CN1247628C - Composite nano material modified emulsion and its preparation method - Google Patents

Composite nano material modified emulsion and its preparation method Download PDF

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CN1247628C
CN1247628C CN 200310112822 CN200310112822A CN1247628C CN 1247628 C CN1247628 C CN 1247628C CN 200310112822 CN200310112822 CN 200310112822 CN 200310112822 A CN200310112822 A CN 200310112822A CN 1247628 C CN1247628 C CN 1247628C
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CN1556120A (en
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马胜军
李敏
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中国化工建设总公司常州涂料化工研究院
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Abstract

本发明涉及一种复合纳米材料改性的乳液及其制备方法,它是用无机纳米材料改性丙烯酸酯类乳液,无机纳米材料是纳米氧化铝粉体和纳米硅溶胶的复配物,用量为250~2500重量份,纳米氧化铝粉体占纳米硅溶胶固体含量的5~30%;丙烯酸酯类乳液用量为2500重量份,乳液的固体含量为40±5%,上述百分数为重量百分数。 The present invention relates to a composite nanomaterial modified emulsion and a preparation method, which is modified with an inorganic nanomaterials acrylate emulsion, inorganic nanomaterial is a nano-alumina powder and the nano-silica complex was in an amount of 250 to 2500 parts by weight, nano-alumina powder from 5 to 30 percent solids silica sol nanometers; acrylate emulsion in an amount of 2500 parts by weight, the solid content of the emulsion was 40 ± 5%, the above percentages are by weight. 该改性乳液的制备方法,首先按配方比例将纳米氧化铝粉体和纳米硅溶胶混合,再进一步用超声波分散至分散体粒度为100~200nm得到复配物,然后按配方比例对丙烯酸酯类乳液进行改性即可。 The modified emulsion preparation method, the ratio of the first nano-alumina according to the formula powder and the nano-silica sol, and further dispersed by an ultrasonic dispersion particle size was 100 ~ 200nm obtained compound was then formulated ratio of acrylate emulsion can be modified. 乳液的稳定性较单纯用硅溶胶或氧化铝粉体改性的乳液大幅度提高,涂膜耐水性和耐碱性明显改善。 Emulsion stability than the pure silica sol substantial increase or modified alumina powder emulsions, water resistance and alkali resistance film significantly improved.

Description

复合纳米材料改性的乳液及其制备方法 Emulsion modified nanocomposite and its preparation method

技术领域 FIELD

本发明涉及一种复合纳米材料改性的乳液及其制备方法。 The present invention relates to an emulsion of modified nanocomposite and its preparation method.

背景技术 Background technique

用纳米材料改性乳液,通常采用纳米溶胶或纳米粉体。 With a nanomaterial modified emulsion usually Nanoparticles or nanopowders. 用纳米溶胶如硅溶胶改性乳液,一般采用物理复合,即将乳液和纳米溶胶在机械搅拌下混合。 The silica sol-modified nano-emulsions, generally using physical complex, i.e. the emulsion and mixing Nanoparticles mechanical stirring. 这样改性的乳液,虽然在涂膜硬度、回粘性、透气性和附着力等方面有所改善,但由于是物理复合,不能充分发挥纳米溶胶的改性作用,而且改性后乳液的贮存稳定性存在一定问题。 Such aspects of the modified emulsion, although the film hardness after tack, adhesion and the like permeability improvement, it is a physical composite, can not give full play to the role of nano-modified sol, and the modified storage-stable emulsion nature there are certain problems. 另外,也有采用化学复合,即纳米溶胶参与有机单体的聚合反应,纳米溶胶与乳胶粒子形成了一定量的化学键,使二者之间相容性改善,从而提高了涂膜的性能,但是在乳液合成和贮存期间稳定性差。 Further, there is also a chemical compound, i.e. sol participate in the polymerization reaction of the nano organic monomer, and the latex particles are formed nanosol a certain amount of chemical bonds that improve compatibility between them, thereby improving the performance of the coating, but poor stability during emulsion polymerization and storage. 用纳米粉体改性有机乳液,也可以将纳米粉体机械分散到乳液中,改善乳液性能,由于纳米粉体,其粒度为纳米级,极易团聚难分散均匀,因而纳米粉体的特性不能充分体现。 Nano modified organic powder emulsions, nano powder may be mechanically dispersed into the emulsion, to improve the emulsion properties, since the nano powder having a particle size of nanometer, is difficult to agglomerate easily dispersed uniformly, and thus nano powder characteristics can not be fully reflect. 在乳液合成时,加入纳米粉体并把纳米粒子包裹到有机胶粒中形成核-壳结构,部分解决了纳米粉体的易团聚性。 When emulsion polymerization, was added and the parcel nanopowders nanoparticles into an organic micelle forming the core - shell structure, easy to join a partial solution nano powder. 但是,由于纳米粉体比表面积大,表面能高,一方面造成乳液合成时易产生大量残渣或造成乳液胶凝,另一方面很难形成理想的核-壳结构的乳液。 However, due to the large specific surface area nano powder, high surface energy, resulting in an aspect easy to generate large debris resulting emulsion gelled or emulsion polymerization, on the other hand is difficult to form over the core - shell structure of the emulsion.

