CN1493601A - Aqueous emulsion type fluorine containing water repellent oil repellent agent and its preparation method - Google Patents

Aqueous emulsion type fluorine containing water repellent oil repellent agent and its preparation method Download PDF

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CN1493601A
CN1493601A CN 03141771 CN03141771A CN1493601A CN 1493601 A CN1493601 A CN 1493601A CN 03141771 CN03141771 CN 03141771 CN 03141771 A CN03141771 A CN 03141771A CN 1493601 A CN1493601 A CN 1493601A
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water
cf2
fluorine
acrylate
meth
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CN 03141771
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韩哲文
李欣欣
王艳
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华东理工大学
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Abstract

An aqueous emulsion type fluoric hydrophobing-oleophobing agent is prepared from monomer, emulsifier and water through ultrasonic treating and triggered polymerizing. Its advantages are high hydrophobicity and oleophobicity, low cost, low polymerizing temp and high polymerizing speed.

Description

一种水乳型含氟拒水拒油剂及其制备方法 An aqueous emulsion type water and oil repellent and fluorine-containing preparation

技术领域 FIELD

本发明涉及一种不含有机溶剂的水乳型含氟拒水拒油剂及其制备方法。 The present invention relates to water emulsion which does not contain a fluorinated organic solvent and water and oil repellent preparation.

背景技术 Background technique

含氟高分子具有许多的优异性能,如卓越的抗水和抗油性、耐老化、耐高温、极低表面张力和化学稳定性等等。 The fluorine-containing polymer having a number of excellent properties, such as excellent water resistance and oil resistance, aging resistance, high temperature resistance, low surface tension and chemical stability and the like. 将(甲基)丙烯酸全氟烷基乙酯的共聚物用于织物的憎水、憎油整理剂的设计已是众所周知,从环境和安全性考虑,此类整理剂已由最初的溶解在有机溶剂中发展到现在的水系分散液。 The hydrophobic (meth) acrylate, perfluoro alkyl ethyl acrylate copolymer for fabric design oleophobic finishing agents are well known, from the environmental and safety considerations, has been the first such finishing agent dissolved in an organic solvent developed to the aqueous dispersion.

由于含有全氟烷基(简称Rf)基团的(甲基)丙烯酸酯是不溶于水的,而为了得到良好的拒水拒油性能,共聚物中往往需要有较高的氟含量,因此,其在水介质的良好分散一直是技术上的难点。 Since the perfluoroalkyl group (referred to an Rf) (meth) acrylate groups are not soluble in water, and to obtain good water and oil repellent properties, the copolymer often requires a higher fluorine content, and therefore, its well dispersed in an aqueous medium has been technical difficulties. 为了解决这个难题,一般都采用加入较大量的其他助剂的方法,此类助剂是在水中和氟单体中都有高溶解度的有机溶剂,溶剂的使用有助于单体从单体液滴往聚合物乳胶粒中扩散,如美国专利US08/048,350在聚合时加入丙酮作为聚合用助溶剂,日本专利JP309562/1999提出将水溶性的高粘度溶剂(25℃时粘度在3cP以上)如三乙二醇、二丙二醇二甲醚等加入到水中组成复合水系介质。 To solve this problem, generally used other additives adding a large number of methods, such adjuncts in water and the fluoromonomer has a high solubility in an organic solvent, the solvent from the monomer droplets help monomer to the polymer latex particles in the diffusion, as U.S. Patent No. US08 / 048,350 acetone was added in the polymerization as a polymerization co-solvent, Japanese Patent JP309562 / 1999 is a high viscosity water soluble solvent (a viscosity at 25 ℃ 3cP above) such as triethylamine glycols, dipropylene glycol dimethyl ether complex was added to the aqueous medium composed of water. 但是溶剂的使用会导致水系分散液燃点下降,或者残留于被处理物中,这是很不利的。 However, use of a solvent will result in decreased ignition aqueous dispersion, or remaining in the material to be treated, which is very unfavorable. 不论使用何种溶剂,都会增大使体系的VOC值(挥发性有机物),对环境不利。 Regardless of the solvent used, so the system will increase the value of VOC (volatile organic compounds), environmentally undesirable. 为了解决氟单体的稳定分散和聚合,也可以使用较大量的含氟表面活性剂作为乳化剂,但是这会增加乳液的成本。 In order to stabilize the dispersion and solution polymerization of the fluoromonomer, may be used relatively large amounts of the fluorinated surfactant as an emulsifier, but this increases the cost of the emulsion.

