键可聚合官能基的单羧酸与不同的具碳-碳双键可聚合官能基的二羧酸的混合物。 The mixture carbon double bond polymerizable functional group of the dicarboxylic acid - carbon double bond polymerizable functional group with a monocarboxylic acid having different carbon - is used having 4 to 5 carbon [0089] Example.

[0090] 所得的水性丙烯酸酯乳液,基本组成及乳液物性、涂膜物性及乳液作业性,如表1 所示。 [0090] The resulting aqueous acrylic emulsion base composition and physical properties of the emulsion, the emulsion coating properties and workability, as shown in Table 1.

[0091] 关于比较例1〜4 [0091] Comparative Examples 1 ~ 4

[0092] 传统上水性丙烯酸酯乳液,其酸价常较本发明所得者高,或即使其酸价低至如同本发明所得,但其是于乳液聚合中采用乳化剂。 [0092] The aqueous acrylic emulsion conventionally, acid value obtained by the present invention is often relatively high, or, if an acid obtained as the lowest to the present invention, but it is the use of emulsifiers in the emulsion polymerization. 为供比较,以酸价较本发明高的水性丙烯酸酯乳液作为比较例1〜2及酸价低至如同本发明所得而采用常规乳化剂CMC(12R)进行乳液聚合者作为比较例3〜4。 Is for comparison, a higher acid value of the present invention the aqueous acrylic emulsion as Comparative Examples 1 to 2 and the resulting acid as the lowest to the present invention, conventional emulsifiers employed CMC (12R) by emulsion polymerization of 3 to 4 as a comparative example . 其基木组成及乳液物性、涂膜物性及乳液作业性,如表2所示。 Wood-based emulsion composition and its physical properties, coating properties and workability emulsion as shown in Table 2.

[0093] 实施例1〜5 :依表1内的基本组成所示 [0093] Example 1 ~ 5: 1, according to the basic composition shown in Table

[0094] (1)于反应槽内,加入无机碱液0.2〜2. Owt %、及秤取蒸镏水(先加入占参与聚合反应的反应物的40〜60wt%的蒸镏水),开始以转速约150〜300RPM搅拌,维持于70〜 95 "C。 [0094] (1) in a reaction vessel, adding an inorganic alkali 0.2~2. Owt%, weighed and distilled water (40~60wt% was added to the reaction product of the polymerization reaction accounts for distilled water), begins rotation speed of about 150~300RPM stirred, maintained at 70~ 95 "C.

[0095] (2)加入羧酸类单体(A)如丙烯酸、甲基丙烯酸或巴豆酸及依康酸单体(占全部单体的约2〜9wt% )。 [0095] (2) adding a carboxylic acid monomer (A) such as acrylic acid, methacrylic acid or crotonic acid, and itaconic acid monomer (comprises about 2~9wt% of all monomers).

[0096] (3)于约20分钟到达设定温度,加入硫酸盐的过氧化物起始剂0. 2〜1. 后, 开始缓慢滴加丙烯酸烷基酯单体(B)如甲基丙烯酸甲酯、甲基丙烯酸乙基酯、甲基丙烯酸异丁酯、甲基丙烯酸第三丁酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸2-乙己酯(占全部单体的约40〜50Wt% )并于2. 0〜4. 5小时完成滴加,并保持温度及转速继续反应约2〜3小时。 After [0096] (3) in about 20 minutes to reach the set temperature, peroxide initiator sulfate 0.5 2~1., Slowly added dropwise alkyl acrylate monomer (B) such as methyl acrylate, methyl, ethyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate (monomer comprises from about 40~50Wt% of all ) and added dropwise to complete 2. 0~4. 5 hours, and the reaction was continued keeping the temperature and speed for about 2 to 3 hours.