发明内容 SUMMARY

本发明的目的在于,提供一种复合纳米材料改性的乳液及其制备方法,该乳液的贮存稳定性大幅度提高,成膜后涂膜的耐水性和耐碱性明显改善,制备方法简单,纳米材料的改性效果明显。 Object of the present invention is to provide a composite nanomaterial modified emulsion and a preparation method, the storage stability of the emulsion is greatly improved, the water resistance and alkali deposition coating film significantly improved, simple preparation method, nanomaterials significant modifying effect.

实现本发明目的的技术方案:一种复合纳米材料改性的乳液,它是用无机纳米材料改性丙烯酸酯类乳液,无机纳米材料是纳米氧化铝粉体和纳米硅溶胶的复配物,用量为250~2500重量份,纳米氧化铝粉体占纳米硅溶胶固体含量的5~30%;丙烯酸酯类乳液用量为2500重量份,乳液的固体含量为40±5%,上述百分数为重量百分数。 This object is achieved technical solutions: A modified nano composite emulsion, it is modified acrylate emulsion of inorganic nanomaterials, inorganic nanomaterial is a nano-alumina powder and the nano-silica complex was used in an amount 250 to 2500 parts by weight, nano-alumina powder from 5 to 30 percent solids silica sol nanometers; acrylate emulsion in an amount of 2500 parts by weight, the solid content of the emulsion was 40 ± 5%, the above percentages are by weight.

上述乳液中,所述纳米氧化铝粉体粒径为5~50纳米;所述纳米硅溶胶的颗粒粒度为5~30纳米,固体含量为20~40%。 The above emulsion, the nano-alumina powder particle diameter of 5 to 50 nanometers; silica sol of the nano-particle size of 5 to 30 nm, solids content of 20 to 40%.

上述乳液中,所述丙烯酸酯类乳液是丙烯酸酯乳液、苯丙乳液、醋丙乳液中的一种或几种。 The above emulsion, the emulsion is an acrylate acrylic emulsion, acrylic emulsion, acrylic emulsion vinegar of one or more. 可以由下述重量份的原料组成:单体1000份;乳化剂10~25份;引发剂5~20份;偶联剂0.1~20份;去离子水1500份。 It may be made of the following raw materials in parts by weight: 1000 parts monomer; 10 to 25 parts emulsifier; 5 to 20 parts initiator; and 0.1 to 20 parts coupling agent; 1500 parts of deionized water.