将超声波技术引入乳液聚合近来受到关注,如王琪等利用超声波辐射方法进行甲基丙烯酸甲酯微乳液聚合研究(高等学校化学学报,1237-1240:2001)。 The ultrasonic technology is introduced emulsion attention recently, Wang Qi, etc. using ultrasonic radiation such as a method microemulsion polymerization of methyl methacrylate (Chemical Journal, 1237-1240: 2001). 但是将超声波技术应用于高氟含量的拒水拒油乳液的制备还未见报道。 But the ultrasound technology used in the preparation of high fluorine content of the water and oil repellent lotion has not been reported.

含氟乳液聚合引发剂一般使用2,2'-偶氮双(2-脒基丙烷)二盐酸盐或者2,2'-偶氮双(异丁脒)二盐酸盐,此类引发剂是水溶性的,而且可以在低温引发,不过价格高昂,而且容易分解,要求低温储存。 The fluorine-containing polymerization initiator is generally used 2,2'-azobis (2-amidinopropane) dihydrochloride or 2,2'-azobis (isobutyramidine) dihydrochloride, such initiators It is water soluble and can be triggered at a low temperature, but expensive, and prone to break down, requiring low temperature storage.

发明内容 SUMMARY

本发明需要解决的技术问题是公开一种水乳型含氟拒水拒油剂及其制备方法,该水乳型含氟拒水拒油剂不含有机溶剂,以克服现有技术存在的上述缺陷,满足有关部门的需要。 The present invention is a technical problem to be solved is to disclose a water emulsion fluorinated water and oil repellent and a preparation method, the aqueous emulsion type water and oil repellent containing no fluorine-containing organic solvent, to overcome the above-mentioned prior art present defects, to meet the needs of the departments concerned.

本发明的水乳型含氟拒水拒油剂为由单体、乳化剂及水经超声波技术预乳化,然后在引发剂下引发聚合而获得的含氟共聚物在水介质中的乳液,其优选的重量百分比含量包括:含氟共聚物 5~40%乳化剂 0.5~4%水 余量所说的单体为单体A1和单体A2的混合物,其中:单体A1占共聚物总重量的百分数为35%~90%,如果低于35%,那么抗水、拒油、防污能力不够;同时也应小于90%,如果太高,起增溶作用的A2单体将过少,导致分散能力下降。 Water emulsion of the present invention, the fluorine-containing water and oil repellent by the monomers, emulsifier and water pre-emulsified by ultrasonic technology, and then a polymerization initiator to obtain a fluorine-containing copolymer emulsion in an aqueous medium in the initiator, which the preferred weight percentage content comprising: a fluorine-containing copolymer of 5 to 40% emulsifier 0.5 to 4% water remainder of said monomer is a monomer mixture of monomer A1 and A2, wherein: A1 based on the total monomer weight of the copolymer percentage of 35% to 90%, if less than 35%, the water resistance, oil repellency, anti-fouling ability is not enough; should also be less than 90%, if too high, since the solubilization of the monomer A2 is too small, lead to a decline dispersion capability. 50%~80%的含量是比较合适的,如此分散稳定性和抗水抗油持久性能达到良好平衡;单体A2占共聚物总重量的百分数为10%~65%。 50% to 80%, by weight is more appropriate, so the dispersion stability of the oil and water-resistant anti-rupture properties of a good balance; A2 percentage of the total monomer weight of the copolymer is 10% to 65%.

所述及的单体A1为由具有Rf基的(甲基)丙烯酸全氟烷基乙酯;所述具有Rf基的(甲基)丙烯酸全氟烷基乙酯是指全氟烷基位于(甲基)丙烯酸酯的醇残基部分的化合物,其结构如下式所示: The monomers A1 and by (meth) acrylate, perfluoroalkyl acrylate having a Rf group; a group having a Rf (meth) acrylate, perfluoroalkyl acrylate refers to a perfluoroalkyl group at ( methyl) compounds alcohol residue moiety acrylate, the following structure formula:

其中:Rf基最好是全部氢原子被氟原子取代,末端部分的结构以-CF2CF3为佳;Rf基可以是直链结构,也可以是支链结构,以直链结构为佳;Rf基的碳原子数以2~20个为佳,6~16个更佳;R是H或CH3;A是O、S或NR;R1是含1~15个碳原子的亚烷基;可以举出更具体的例子:CH2=CHCOOCH2CH2(CF2)3CF3CH2=CHCOOCH2CH2(CF2)5CF3CH2=CHCOOCH2CH2(CF2)7CF3CH2=CHCOOCH2CH2(CF2)9CF3CH2=CHCOOCH2CH2(CF2)11CF3CH2=CHCOOCH2CH2(CF2)13CF3CH2=CHCOOCH2CH2(CF2)15CF3CH2=CHCOOCH2CH2(CF2)17CF3CH2=C(CH3)COOCH2CH2(CF2)3CF3CH2=C(CH3)COOCH2CH2(CF2)5CF3CH2=C(CH3)COOCH2CH2(CF2)7CF3CH2=C(CH3)COOCH2CH2(CF2)9CF3CH2=C(CH3)COOCH2CH2(CF2)11CF3CH2=C(CH3)COOCH2CH2(CF2)13CF3CH2=C(CH3)COOCH2CH2(CF2)15CF3CH2=CHCOOCH2CH2NSO2(CF2)5CF3CH2=CHCOOCH2CH2(CF2)5CF3 Wherein: Rf groups and preferably all hydrogen atoms are substituted with fluorine atoms, the structure of the end portion to preferably -CF2CF3; an Rf group may be a straight chain structure or a branched structure, preferably a straight chain structure; an Rf group carbon atoms, preferably from 2 to 20, more preferably 6 to 16; R is H or CH3; a is O, S or NR; R1 is an alkylene group having 1 to 15 carbon atoms; may include more specific examples: CH2 = CHCOOCH2CH2 (CF2) 3CF3CH2 = CHCOOCH2CH2 (CF2) 5CF3CH2 = CHCOOCH2CH2 (CF2) 7CF3CH2 = CHCOOCH2CH2 (CF2) 9CF3CH2 = CHCOOCH2CH2 (CF2) 11CF3CH2 = CHCOOCH2CH2 (CF2) 13CF3CH2 = CHCOOCH2CH2 (CF2) 15CF3CH2 = CHCOOCH2CH2 ( CF2) 17CF3CH2 = C (CH3) COOCH2CH2 (CF2) 3CF3CH2 = C (CH3) COOCH2CH2 (CF2) 5CF3CH2 = C (CH3) COOCH2CH2 (CF2) 7CF3CH2 = C (CH3) COOCH2CH2 (CF2) 9CF3CH2 = C (CH3) COOCH2CH2 ( CF2) 11CF3CH2 = C (CH3) COOCH2CH2 (CF2) 13CF3CH2 = C (CH3) COOCH2CH2 (CF2) 15CF3CH2 = CHCOOCH2CH2NSO2 (CF2) 5CF3CH2 = CHCOOCH2CH2 (CF2) 5CF3

基于经济和实用的原因,单体A1最好是上述的具有不同Rf基结构的两种或多种单体的混合物。 For economic and practical reasons, the monomer mixture of A1 is preferably two or more monomers having different Rf group structure described above.

按照本发明,单体A2为除A1以外的其他乙烯基单体中的一种及其混合物,单体A2可以降低成本,并提供特殊衬层的黏着力、硬度、成膜性、交联性和附着力等作用,优选的单体A2包括苯乙烯、乙烯、丙烯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸、(甲基)丙烯酸乙酯、丙烯酸月桂酸酯、氯乙烯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、乙烯基吡咯烷酮、苯乙烯、二乙烯基苯、丙烯酰胺、N-羟甲基丙烯酰胺、乙酸乙烯酯、丙酸乙烯酯、(甲基)丙烯睛或(甲基)丙烯酸缩水甘油酯等中的一种;所述及的乳化剂包括阴离子型、阳离子型或非离子型中的一种;所述及的阴离子表面活性剂包括C7~C21的羧酸盐;C8~C18的烷基硫酸盐类,如十二烷基硫酸钠等;脂肪磺酸盐如十二烷基磺酸钠等;脂肪苯磺酸盐类,如十二烷基苯磺酸钠等;磷酸酯如罗地亚公司 According to the present invention, the monomers A2 is other vinyl monomers other than A1, and mixtures of one monomer A2 may reduce costs, and provide special liner adhesion, hardness, film-forming, crosslinkable and the role of adhesion and the like, A2 preferred monomers include styrene, ethylene, propylene, (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate, ethyl acrylate, laurate, vinyl chloride, (meth) acrylate, hydroxypropyl (meth) acrylate, vinyl pyrrolidone, styrene, divinylbenzene, acrylamide, N- methylol acrylamide, vinyl acetate an ester, vinyl propionate, (meth) acrylonitrile or (meth) acrylate and the like; and the emulsifiers include anionic, cationic or nonionic in one kind; the mentioned anionic surfactants include carboxylates of C7 ~ C21; C8 ~ C18 alkyl sulfates such as sodium lauryl sulfate and the like; aliphatic sulfonates such as sodium dodecyl sulfate and the like; aliphatic benzenesulfonic acid salts such as sodium dodecylbenzenesulfonate and the like; phosphates such as Rhodia RhodafacRE-610等。 RhodafacRE-610 and the like.