[0097] (4)关闭加热器但继续搅拌使其自然降温。 [0097] (4) so ​​as to close the heater but stirring was continued for natural cooling. 待温度降至40°C后,以水稀释pH调整剂后,缓慢加入约15分钟,使pH值达到8〜9。 After the temperature was lowered to 40 ° C, diluted with water and the pH adjusting agent, was slowly added for about 15 minutes to bring the pH to 8-9. 结束反应而得水性丙烯酸酯乳液。 Completion of reaction to give an aqueous acrylic emulsion. 其组成分及所得的压克力水性丙烯酸酯乳液及干燥涂膜的物性,如表1所示。 The resulting set of components and which acrylic aqueous acrylic emulsion and drying the coating film physical properties as shown in Table 1. 且从所得到的聚合物微球粒径分布曲线可以直接得出微球粒径的分布情况,其代表图如图1所示。 Polymeric microspheres and from the particle size distribution curve obtained can be directly obtained microsphere size distribution, which represents shown in Figure 1.

[0098] 乳液作业性: [0098] Emulsion workability:

[0099] 对由实施例1〜5而得的无乳化剂的压克力树脂68. 2wt%,搭配如混凝土、硅砂等骨材11. #t%,与各种填充粉11. #t%、色料6. 8wt%制成地板材产品,检查此等的混合性,密着性、重涂性。 [0099] The various embodiments emulsifier-free powder filled acrylic resin obtained by embodiments 1 ~ 5 68. 2wt%, with the concrete, aggregate such as silica sand 11. # t%, and 11. # t% , the toner is made of sheet products 6. 8wt%, the inspection of these mixed, adhesion, recoatability. [0100] 比较仿! [0100] Comparative imitation! ] 1〜4 ] ~ 4

[0101] 依表2内的基本组成所示,与实施例1〜5同法合成水性丙烯酸酯乳液。 [0101] By basic composition shown in Table 2, the same method of Example 1 ~ 5 embodiment aqueous acrylic emulsion polymerization. 其组成分及所得的压克力水性丙烯酸酯乳液及干燥涂膜的物性,如表2所示。 The resulting set of components and which acrylic aqueous acrylic emulsion and the physical properties of the dried coating film, as shown in Table 2.

[0102] 表1 :实施例的乳液组成、乳液物性、乳液作业性及涂膜物性 [0102] Table 1: Composition Emulsion embodiment, the physical properties of the emulsion, the emulsion workability and coating properties

Figure CN102464754AD00111

[0104] 表2 :供比较用的水性丙烯酸酯乳液组成分及物性 [0104] Table 2: for comparison an aqueous emulsion of acrylic minutes and physical properties

[0105] [0105]

Figure CN102464754AD00121

[0106] 由表1可知本发明方法制得的水性丙烯酸酯乳液,如实施例5的玻璃转移温度较低(-9.00°C ),实施例3的玻璃转移温度较高(8.48°C )的差别,但可因应涂膜制品的物性要求,予以调合使用。 [0106] Table 1 shows that the method of the present invention to obtain aqueous acrylic emulsion as described in Example lower glass transition temperature of 5 (-9.00 ° C), the implementation of a high glass transition temperature of Example 3 (8.48 ° C) of difference, but it may be due to the physical properties required of the film article, blending be used. 而实施例3的水性丙烯酸酯乳液的干膜,其硬度较硬,则可较宜适用于面涂涂料方面。 The dry film an aqueous acrylic emulsion of Example 3, the hardness harder, be more appropriate application to such top coating. 本发明方法制得的水性丙烯酸酯乳液的涂膜有较高的物性及较低的吸水率可适用于各类建筑的防水工程。 The aqueous acrylic emulsion coating method of the present invention obtained have a higher low water absorption properties and applicable to all types of building waterproofing.

[0107] 由本发明方法而得的水性压克力树脂乳化液,不论所采用的羧酸单体(A)为具碳-碳双键可聚合官能基的单羧酸及/或二羧酸,可采用不同的无机碱液进行无乳化剂的乳液聚合,制得的水性丙烯酸酯乳液的储存安定性、冻结安定性良好,可适用各种作业环境使用。 [0107] The resin from the aqueous acrylic emulsion obtained by the method according to the present invention, a carboxylic acid monomer (A) is used regardless of having a carbon - carbon double bond polymerizable functional group of monocarboxylic acid and / or dicarboxylic acids, inorganic alkali using different emulsifier-free emulsion polymerization, to obtain an aqueous acrylic emulsion storage stability, good freeze stability, suitable for all operating environments. 且因不含有机溶剂,对使用作涂料者而言,在安全卫生方面是较宜的。 And because no organic solvent, using as coating material are concerned, in terms of safety and health is the more appropriate. 尤其最适宜使用在要求黏着强度、机械强度较高的制品中残留溶剂的标准严格的建材。 Most particularly suitable for use in adhesive strength requirements, high mechanical strength article stringent criteria of residual solvent in building materials.

