CN102250281A - Cation acrylate emulsion - Google Patents

Cation acrylate emulsion Download PDF

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CN102250281A
CN102250281A CN 201110166301 CN201110166301A CN102250281A CN 102250281 A CN102250281 A CN 102250281A CN 201110166301 CN201110166301 CN 201110166301 CN 201110166301 A CN201110166301 A CN 201110166301A CN 102250281 A CN102250281 A CN 102250281A
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acrylate
emulsion
cation
monomer
acid
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CN 201110166301
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Chinese (zh)
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余洁
傅乐峰
郑柏存
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上海三瑞高分子材料有限公司
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Abstract

The invention discloses a cation acrylate emulsion which comprises deionized water, an initiator, an emulsifier, styrene, a C4-C12 alkyl acrylate unsaturated monomer, a C4-C20 methyl acrylate unsaturated monomer, a C7-C12 alkylamino (methyl) acrylate cation monomer, an acrylamide functional monomer and acid. The cation acrylate emulsion is obtained by neutralizing a polymer emulsion with acid through an emulsion polymerization method. The cation acrylate emulsion has good sealing and separation obstructing performances on aqueous spots such as wood effusion, tannic acid, water damage, smoke spot, doodle, aqueous ink smudge and saline and alkaline spot, and can be used for preparing aqueous wood paint and first coat and face coat of internal and external wall paint, wherein the paint has a spot sealing performance; and the cation acrylate emulsion has good adhesive attraction on various substrates, especially harsh substrates and can be applied to first coat formulas of metal, plastic, leather, paper and fiber.

Description

阳离子丙烯酸酯乳液 Cationic acrylic emulsion

技术领域 FIELD

[0001] 本发明涉及一种聚合物,具体地说是一种阳离子丙烯酸酯乳液,尤其是一种对水性污渍具有封闭性能以及对各种基材具有良好附着力的丙烯酸酯乳液。 [0001] The present invention relates to a polymer, in particular a cationic acrylic emulsion, in particular an aqueous stains having a sealing ability and a good adhesion to various substrates acrylate emulsion.

背景技术 Background technique

[0002] 作为水性涂料和水性漆,目前面临的主要技术问题之一是对水性污渍的封闭阻隔性,即解决基材渗色、提高对污渍的覆盖力的问题。 [0002] As a water-based paint and water-based coatings, one of the major technical problems currently facing closed barrier property against water stains, i.e., solve the problem of the substrate bleeding, improved covering power of soiling. 如水性木器漆应用方面,对于一些富含单宁酸的木材如印茄木、橡木、软木等含有水溶性的发色基团化合物,容易导致涂膜渗色或变色;内墙乳胶漆应用方面,原有墙面的水渍、烟渍、涂鸦、水性墨渍等非常难以覆盖,容易渗透到面涂表面。 Wood applications such as water, for some tannic acid, such as wood merbau, oak, cork containing water-soluble chromophore compound, easily lead to bleeding or discoloration of the coating; Interior Latex Paint application original wall water stains, smoke stains, graffiti, and other aqueous ink stains are very difficult to cover, easily penetrate the surface of the topcoat. 在传统的水性涂料或水性漆体系中,解决渗色或提高对污渍覆盖力的方法就是大量使用活性颜料或封闭剂(锌、铝或钛的化合物)。 In conventional aqueous paints or aqueous paint systems, solve or improve bleeding stains covering power method is widely used (zinc, aluminum or titanium compound) or reactive pigments blocking agent. 这些解决的措施或只能配制色漆,或存在相容性的问题;同时对膜的性能也有很大的影响。 These measures can only be resolved or formulated paint, or the existence of compatibility problems; but also has a great influence on the performance of the membrane.

发明内容 SUMMARY

[0003] 本发明的目的是针对现有技术的不足而提供的一种阳离子丙烯酸酯乳液。 [0003] The object of the present invention is a cationic acrylic emulsion for the deficiencies of the prior art provided. 它具有优异的附着力、成膜性能;阳离子特殊官能基团和水性渍中的有色基团反应键合,从而起到优异的封闭阻隔作用。 It has excellent adhesion, film-forming properties; cationic functional groups, and special stains in aqueous colored reaction bonded groups, which play an excellent barrier effect closure.