所述及的阳离子型包括C12~C18的烷基季铵盐、醚结构的季铵盐、烷基双胍盐酸盐等;所述及的非离子型包括聚氧化乙烯羧酸酯、多元醇酸酸酯、聚氧化乙烯烷基醚、聚氧化乙烯烷芳基醚、聚氧化乙烯酰胺等等。 And the cationic quaternary ammonium salts include C12 ~ C18 alkyl group, and an ether quaternary ammonium salt structure, alkyl biguanide hydrochloride and the like; and the nonionic include polyoxyethylene carboxylic acid esters, Alkyd esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ether, polyoxyethylene amide and the like.

乳化剂可以是上述一种或者多种的组合,优选是离子型与非离子型复合使用。 Emulsifiers may be one or more of the above-described combinations, preferred are ionic and non-ionic compound used.

本发明的水乳型含氟拒水拒油剂的制备方法包括如下步骤:(1)将单体混合物、水、乳化剂加入容器中,放入超声波清洗机内进行超声一定时间得到稳定的预乳液,此技术是熟知可行的,有关专业人员可以方便地实施。 Water emulsion prepared according to the present invention, the fluorine-containing water and oil repellent comprising the steps of: (1) the monomer mixture, of water, an emulsifier added to the container, placed in an ultrasonic cleaner for a predetermined time to obtain a stable ultrasonic pre emulsions, are well known in this technology possible, can be easily implemented relevant professionals.

(2)加入引发剂,引发剂优选水溶性过氧化物,如过氧化氢—氯化亚铁、过硫酸铵—亚硫酸氢钠、过硫酸钾—氯化亚铁、过硫酸钾—伯十二碳硫醇等,体系中还可以加入催化量的水溶性铜盐如硫酸铜为催化剂;引发剂的用量为单体重量份的0.1~3%;聚合反应温度可在较宽的范围内改变,即30℃~120℃。 (2) addition of the initiator, a water-soluble initiator is preferably a peroxide, such as hydrogen peroxide - ferrous chloride, ammonium persulfate - sodium bisulfite, potassium persulfate - ferrous chloride, potassium persulfate - ten primary two carbon mercaptan, the system may also be added a catalytic amount of a soluble copper salt such as copper sulfate catalyst; the amount of initiator is 0.1 to 3% by weight of the monomers parts; polymerization temperature can vary over a wide range , i.e. 30 ℃ ~ 120 ℃. 最好是在40~60℃;为控制分子量,反应体系中可以加入链转移剂例如十二烷基硫醇、四氯化碳或四溴化碳,链转移剂的用量为单体重量份的0.05~1%。 Preferably at 40 ~ 60 ℃; to control molecular weight, may be added to the reaction system a chain transfer agent such as dodecyl mercaptan, carbon tetrachloride or carbon tetrabromide chain transfer agent parts by weight of monomer 0.05 to 1%.

适合于使用本发明的水乳型拒水拒油剂来处理的物品可以是各种纤维制品,如棉、麻、羊毛、聚酰胺、聚丙烯、聚丙烯腈、聚酯等天然动植物纤维或者化学合成纤维。 Water emulsion suitable for use according to the present invention is water and oil repellent article may be treated to various fiber products, natural plant and animal fibers such as cotton, hemp, wool, polyamide, polypropylene, polyacrylonitrile, polyester, etc., or synthetic chemicals. 本发明的水分散液可以采用浸滞、涂布的方法使其附着在被处理物的表面上,再采用干燥的方法处理。 Aqueous dispersion of the present invention may employ slow dip coating method so as adhere to the surface to be processed, and then using the drying process. 本发明制备的拒水拒油剂也可以用于一些硬质表面如内外墙防污涂料、船舶涂料、瓦、砖、水泥、混凝土等的涂层。 Water and oil repellent may also be used in some hard surface coatings prepared according to the invention as interior and exterior coatings, marine coatings, tiles, brick, cement, concrete and the like.

与以前的技术相比,本发明的水乳型含氟拒水拒油剂具有优异的拒水拒油,并且不含有对环境不利的有机溶剂,同时也不采用较昂贵的引发剂2,2'-偶氮双(2-脒基丙烷)二盐酸盐或者2,2'-偶氮双(异丁脒)二盐酸盐,聚合温度较低,聚合速度较快,将具有十分广泛的应用前景。 Compared with the prior art, water emulsion of the present invention, the fluorine-containing water and oil repellent having excellent water and oil repellent, and does not contain environmentally undesirable organic solvent, while not using more expensive initiator 2,2 '- azobis (2-amidinopropane) dihydrochloride or 2,2'-azobis (isobutyramidine) dihydrochloride, lower temperature polymerization, the polymerization speed, having a very broad prospects.

具体实施方式 detailed description

下面根据实施例来更具体地解释本发明,但本发明不受这些实施例的限定。 The following more specifically explain the present invention in accordance with examples, but the present invention is not limited to these embodiments.