[0108] 而由比较例1〜2采用过量的羧酸,所得到的乳液的酸价高,而使吸水率上升,虽然比较例1〜2可得平均粒径115nm的乳液,但是其储存安定性及冻结安定性差,其与骨材的混合性虽然良好,但是其密着性及重涂性不佳,并不适用于各种作业环境。 [0108] Comparative Examples 1 to 2 and by the use of excess carboxylic acid prices resulting emulsion, the water absorption increases, while Comparative Examples 1~2 may be an emulsion average particle size of 115nm, but its storage stability freeze resistance and poor stability, which is mixed with the aggregate, although good, but the adhesion and poor recoatability, does not apply to a variety of operating environments. 而比较例3〜 4的酸价低至如同本发明所得,虽然所得到的乳液的储存安定性及冻结安定性良好,但是采用常规乳化剂CMC(12R)进行乳液聚合,所得乳液的粒径变大且涂膜三日吸水率上升,且其与骨材的混合性、密着性及重涂性亦不佳,并不适用于各种作业环境。 Comparative Examples 3 ~ 4 to the lowest acid obtained as in the present invention, although the freezing and storage stability of the resulting emulsion stability is good, but using conventional emulsifiers CMC (12R) emulsion polymerization, the resultant emulsion particle diameter becomes and coating the 3rd large increase in water absorption, and is mixed with the aggregate, the adhesion is poor and re-coating also does not apply to a variety of operating environments.

Claims (4)

  1. 1. 一种无乳化剂的丙烯酸酯乳液聚合方法,其特征在于,包括下述工序:1)制备由纯水40〜60wt %、具碳-碳双键可聚合官能基的羧酸单体A2〜9wt %、和甲基丙烯酸烷酯或丙烯酸烷酯单体B 40〜50wt%为主成分而成的反应系;2)以0. 2〜2衬%的无机碱液调整反应在pH9. 0〜13. 0的范围内;3)保持该反应于温度70〜95 °C且以转速150〜300rpm搅拌30分钟,采用0. 2〜 1. Owt %的过硫酸钠,过硫酸钾,过硫酸铵而成的群体选出的一种或一种以上作为起始剂予以起始化,进行乳化聚合;4)于反应末期以由氨水、三甲胺、单乙醇胺、二甲基乙醇胺、二甲基乙醇胺、2-胺基-2-甲基丙醇而成的群体中选出一种或一种以上的有机胺类调整所得到的水性树脂乳化液的PH值于7. 0〜9. 5的范围内,得到粒径100〜130nm均一且分布极窄小的水性压克力聚合体。 An emulsifier-free emulsion polymerization of acrylates method comprising the following steps: 1) Preparation of pure water 40~60wt%, having a carbon - carbon double bond acid monomer A2 polymerizable functional groups the reaction system formed ~9wt%, and alkyl methacrylates or alkyl acrylates as the main component monomer B 40~50wt%; 2) 0.5% of an inorganic alkaline liner 2~2 adjusting reaction pH9 0. within a range of 0 ~ 13;. 3) to hold the speed of the reaction and stirred at a temperature of 70~95 ° C 150~300rpm 30 min using 0. 2~ 1. Owt% of sodium persulfate, potassium persulfate, persulfuric acid ammonium groups selected from one or more of starting to be used as an initiator, emulsion polymerization; 4) at the end of the reaction to ammonia, trimethylamine, monoethanolamine, dimethylethanolamine, dimethyl ethanolamine, 2-amino-2-methylpropanol groups selected from one or more organic amine PH aqueous resin emulsion is adjusted to a value obtained by 7. 0 ~ 9. 5 the range, and to give a uniform particle size distribution is very narrow 100~130nm aqueous acrylic polymer.
  2. 2.根据权利要求1所述的聚合方法,其中,所具述碳-碳双键可聚合官能基的羧酸单体A是由丙烯酸、甲基丙烯酸、依康酸和巴豆酸群体选出的一种或一种以上 2. A polymerization process according to claim 1, wherein said having a carbon - carbon double bond polymerizable carboxylic acid functional group A monomer is selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid group, and one or more
  3. 3.根据权利要求1所述的聚合方法,其中,所述甲基丙烯酸烷酯或丙烯酸烷酯单体B是甲基丙烯酸甲酯、甲基丙烯酸乙基酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸第三丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸第三丁酯、丙烯酸2-乙己酯、甲基丙烯酸2-乙己酯、甲基丙烯酸月桂酯、丙烯腈、丙烯腈群体选出的一种或一种以上。 The polymerization process according to claim 1, wherein said alkyl methacrylates or alkyl acrylates B monomer is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl yl isobutyl acrylate, tertiary butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylate, lauryl methacrylate, acrylonitrile, acrylonitrile groups selected from one or more.
  4. 4.根据权利要求1所述的聚合方法,其中,所述无机碱液是由氢氧化钠、氢氧化钾、磷酸三钠群体选出的一种或一种以上。 The polymerization process according to claim 1, wherein said inorganic alkali is selected from sodium hydroxide, potassium hydroxide, trisodium phosphate groups, one or more.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554342A (en) * 2013-11-13 2014-02-05 宁波市鄞州科启动漫工业技术有限公司 Method for surface modification of polymer particles
CN103709303A (en) * 2014-01-13 2014-04-09 张家港保税区康得菲尔实业有限公司 Preparation method of water-based acrylate emulsion for coating