[0004] 本发明的目的是这样实现的: [0004] The object of the present invention is implemented as follows:

一种阳离子丙烯酸酯乳液,包括去离子水、引发剂、乳化剂、苯乙烯、C4〜C12的丙烯酸烷基酯不饱和单体、C4〜C2tl的甲基丙烯酸酯类不饱和单体、C7〜C12的烷氨基(甲基)丙烯酸酯阳离子单体、丙烯酰胺类功能性单体、酸,其各组分含量(以重量计)为: 去离子水55-75% ; 乳化剂0. 1-3% ; 引发剂0. 1-0. 8%; 苯乙烯0-10% ; A cationic acrylic emulsion comprising deionized water, initiator, emulsifier, styrene, C4~C12 alkyl acrylate unsaturated monomer, C4~C2tl methacrylates unsaturated monomers, C7~ C12 alkylamino (meth) acrylate monomer is a cationic, acrylamide-based functional monomer, an acid, which content of each component (in weight): 55-75% deionized water; emulsifying agents 0. 1- 3%; 0. 1-08% initiator;. 0-10% styrene;

C4〜C12的丙烯酸烷基酯单体1-30% ; C4~C12 alkyl acrylate monomer 1-30%;

C4〜C2tl的甲基丙烯酸酯单体10-40% ; C4~C2tl methacrylate monomer 10 to 40%;

C7〜C12的烷氨基(甲基)丙烯酸酯阳离子单体4-15% ; C7~C12 alkylamino (meth) acrylate 4-15% cationic monomer;

丙烯酰胺类功能单体0-5% ; Acrylamide functional monomer 0-5%;

酸0. 5-3. 5% ; Acid 0. 5-35%;

通过乳液聚合法制备并通过酸中和聚合物乳液而得。 And obtained by emulsion prepared by emulsion polymerization of polymer by acid neutralization.

[0005] 所述乳化剂是十二烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠、脂肪醇聚氧乙烯醚中的一种或几种。 [0005] the emulsifier is sodium lauryl sulfate, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether is one or more.

[0006] 所述C4〜C12的丙烯酸烷基酯是丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸癸酯或丙烯酸异辛酯中的一种或几种。 [0006] The C4~C12 alkyl acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate isooctyl acrylate, or of one or more .

[0007] 所述C4〜C2tl的甲基丙烯酸酯单体是甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸丁酯、甲基丙烯酸苄酯、甲基丙烯酸环己酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异冰片酯、甲基丙烯酸十二烷基(月桂)酯、甲基丙烯酸十八烷基酯或一缩二乙二醇二甲基丙烯酸酯中的一种或几种。 [0007] The C4~C2tl methacrylate monomers are methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, methyl acrylate, benzyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, isobornyl methacrylate, dodecyl (lauryl) stearyl acrylate, methacrylate or a Semidiethylenetriamine one or more glycol dimethacrylate ester.

[0008] 所述C7〜C12的烷氨基(甲基)丙烯酸酯阳离子单体是丙烯酸二甲氨基乙酯、丙烯酸二乙氨基乙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯、甲基丙烯酸-2-叔丁基氨基乙酯中的一种或几种。 [0008] The alkylamino C7~C12 (meth) acrylic cationic monomer is dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, ethyl methacrylate, 2-t-butylaminoethyl methacrylate of one or more.

[0009] 所述酸是盐酸、甲酸或乙酸中的一种。 The [0009] acid is a hydrochloric acid, formic acid or acetic acid.

[0010] 所述丙烯酰胺类功能性单体是、N,N- 二甲基丙烯酰胺、N—轻甲基丙烯酰胺中的一种或两种。 [0010] The acrylamide functional monomers, N, N- dimethylacrylamide, N- dimethylacrylamide light of one or both.

[0011] 所述引发剂为过硫酸钾、过硫酸铵、过硫酸钠、异丙苯过氧化氢、2,2-偶氮(2-脒基丙烷)二氢氯化物中的一种或几种。 [0011] The initiator is potassium persulfate, ammonium persulfate, sodium persulfate, cumene hydroperoxide A 2,2-azobis (2-amidinopropane) dihydrochloride or several species.