实施例1在200ml烧杯中混合下列成分:甲基丙烯酸全氟烷基乙基酯30g、丙烯酸月桂酸酯10g、甲基丙烯酸丁酯8g、N-羟甲基丙烯酰胺1g、甲基丙烯酸羟丙酯1g、十二烷基硫醇0.25g、十二烷基硫酸钠1.5g、烷基酚聚氧乙烯醚-10 0.5g、去离子水170g,置于SK1200H型超声波清洗器预乳化1小时,得到稳定的水分散液。 Example 1 The following ingredients mixed in a 200ml beaker: perfluoroalkylethyl methacrylate ester 30g, lauryl methacrylate 10g, butyl methacrylate 8g, N- methylol acrylamide 1g, hydroxypropyl methacrylate, ester 1g, dodecyl mercaptan 0.25g, sodium lauryl sulfate 1.5g, alkylphenol ether -10 0.5g, 170g of deionized water, placed SK1200H ultrasonic cleaner pre-emulsified for 1 hour a stable aqueous dispersion. 将预乳液加入装有搅拌器、温度计和冷凝器的玻璃反应器中,然后加入碳酸氢钠0.3g、过硫酸钾0.3g、亚硫酸氢钠0.15g、硫酸铜0.025g,通氮去氧,搅拌加热,水浴升温至50℃,3分钟后出现乳光,继续反应5小时,得固含量23.5%的乳胶液约223g。 The pre-emulsion was added with a stirrer, a thermometer and a glass condenser, and sodium bicarbonate 0.3g, potassium persulfate 0.3g, sodium bisulfite 0.15g, 0.025 g of copper sulfate, a nitrogen-deoxy, was heated with stirring in a water bath warmed to 50 ℃, opalescent after three minutes, the reaction was continued for 5 hours 23.5% of the solids content of the latex of about 223g.

实施例2混合下列成分:丙烯酸全氟烷基乙基酯35g、丙烯酸十八酯13g、N-羟甲基丙烯酰胺1g、丙烯酸羟乙酯1g、十二烷基硫醇0.25g、十八烷基三甲基氯化胺1.5g、去离子水160g,置于USC-102型超声波清洗器预乳化0.5小时,得到稳定的水分散液。 Embodiment 2 The following ingredients were mixed: acrylic perfluoroalkylethyl acrylate 35g, stearyl acrylate 13g, N- methylol acrylamide 1g, hydroxyethyl acrylate 1g, dodecyl mercaptan 0.25g, octadecane trimethyl ammonium chloride 1.5g, 160g of deionized water, placed USC-102 ultrasonic cleaner pre-emulsified for 0.5 hour to obtain a stable aqueous dispersion. 将预乳液加入装有搅拌器、温度计和冷凝器的玻璃反应器中,然后加入碳酸氢钠0.3g、过硫酸胺0.3g、亚硫酸氢钠0.15g,通氮去氧,搅拌加热至水浴45℃反应5小时,得固含量28.6%的乳胶液约183g。 The pre-emulsion was added to a glass reactor equipped with a stirrer, thermometer and condenser, followed by addition of sodium bicarbonate 0.3g, amine persulfate 0.3g, sodium bisulfite 0.15g, a nitrogen deoxygenated water bath with stirring and heated to 45 ℃ reaction for 5 hours, 28.6% of the solids content of the latex of about 183g.

实施例3~8基本上按照实施例1或2的方法制备含氟乳液,其单体组成配方列于表1中:表1实施例3-8中的单体用量(重量份)单体 3 4 5 6 7 8丙烯酸全氟烷基乙酯 70 80 50 - - -甲基丙烯酸全氟烷基乙酯 - - - 60 70 60丙烯酸月桂酸酯 20 - 30 25 - 30丙烯酸硬脂酸酯 20 - - 30 -偏氯乙烯 10 0 20 15 0 10丙烯酸-2-羟乙酯 - 2 - - 2甲基丙烯酸-3-羟基丙酯 2 - - 2 - -N-羟基丙烯酰胺 2 2 2 2 2 2 Examples 3 to 8 fluorine-containing emulsion was prepared substantially according to Example 1 or 2 in which the monomer composition formulations are listed in Table 1: Monomer Amount (parts by weight) of monomer 3-8 Table 1 Example 3 45678 perfluoroalkyl ethyl acrylate 70 80 50 - - - perfluoroalkyl ethyl methacrylate - - - 60 70 60 lauryl methacrylate 20--3025--30 acrylate monostearate 20-- - 30 - vinylidene chloride 1002015010 acrylate, 2-hydroxyethyl acrylate - 2 - - 2-hydroxybutyl methacrylate, 2 - - 2 - -N- hydroxy-acrylamide 222 222