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4151143A (en) * 1977-08-19 1979-04-24 American Cyanamid Company Surfactant-free polymer emulsion coating composition and method for preparing same
US5342878A (en) * 1991-12-30 1994-08-30 Ppg Industries, Inc. Base neutralized, stable, aqueous dispersion of a hydroxyl functional acrylic polymer and coating compositions prepared therefrom
US20070116660A1 (en) * 2003-12-09 2007-05-24 Basf Aktiengesellschaft Copolymers based on tertbutyl(meth) acrylate and use thereof
CN101220223A (en) * 2007-12-14 2008-07-16 中山大学 Method for formulating optics color changing type false proof aqueous intaglio printing ink
CN101519561A (en) * 2009-04-03 2009-09-02 西安华泰有色金属实业有限责任公司 Method for preparing ultraviolet-screening, transparent, heat-insulation paint

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4151143A (en) * 1977-08-19 1979-04-24 American Cyanamid Company Surfactant-free polymer emulsion coating composition and method for preparing same
US5342878A (en) * 1991-12-30 1994-08-30 Ppg Industries, Inc. Base neutralized, stable, aqueous dispersion of a hydroxyl functional acrylic polymer and coating compositions prepared therefrom
US20070116660A1 (en) * 2003-12-09 2007-05-24 Basf Aktiengesellschaft Copolymers based on tertbutyl(meth) acrylate and use thereof
CN101220223A (en) * 2007-12-14 2008-07-16 中山大学 Method for formulating optics color changing type false proof aqueous intaglio printing ink
CN101519561A (en) * 2009-04-03 2009-09-02 西安华泰有色金属实业有限责任公司 Method for preparing ultraviolet-screening, transparent, heat-insulation paint

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
庄严等: "无皂乳液聚合技术及其应用", 《涂料工业》 *
黄志虹等: "丙烯酸酯无皂乳液稳定性能研究", 《功能高分子学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554342A (en) * 2013-11-13 2014-02-05 宁波市鄞州科启动漫工业技术有限公司 Method for surface modification of polymer particles
CN103709303A (en) * 2014-01-13 2014-04-09 张家港保税区康得菲尔实业有限公司 Preparation method of water-based acrylate emulsion for coating
CN103709303B (en) * 2014-01-13 2016-06-22 张家港保税区康得菲尔实业有限公司 A coating method for preparing an aqueous acrylic emulsion

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