[0012] 所述乳液聚合法是在乳化剂存在下、通过机械搅拌使烯属不饱和单体分散水中并在引发剂作用下进行自由基聚合,并通过酸中和聚合物乳液。 [0012] The emulsion polymerization is in the presence of an emulsifier by mechanical stirring ethylenically unsaturated monomer is dispersed in water and a radical polymerization initiator under the action of an acid and neutralized polymer emulsion.

[0013] 所述聚合温度为60-95°C。 [0013] The polymerization temperature is 60-95 ° C.

[0014] 本发明对水性污渍如木材渗出物、单宁酸、水渍、烟渍、涂鸦、水性墨渍、盐碱渍具有良好的封闭阻隔性能,可用于配制具有污渍封闭性能的水性木器涂料、内外墙涂料的底涂和面涂。 [0014] The present invention is an aqueous wood stains exudates, tannic acid, water stains, smoke stains, graffiti, aqueous ink stains, salt stains have good barrier properties closed, for the formulation with the aqueous stain-blocking properties of wood paint, interior and exterior paint primer and top coat.

[0015] 本发明对多种基材特别是一些苛刻基材表面具有良好的附着力。 [0015] The present invention has good adhesion to the surface of some of the more demanding substrates especially substrates Yes. 可应用于金属、 塑料、皮革、纸张、纤维的底涂配方中。 It can be applied to metal, plastic, leather, paper, primer formulation fibers.

具体实施方式 detailed description

[0016] 本发明的制备包括以下步骤: Preparation of the present invention [0016] comprising the steps of:

(a)先将去离子水和乳化剂加入反应釜中,均勻混合,加热至起始温度30-60°C ; (A) First of deionized water and added to the kettle emulsifier, uniformly mixed, heated to the starting temperature of 30-60 ° C;

(b)然后将C7〜C12的烷氨基(甲基)丙烯酸酯阳离子单体、苯乙烯、C4〜C12的丙烯酸烷基酯单体、C4〜C2tl的甲基丙烯酸酯单体、丙烯酰胺类功能单体中均勻混合; (B) then alkylamino C7~C12 (meth) acrylic cationic monomers, styrene, C4~C12 alkyl acrylate monomers, C4~C2tl methacrylate monomers, acrylamide-based function monomer uniformly mixed;

(c)在反应釜中加入引发剂和步骤(b)所述单体混合物,控温在反应温度60〜95°C, 搅拌反应; (C) adding to the reaction kettle initiator and the step (b) the monomer mixture, the reaction temperature at a temperature of 60~95 ​​° C, stirring the reaction;

(d)反应结束后,控温在60〜85°C,加入酸中和,搅拌得本发明所述阳离子丙烯酸酯乳液。 After the (D) reaction temperature at 60~85 ° C, and the acid was added, with stirring to obtain the present invention the cationic acrylic emulsion.

[0017] 实施例1 [0017] Example 1

将615克去离子水、15克脂肪醇聚氧乙烯醚硫酸钠、10克脂肪醇聚氧乙烯醚加入反应釜中,开启搅拌,均勻混合,加热至35°C。 The 615 g of deionized water, 15 g of polyoxyethylene fatty alcohol ether sulfate, 10 g fatty alcohol polyoxyethylene ether were added to the reaction kettle, stirred open, uniformly mixed and heated to 35 ° C.

[0018] 将100克丙烯酸丁酯、33g丙烯酸乙酯、170克甲基丙烯酸甲酯和45克甲基丙烯酸二乙氨基乙酯置于烧杯中,搅拌均勻。 [0018] 100 g of butyl acrylate, 33g of ethyl acrylate, 170 g methyl methacrylate and 45 g dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate placed in a beaker, stir.

[0019] 将5克过硫酸钾和上述单体混合物加入反应釜中,搅拌升温至90°C反应。 [0019] 5 g of potassium persulfate and the monomer mixture was added to the kettle, stirred reaction warmed to 90 ° C. 反应约2h,待反应完全后,降温至80°C,加入7克甲酸,搅拌Ih得到均勻微黄色乳液即为本发明所述的阳离子丙烯酸酯乳液。 For about 2h, until the reaction is complete, cooled to 80 ° C, 7 g of formic acid was added, stirred for Ih to obtain a cationic emulsion of a homogeneous yellowish present invention is the acrylic emulsion.