实施例9测试方法:抗水性的实验可以用以下方法进行:将一系列由水和异丙醇(IPA)配制的标准试液(列于表2中)滴加到试样上。 Test method of Example 9: water resistance experiments can be performed by the following method: A series of standard test solution prepared from water and isopropanol (of IPA) (listed in Table 2) was added dropwise to the sample. 自低标号(防水性试验标号1)开始,在至少相距2英寸的三个位置上各滴上一滴(直径约5mm或体积0.05ml)。 From low grade (water resistance test numeral 1) starts, at least at three positions spaced 2 inches on each of a drop (approximately 5mm in diameter or volume 0.05ml). 观察这些液滴10秒钟。 These droplets were observed for 10 seconds. 如果在10秒钟后,三个液滴中有两个看起来仍然是球形至半球形,则在邻近的位置上滴上3滴高一号数的试液,并观察10秒钟。 If after 10 seconds, there are two three drops are still spherical to hemispherical appear, at a position adjacent drops of test solution 3 drops One high, and observed for 10 seconds. 继续下去,直至一种试液的3个液滴中有2个不能保持球状至半球状为止。 Continue until one kind of test solution 3 with 2 drops in can not be maintained until the spherical hemispherical. 试样的防水性就是3个液滴中有2个保持球形至半球形的最高标号。 Sample 3 is the waterproof drops have 2 to remain spherical to hemispherical, with the highest numbers.

表2标准水试液防水性试验标号 组成%IPA %水 防水性试验标号 组成%IPA %水1 2 98 7 50 502 5 95 8 60 403 10 90 9 70 304 20 80 10 80 205 30 70 11 90 106 40 60 12 100 0抗油性采用以下的方法进行:对于聚合物样品按修订的AATCC标准试验方法No.118进行抗油性试验,其方法如下:将一系列有机液体(列于表3中)滴加到聚合物样品上。 Table 2 Test waterproofness water standard test solution consisting numeral% IPA% Test aqueous water repellent composition numeral% IPA% Water 1 2 9,875,050,259,586,040,310 9,097,030,420,801,080,205. 11 30 70 90 106 4060121000 oil repellency using the following method: a sample of the polymer according to AATCC standard test method revised anti No.118 oil test method is as follows: the number of organic liquids (listed in table 3) was added dropwise to the polymer sample. 开始时在至少5mm的三个位置上各滴上1滴(直径约5mm或体积0.05ml)最低标号的试液(抗油性试验标号1)。 At three positions on each of at least 5mm drops of test solution 1 drop (approximately 5mm in diameter or volume 0.05ml) at the start of the lowest numbered (reference numeral oil repellency Test 1). 观察这些液滴30秒钟。 These droplets were observed for 30 seconds. 如果在这个时间后,三个液滴中有2个仍然是球形或半球形并且液滴周围没有芯吸现象,则在邻近的位置再滴上3滴高一标号的试液并同时观察30秒钟。 If, after this time, there are two three drops remain spherical or hemispherical, with no wicking phenomenon and around the droplets, at a position adjacent to the test solution and then dropwise 3 drops of a high reference and simultaneously observed for 30 seconds bell. 直至一种试液的3个液滴中有两个不能保持球形至半球形或出现浸润现象为止,聚合物样品的抗油性就是30秒钟内3个液滴中的两个保持球形至半球形且无浸润现象的最高标号试液。 3 until the one kind of test solution two droplets can not be maintained until the spherical to hemispherical or infiltration occurs, oil repellency polymer sample is within 30 seconds in two three drops remain spherical to hemispherical, with and no infiltration of the highest grade test solution.

表3抗油性试验抗油性试验标号 试液1 Nojol*纯化矿物油(*plough 公司商品名)2 65/35 Nojol/正十六烷3 正十六烷4 正十四烷5 正十二烷6 正庚烷采用上述方法,将聚合物乳液涂于18mm×18mm的石英片上,形成均匀的薄膜,于130℃热处理3-5分钟,测量聚合物样品的防水、防油性。 Table 3 Test oil repellency Oil repellency Test 1 Nojol * reference sample solution is purified mineral oil (* plough Company tradename) 2 65/35 Nojol / n-hexadecane 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-heptane by the above method, the polymer emulsion was coated on a 18mm × 18mm quartz plate to form a uniform thin film, a heat treatment at 130 ℃ 3-5 minutes, the polymer sample is measured waterproof, oil repellency.

表4实施例样品的抗水抗油性原液 抗水性 抗油性实施例1 12 5实施例2 12 6实施例3 12 6实施例4 12 6实施例5 12 5实施例6 12 6实施例7 12 6实施例8 12 6由上述试验可见,本发明的水乳型含氟拒水拒油剂的防水性均达到12#,防油性达到5~6#,乳液显示出良好的拒水拒油性。 Table water resistant oil repellency liquid water repellency oil repellency Embodiment Example 4 Example Sample of Example 1 125 Example 21263126 Example 4 126 Example 5 125 Example 6 126 Example 7 126 embodiment Example 8126 seen from the above test, water emulsion of the present invention, the fluorine-containing water- and oil-average water resistance reaches # 12, the oil repellency of 5 to # 6, the emulsion exhibits excellent water and oil repellency.