上述乳液中,所述丙烯酸酯类乳液采用半连续合成工艺,具体步骤是,在反应器内加入部分乳化剂、引发剂和去离子水,搅拌下升温至84~88℃,10分钟后同时滴加剩余的乳化剂、引发剂和去离子水混合液及单体和偶联剂的混合液,滴加时间1.5~2小时,聚合温度在84~88℃,滴加完毕再于86~90℃保温1小时,降温至40~50℃,过滤、放料即为丙烯酸酯类乳液。 The above emulsion, the semi-continuous emulsion acrylic synthetic process, particularly steps, part of the emulsifier is added in the reactor, the initiator and deionized water, under stirring warmed to 84 ~ 88 ℃, after 10 minutes while the dropwise adding remaining emulsifiers, an initiator, and a mixture of deionized water and a mixture of monomers and coupling agents dropwise over 1.5 to 2 hours, the polymerization temperature is 84 ~ 88 ℃, addition was complete and then at 86 ~ 90 ℃ incubated for 1 hour, cooling to 40 ~ 50 ℃, filtered, namely discharge acrylate emulsion.

上述乳液中,所述单体是甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸异辛酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸、丙烯酸、苯乙烯、醋酸乙烯酯中的一种或几种。 The above emulsion, the monomer is methyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate , methacrylic acid, acrylic acid, styrene, vinyl acetate, one or several. 所述乳化剂为非离子型乳化剂或阴离子型乳化剂。 The non-ionic emulsifier or emulsifiers anionic emulsifiers. 例如,十二烷基硫酸钠、十二烷基苯磺酸钠、MS-1、HMPS、烷基酚聚氧乙烯醚等。 For example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, MS-1, HMPS, polyoxyethylene alkylphenol ether. 所述引发剂为过硫酸铵或过硫酸钾。 The initiator is ammonium persulfate or potassium persulfate. 所述偶联剂是硅烷偶联剂或者是钛酸酯偶联剂。 The coupling agent is a silane coupling agent or a titanate coupling agent. 其中硅烷偶联剂可以是含氨基、乙烯基、环氧基或甲基丙烯酰氧基的硅烷偶联剂中的一种或多种。 Wherein the amino group-containing silane coupling agent may be, one or more vinyl, epoxy or methacryloxy silane coupling agent in the.

制备上述复合纳米材料改性的乳液的方法,首先按配方比例将纳米氧化铝粉体和纳米硅溶胶混合,再进一步用超声波分散至分散体粒度为100~200nm得到复配物,然后按配方比例用复配物对丙烯酸酯类乳液进行改性即可。 Preparation of the composite material nanoemulsion modified method, first by the ratio of the nano-alumina powder formulation nanometers and silica sol, and further dispersed by an ultrasonic dispersion particle size was 100 ~ 200nm obtained compound was then formulated proportions It can be modified acrylate emulsion of a complex thereof.

在上述制备方法中,所述用复配物改性丙烯酸酯类乳液的方法是,在搅拌下加到已合成的丙烯酸酯类乳液中混拼完成改性,或者是将复配物加到反应器中,与组成丙烯酸酯类乳液的各组分,一起进行乳液聚合完成改性。 In the method of the above production process, the compound was modified with acrylate emulsion is Blending added with stirring to complete the modification of the synthesized acrylic emulsion, or the complex was added to the reaction vessel, with each of the constituents of the acrylate emulsion, the emulsion polymerization is completed with the modification.