[0020] 实施例2 [0020] Example 2

将650克去离子水、10克脂肪醇聚氧乙烯醚硫酸钠、10克脂肪醇聚氧乙烯醚加入反应釜中,开启搅拌,均勻混合,加热至60°C。 The 650 g of deionized water, 10 g of polyoxyethylene fatty alcohol ether sulfate, 10 g fatty alcohol polyoxyethylene ether were added to the reaction kettle, stirred open, uniformly mixed and heated to 60 ° C.

[0021] 将40克苯乙烯、100克丙烯酸丁酯、100克甲基丙烯酸甲酯和70克丙烯酸二乙氨基乙酯置于烧杯中,搅拌均勻。 [0021] 40 g of styrene, 100 g butyl acrylate, 100 g of methyl methacrylate and 70 g of acrylic acid diethylaminoethyl placed in a beaker, stir.

[0022] 将6克过硫酸钠和上述单体混合物加入反应釜中,搅拌升温至80°C反应。 [0022] 6 g of sodium persulfate and the monomer mixture was added to the kettle, stirred reaction warmed to 80 ° C. 反应约池,待反应完全后,加入14克乙酸,搅拌Ih得到均勻微黄色乳液即为本发明所述的阳离子丙烯酸酯乳液。 For about pool, until the reaction was completed, 14 grams of acetic acid was stirred for Ih to obtain a cationic emulsion of a homogeneous yellowish present invention is the acrylic emulsion.

[0023] 实施例3 [0023] Example 3

将700克去离子水、7克脂肪醇聚氧乙烯醚硫酸钠、3克脂肪醇聚氧乙烯醚加入反应釜中,开启搅拌,均勻混合,加热至50°C。 700 g of deionized water, 7 g fatty alcohol polyoxyethylene ether sulfate, 3 g fatty alcohol polyoxyethylene ether were added to the reaction kettle, stirred open, uniformly mixed and heated to 50 ° C.

[0024] 将70克苯乙烯、20克丙烯酸丁酯、65克甲基丙烯酸甲酯、20克羟甲基丙烯酰胺和92克甲基丙烯酸-2-叔丁基氨基乙酯置于烧杯中,搅拌均勻。 [0024] 70 g of styrene, 20 g of butyl acrylate, 65 g of methyl methacrylate, 20 g methylol acrylamide and 92 grams of methacrylic acid-2-tert-butylaminoethyl methacrylate placed in a beaker, stir.

[0025] 将2克过硫酸钾和上述单体混合物加入反应釜中,搅拌升温至75°C反应。 [0025] 2 g of potassium persulfate and the monomer mixture was added to the kettle, stirred reaction warmed to 75 ° C. 反应约3h,待反应完全后,加入21克甲酸,搅拌Ih得到均勻微黄色乳液即为本发明所述的阳离子丙烯酸酯乳液。 For about 3h, After completion of the reaction, 21 g of formic acid was added, stirred for Ih to obtain a cationic emulsion of a homogeneous yellowish present invention is the acrylic emulsion.

[0026] 以上实施例,用来列举说明发明的目的、技术内容、特点及功效,本发明保护范围并非局限于这些实施例。 [0026] the above embodiment, for illustrative purposes include, technical contents, characteristics and effects of the invention, the scope of the present invention is not limited to these embodiments.

Claims (10)