Claims (10)

  1. 1.一种水乳型含氟拒水拒油剂,其特征在于,为由单体、乳化剂及水经预乳化,然后聚合而获得的含氟共聚物在水介质中的乳液;所说的单体为单体A1和单体A2的混合物,其中:单体A1占共聚物总重量的百分数为35%~90%,单体A2占共聚物总重量的百分数为10%~65%;所述及的单体A1为由具有全氟烷基(简称Rf)的(甲基)丙烯酸全氟烷基乙酯,其结构如下式所示: A fluorine-containing water emulsion water and oil repellent, characterized in that, by the monomer, water, emulsifier and pre-emulsion, and then polymerizing the fluorine-containing copolymer obtained by an emulsion in an aqueous medium; said monomers are monomers A1 and A2 of the monomer mixture, wherein: the monomer percentage of A1 is 35% to 90% of the total weight of the copolymer, the monomers A2 percentage of the total weight of the copolymer is 10% to 65%; and the monomer having a perfluoroalkyl group by A1 (referred Rf) a (meth) acrylate, perfluoroalkyl acrylate, which is shown in the following structural formula: R是H或CH3;A是O、S或NR;R1是含1~15个碳原子的亚烷基;单体A2为除单体A1以外的其他乙烯基单体中的一种及其混合物;所述及的乳化剂为阴离子型、阳离子型或非离子型中的一种及其混合物。 R is H or CH3; A is O, S or NR; R1 is an alkylene group having 1 to 15 carbon atoms; A2 is a monomer other vinyl monomers other than the monomers A1 in the mixture of one and ; and the emulsifiers are anionic, cationic or non-ionic and mixtures of one.
  2. 2.根据权利要求1所述的水乳型含氟拒水拒油剂,其特征在于,Rf为全部氢原子被氟原子取代,末端部分的结构为-CF2CF3。 The fluorine-water emulsion as claimed in claim 1, said water and oil repellent, characterized in that, an Rf of all hydrogen atoms are substituted by fluorine atoms, the structure of the end portion is -CF2CF3.
  3. 3.根据权利要求2所述的水乳型含氟拒水拒油剂,其特征在于,Rf是直链结构或支链结构。 The water emulsion as claimed in claim 2, said fluorine-containing water and oil repellent, characterized in that, an Rf linear structure or a branched structure.
  4. 4.根据权利要求3所述的水乳型含氟拒水拒油剂,其特征在于,Rf的碳原子数为2~20个。 Water emulsion according to claim 3, the fluorine type water and oil repellent, wherein the number of carbon atoms in Rf is from 2 to 20.
  5. 5.所述的单体A1是以下单体的一种或者多种的混合物:CH2=CHCOOCH2CH2(CF2)5CF3CH2=CHCOOCH2CH2(CF2)7CF3CH2=CHCOOCH2CH2(CF2)9CF3CH2=CHCOOCH2CH2(CF2)11CF3CH2=CHCOOCH2CH2(CF2)13CF3CH2=CHCOOCH2CH2(CF2)15CF3CH2=CHCOOCH2CH2(CF2)17CF3CH2=C(CH3)COOCH2CH2(CF2)3CF3CH2=C(CH3)COOCH2CH2(CF2)5CF3CH2=C(CH3)COOCH2CH2(CF2)7CF3CH2=C(CH3)COOCH2CH2(CF2)9CF3CH2=C(CH3)COOCH2CH2(CF2)11CF3CH2=C(CH3)COOCH2CH2(CF2)13CF3CH2=C(CH3)COOCH2CH2(CF2)15CF3。 The said monomer A1 is a mixture of the following monomers or more of: CH2 = CHCOOCH2CH2 (CF2) 5CF3CH2 = CHCOOCH2CH2 (CF2) 7CF3CH2 = CHCOOCH2CH2 (CF2) 9CF3CH2 = CHCOOCH2CH2 (CF2) 11CF3CH2 = CHCOOCH2CH2 (CF2 ) 13CF3CH2 = CHCOOCH2CH2 (CF2) 15CF3CH2 = CHCOOCH2CH2 (CF2) 17CF3CH2 = C (CH3) COOCH2CH2 (CF2) 3CF3CH2 = C (CH3) COOCH2CH2 (CF2) 5CF3CH2 = C (CH3) COOCH2CH2 (CF2) 7CF3CH2 = C (CH3) COOCH2CH2 (CF2) 9CF3CH2 = C (CH3) COOCH2CH2 (CF2) 11CF3CH2 = C (CH3) COOCH2CH2 (CF2) 13CF3CH2 = C (CH3) COOCH2CH2 (CF2) 15CF3.