本发明的技术效果:采用本发明的技术方案的复合纳米材料改性的丙烯酸酯乳液,由于所用纳米材料是纳米氧化铝粉体和纳米硅溶胶,它可以使乳液同时获得两种纳米材料的特性,特别是在制备本发明乳液时,复配两种纳米材料,对于纳米氧化铝粉体而言,纳米硅溶胶实质上起到分散剂的作用,因为硅溶胶粒子是纳米级而且大部分颗粒粒度在15nm左右,表面有大量羟基。 Technical effects of the invention: The modified nanocomposite aspect of the present invention, acrylic emulsion, since the nano-material is nano-alumina and nano silica powder, which can simultaneously obtain properties of both the emulsion nanomaterials , particularly in the preparation of the emulsion of the present invention, two kinds of complex nanomaterials for nano-alumina powder, the silica nano substantially functions as a dispersant, because silica particles are nanoscale size and majority of the particles about 15nm, a large number of surface hydroxyl groups. 这种硅溶胶粒子能渗透到纳米氧化铝粉体的团聚体间隙里并吸附在纳米氧化铝粉体的粒子表面,在超声波分散作用下,纳米氧化铝粉体能很好的分散并稳定在纳米硅溶胶中。 Such silica particles can penetrate into the nano-alumina powder agglomerates in the gap, and adsorbed on the surface of nanometer alumina particles, under the action of ultrasonic dispersion, nano-alumina powder can be well dispersed and stabilized in the nano silica sol. 克服了已有技术中因纳米粉体聚集所带来的各种弊病。 Overcome various shortcomings of prior art Yin Nami powder aggregation brings. 同时分散良好的两种纳米材料之间相互还具有协同稳定作用,因而用这种方法获得的复配物再进一步改性丙烯酸酯类乳液,其贮存稳定性大大优于单独使用一种纳米材料改性的同类乳液,在成膜后,耐水性方面明显优于未改性的同类乳液。 Each also has a synergistic stabilizing effect between two well dispersed while nanomaterials, and thus obtained by this method complexation was further modified acrylate emulsion, its storage stability is much better than the use of a nano-modified material alone of the same emulsion after film formation, water resistance superior to similar emulsions unmodified. 此外,采用上述方法复配的纳米材料,在改性丙烯酸酯类乳液时,无论是与有机单体一起聚合,还是直接将复配物与已合成的乳液机械混合,对本发明改性的乳液贮存稳定性均有明显提高。 Further, the above-described method of complex nanomaterials, when modified acrylate emulsion, both polymerized with organic monomers or directly to the complex was mechanically mixed with the synthesized emulsion, an emulsion of the present invention the modification of the storage stability has improved significantly.

具体实施方式 Detailed ways

以下结合实施例对本发明作进一步具体描述,但不局限于此。 The following examples of the present invention will be described in further detail, but is not limited thereto. 实施例中各原料的用量均为重量份,除另有说明外,均为市售工业品。 Example embodiments each feed amounts are parts by weight, unless otherwise indicated, are commercially available industrial products.

实施例11、纳米材料复配物的制备将10重量份纳米氧化铝粉体(粒度20nm),与400重量份纳米硅溶胶(固体含量25%,平均粒度10nm),在容器内搅拌均匀,然后置于超声波分散仪(功率:800瓦)分散至粒度<120nm得到复配物,其中纳米氧化铝粉体占纳米硅溶胶固体量的10%,贮存备用。 Example 11 Preparation of copolymers with nanomaterials 10 parts by weight of the nano-alumina powder (particle size 20 nm), and 400 parts by weight of nano-silica sol (solids content 25%, average particle size 10 nm), stir in the container, and then meter placed in an ultrasonic dispersion (power: 800 W) was dispersed to a particle size <120nm complex was obtained, wherein the nano-alumina powder 10% solids silica sol nanoparticles, stored for later use.

2、丙烯酸酯乳液的配方见表1。 2, acrylic emulsion formulations shown in Table 1.

表1 Table 1

3、改性乳液的制备将2/3的去离子水加入反应器内升温,温度达到84~88℃时,加入乳化剂、引发剂和500份去离子水混合物的20%,10分钟后,开始同时滴加单体和偶联剂的混合液及剩余量的乳化剂、引发剂和500份去离子水的混合液,控制在1.5~2小时内滴加完毕,升温至86~90℃保温1小时,降温至40~50℃过滤、放料制得丙烯酸酯乳液。 3, Preparation of modified emulsion 2/3 of deionized water was added warmed the reactor temperature reached 84 ~ 88 ℃, emulsifier, initiator agent and 500 parts of 20% deionized water mixture, after 10 minutes, start added dropwise a mixture of monomers and the remaining amount of the coupling agent and emulsifier, initiator, and a mixture of 500 parts of deionized water, controlling the addition was complete within 1.5 to 2 hours, warmed to 86 ~ 90 ℃ incubated 1 hour, cooling to 40 ~ 50 ℃ by filtration, to obtain discharge of acrylic emulsion. 搅拌下加入已制得的纳米材料复配物,混合0.5小时得到复合纳米材料改性的丙烯酸酯乳液。 Was added with stirring to prepare nanomaterials complex was mixed 0.5 hours to obtain a modified nanocomposite acrylate emulsion.