  1. 1. 一种阳离子丙烯酸酯乳液,其特征在于该乳液包括去离子水、引发剂、乳化剂、苯乙烯、C4〜C12的丙烯酸烷基酯不饱和单体、C4〜C2tl的甲基丙烯酸酯类不饱和单体、C7〜C12 的烷氨基(甲基)丙烯酸酯阳离子单体、丙烯酰胺类功能性单体及酸,其各组分含量以重量计为:去离子水55-75% ; 乳化剂0. 1-3% ; 引发剂0. 1-0. 8% ; 苯乙烯0-10% ;C4〜C12的丙烯酸烷基酯单体1-30% ;C4〜C2tl的甲基丙烯酸酯单体10-40% ;C7〜C12的烷氨基(甲基)丙烯酸酯阳离子单体4-15% ;丙烯酰胺类功能单体0-5% ;酸0. 5-3. 5% ;通过乳液聚合法制备并通过酸中和聚合物乳液而得。 A cationic acrylic emulsion, wherein the emulsion comprising deionized water, initiator, emulsifier, styrene, C4~C12 alkyl acrylate unsaturated monomer, C4~C2tl methacrylates unsaturated monomers, C7~C12 alkylamino (meth) acrylate monomer is a cationic, acrylamide-based and acid-functional monomer, in which the content of each component by weight: 55-75% deionized water; emulsifying agent 0. 1-3%; 0. 1-08% initiator; styrene 0-10%; C4~C12 alkyl acrylate monomer 1-30%; C4~C2tl of methacrylate monomers body 10-40%; C7~C12 alkylamino (meth) acrylate 4-15% cationic monomer; acrylamide functional monomer 0-5%; acid 0. 5-35%; by emulsion Preparation of the emulsion and the polymer obtained by acid neutralization.
  2. 2.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述乳化剂是十二烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠、脂肪醇聚氧乙烯醚中的一种或几种。 1 according to the cationic acrylic emulsion as claimed in claim, wherein the emulsifier is sodium lauryl sulfate, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether is one or more .
  3. 3.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述C4〜C12的丙烯酸烷基酯是丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸癸酯或丙烯酸异辛酯中的一种或几种。 According to the claim 1 cationic acrylic emulsion, wherein said C4~C12 alkyl acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl isooctyl acrylate or one or more ester.
  4. 4.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述C4〜C2tl的甲基丙烯酸酯单体是甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸丁酯、甲基丙烯酸苄酯、甲基丙烯酸环己酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异冰片酯、甲基丙烯酸十二烷基(月桂)酯、甲基丙烯酸十八烷基酯或一缩二乙二醇二甲基丙烯酸酯中的一种或几种。 According to the claim 1 cationic acrylic emulsion, wherein said C4~C2tl methacrylate monomers are methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, methyl hydroxypropyl acrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, isobornyl methacrylate, dodecyl (lauryl) acrylate, one or more of methyl methacrylate, stearyl acrylate or diethylene glycol dimethacrylate ester.
  5. 5.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述C7〜C12的烷氨基(甲基)丙烯酸酯阳离子单体是丙烯酸二甲氨基乙酯、丙烯酸二乙氨基乙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯、甲基丙烯酸-2-叔丁基氨基乙酯中的一种或几种。 According to the claim 1 cationic acrylic emulsion, wherein said alkylamino C7~C12 (meth) acrylic cationic monomer is dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methyl dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-t-butylaminoethyl methacrylate of one or more.
  6. 6.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述丙烯酰胺类功能性单体是N,N- 二甲基丙烯酰胺、N—轻甲基丙烯酰胺中的一种或两种。 According to the claim 1 cationic acrylic emulsion, wherein said acrylamide functional monomer is N, N- dimethyl acrylamide, N- dimethylacrylamide light of one or both of .
  7. 7.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述酸是盐酸、甲酸或乙酸中的一种。 1 7. The cationic acrylic emulsion according to claim, wherein said acid is a hydrochloric acid, formic acid or acetic acid.
  8. 8.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述引发剂为过硫酸钾、过硫酸铵、过硫酸钠、异丙苯过氧化氢、2,2-偶氮(2-脒基丙烷)二氢氯化物中的一种或几种。 According to the claim 1 cationic acrylic emulsion, wherein the initiator is potassium persulfate, ammonium persulfate, sodium persulfate, cumene hydroperoxide, 2,2-azobis (2-amidino one or more propane) dihydrochloride in.
  9. 9.根据权利要求1所述阳离子丙烯酸酯乳液,其特征在于所述乳液聚合法是在乳化剂存在下、通过机械搅拌使烯属不饱和单体分散水中并在引发剂作用下进行自由基聚合。 1 according to the cationic acrylic emulsion as claimed in claim, wherein said emulsion polymerization is in the presence of an emulsifier by mechanical stirring ethylenically unsaturated monomer is dispersed in water and a radical polymerization initiator under the action .
  10. 10.根据权利要求9所述阳离子丙烯酸酯乳液,其特征在于聚合温度为60-95°C。 9 10. The cationic acrylic emulsion according to claim, wherein the polymerization temperature is 60-95 ° C.
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