  6. 6.根据权利要求1所述的水乳型含氟拒水拒油剂,其特征在于,单体A2包括苯乙烯、乙烯、丙烯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸、(甲基)丙烯酸乙酯、丙烯酸月桂酸酯、氯乙烯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、乙烯基吡咯烷酮、苯乙烯、二乙烯基苯、丙烯酰胺、N-羟甲基丙烯酰胺、乙酸乙烯酯、丙酸乙烯酯、(甲基)丙烯睛或(甲基)丙烯酸缩水甘油酯中的一种及其混合物。 The fluorine-water emulsion as claimed in claim 1, said water and oil repellent, wherein A2 monomers include styrene, ethylene, propylene, (meth) acrylate, butyl (meth) acrylate, , (meth) acrylic acid, (meth) acrylate, lauryl methacrylate, vinyl chloride, (meth) acrylate, hydroxypropyl (meth) acrylate, vinyl pyrrolidone, styrene, divinyl benzene, acrylamide, N- methylol acrylamide, vinyl acetate, vinyl propionate, (meth) acrylonitrile or (meth) acrylate, and mixtures of one.
  7. 7.根据权利要求1~6任一项所述的水乳型含氟拒水拒油剂,其特征在于,重量百分比含量为:含氟共聚物 5~40%乳化剂 0.5~4%水 余量。 The fluorine-water emulsion as claimed in claim any one of claims 1 to 6, water and oil repellent, characterized in that the percentage by weight: 5 to 40% fluorine-containing copolymer emulsifier 0.5 to 4% water remainder the amount.
  8. 8.根据权利要求1~7任一项所述的水乳型含氟拒水拒油剂的制备方法,其特征在于,包括如下步骤:(1)将单体混合物、水、乳化剂采用超声波乳化;(2)加入引发剂,在30℃~120℃的条件下聚合。 The fluorine-containing water emulsion according to any one of claims 1 to 7, wherein the water-repellent oil-repellent preparation, characterized by comprising the steps of: (1) the monomer mixture, of water, ultrasonic emulsifier emulsion; (2) addition of the initiator, the polymerization conditions at the 30 ℃ ~ 120 ℃.
  9. 9.根据权利要求8所述的水乳型含氟拒水拒油剂的制备方法,其特征在于,引发剂包括过氧化氢—氯化亚铁、过硫酸铵—亚硫酸氢钠、过硫酸钾—氯化亚铁或过硫酸钾—伯十二碳硫醇中的一种及其混合物,引发剂的用量为单体重量份的0.1~3%。 Water emulsion according to claim 8, said fluorine-containing water- and oil-repellent preparation, characterized in that the initiator comprises hydrogen peroxide - ferrous chloride, ammonium persulfate - sodium bisulfite, persulfate potassium - ferrous chloride or potassium persulfate - a primary dodecyl mercaptan and mixtures thereof in an amount of initiator is 0.1 to 3% parts by weight of the monomers.
  10. 10.根据权利要求8所述的水乳型含氟拒水拒油剂的制备方法,其特征在于,聚合反应时加入链转移剂,所述及的转移剂包括十二烷基硫醇、四氯化碳或四溴化碳,链转移剂的用量为单体重量份的0.05~1%。 10. The fluorine-water emulsion as claimed in claim 8, the method for preparing water-repellent oil-repellent, wherein the chain transfer agent added during the polymerization reaction, and the transfer agents include dodecyl mercaptan, tetrakis chloride, carbon tetrabromide or carbon, the amount of chain transfer agent parts by weight of a monomer from 0.05 to 1%.
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CN105908510A (en) * 2016-06-23 2016-08-31 无锡市金五星针纺有限公司 Fluorine-containing fabric finishing agent and preparation method thereof
CN105908509A (en) * 2016-06-23 2016-08-31 无锡市金五星针纺有限公司 Fluorine-containing fabric finishing agent and preparation method thereof
CN106279518A (en) * 2016-08-08 2017-01-04 广州市雷曼兄弟电子科技有限公司 Fluorine-containing polymer, waterproof and oil-proof treating agent, preparation method of waterproof and oil-proof treating agent and protection film
WO2018027537A1 (en) * 2016-08-09 2018-02-15 广州市雷曼兄弟电子科技有限公司 Fluorine-containing polymer, waterproof and oilproof treatment agent and preparation method thereof, and protective film
CN106957387A (en) * 2017-03-09 2017-07-18 山东鲁普科技有限公司 Preparation and use method of waterproof coating agent of outdoor exercise rope

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