实施例21、采用实施例1相同配方和方法制备纳米材料复配物。 Example 21 Example 1 using the same formulation and method for preparing nano-material compound thereof.

2、丙烯酸酯乳液的配方与实施例1相同。 2, the same formulation acrylic emulsion Example 1.

3、改性乳液的制备将按实施例1配方和方法制得的复配物和2/3的去离子水(1000份)加到反应器内升温,温度达到84~88℃时,以下再按实施例1的乳液聚合方法在复配物存在下完成乳液聚合,制得复合纳米材料改性的丙烯酸酯乳液。 3, the modified emulsion prepared in Example 1 will be prepared as formulations and the formulations were 2/3 and deionized water (1000 parts) was added to the reactor raised embodiments, the temperature reached 84 ~ 88 ℃, then the following Example 1 an emulsion polymerization process according to embodiments of the present acrylic emulsion polymerization is completed, to make a composite nanomaterial modified compound thereof.

比较例1重复实施例1的过程,只是用纳米硅溶胶取代纳米材料复配物并与实施例1相同的丙烯酸酯乳液机械搅拌混拼。 Comparative Example 1 The procedure of Example 1 was repeated, except nanomaterials substituted compound was purified by silica nano acrylic emulsion and the same machine as in Example 1 was stirred Blending.

比较例2 Comparative Example 2

重复实施例2的过程,只是用纳米硅溶胶取代纳米材料复配物,与组成丙烯酸酯乳液的各组分一起聚合。 The procedure of Example 2 was repeated, except nanomaterials substituted compound was purified by silica nanometers, with each of the constituents polymerization of acrylic emulsion.

比较例3按实施例1丙烯酸酯乳液的配方和方法,制备丙烯酸酯乳液,不加任何纳米材料。 COMPARATIVE EXAMPLE 3 Example 1 formulation and acrylic emulsion, acrylic emulsion was prepared, without any nanomaterial.

实施例31、按实施例1的配方和方法制备纳米材料的复配物。 Example 31, prepared as described complex nanomaterials formulation and process of Example 1.

2、苯丙乳液的配方见表2。 2, styrene-acrylic emulsion formulation of Table 2.

表2 Table 2

3、改性乳液的制备。 3, the modified emulsion prepared.

除采用表2的单体代替实施例1表1的单体外,其余操作均同实施例1,制得的苯丙乳液,搅拌下加入已制得的纳米材料复配物,混合0.5小时得到复合纳米材料改性的苯丙乳液。 In addition to the monomers employed in Example 1 of Table 1 instead of the monomer in Table 2 embodiment, the remaining operations were the same as in Example 1, the obtained acrylic emulsion embodiment, has been added under stirring to prepare nanomaterials complex was mixed 0.5 hours to give styrene-acrylic emulsion modified nano composite material.

实施例41、按实施例1的相同的配方和方法制备纳米材料的复配物。 Example 41, Example compound was prepared in the same formulation and process nanomaterials 1.

2、苯丙乳液的配方与实施例3相同。 2, the same styrene-acrylic emulsion formulation in Example 3.

3、改性乳液的制备。 3, the modified emulsion prepared.

将2/3的去离子水和复配物加入反应器升温,温度达到84~88℃时,以下再按实施例3的乳液聚合方法在复配物存在下完成乳液聚合,得到复合纳米材料改性的苯丙乳液。 When 2/3 of deionized water and added to the reactor complex was heated, the temperature reached 84 ~ 88 ℃, then the emulsion polymerization process in Example 3 to complete the emulsion polymerization in the presence of the compound was changed to give Nanocomposites of styrene-acrylic emulsion.

比较例4重复实施例3的过程,只是用纳米硅溶胶取代纳米材料复配物,并与实施例3相同的丙苯乳液机械搅拌混拼。 Comparative Example 4 The procedure of Example 3 was repeated, except nanomaterials substituted compound was purified by silica nanometers, and in Example 3 of propyl styrene emulsion was stirred mechanically Blending.

比较例5重复实施例4的过程,只是用纳米硅溶胶取代纳米材料复配物,并与组成苯丙乳液的各组分一起聚合。 Comparative Example 5 The procedure of Example 4 was repeated, except nanomaterials substituted compound was purified by silica nano and polymerized together with the components of the composition styrene-acrylic emulsion.

比较例6按实施例3苯丙乳液的配方和方法制备苯丙乳液,不加任何纳米材料。 Comparative Example 6 Preparation of styrene-acrylic latex according to the formula and procedure of Example 3 is acrylic emulsion, without any nanomaterial.

上述实施例1~4和比较例1~6的乳液性能按下述方法检测,结果见表3。 1 to 4, emulsion properties and the above-described embodiments 1 to 6, Comparative Examples as follows, and the results are shown in Table 3.

表3 table 3

检验复合纳米材料改性的乳液的性能。 Performance test of the emulsion of modified nanocomposite.

1、贮存稳定性试验。 1, the storage stability test.

在约100ml的容器(玻璃或塑料制)中装入一定量(留有5%的空间)的待检样品并密封容器。 About 100ml was charged in a container (glass or plastic) in an amount (5% of the left space) sample to be tested and sealing the container. 将容器放入40°±2℃恒温箱中20小时,取出后在23±2℃放置3小时,再称重。 The vessel was placed in 40 ° ± 20 hours 2 ℃ incubator for 3 hours removed 23 ± 2 ℃, reweighed. 样品贮存前后相差不超过称量前重量的1%,打开容器,观察有无硬块、絮凝及分层现象。 The samples were stored before and after the phase difference is not more than 1% by weight of the pre-weighing, the container is opened, to observe whether the lumps, flocculation and stratification.

2、耐水性评价试验用60μm刮涂器将上述乳液涂覆在玻璃板上,在60℃干燥30分钟,再于常温放置48小时成膜。 2, the water resistance evaluation test The above emulsion was coated on a glass plate and dried at 60μm coater 60 ℃ 30 minutes and then at room temperature for 48 hours deposition. 将涂膜浸入水中,目视观察涂膜的起泡状况。 The coating film was immersed in water, blistering condition of the coating film was visually observed.

检验结果见表3由上述检验结果可知,本发明的复合纳米材料改性的乳液,贮存稳定性明显优于用单一纳米材料改性的乳液(比较例1、2、4和5),复合纳米材料改性的乳液耐水性明显优于未改性的乳液(比较例3和6)。 Test results in Table 3. From the above test results, the composite nano-modified material of the invention is an emulsion, the emulsion storage stability was significantly better than with single-modified nano-materials (Comparative Examples 2, 4 and 5), the composite nano emulsion of water-resistant material modification was superior emulsion (Comparative Examples 3 and 6) unmodified. 因此,本发明的改性乳液综合性能更好。 Accordingly, the modified emulsion of the invention better overall performance.

用本发明实施例1~4的改性乳液配制外墙涂料,其涂膜的耐水性、耐碱性和耐人工老化性均明显优于GB/T9755-2001优等品的指标。 Modified Examples 1 to 4 Emulsion exterior paint formulated with the embodiment of the present invention, the water resistance of the coating film, artificial aging resistance and alkali resistance were superior to GB / T9755-2001 Excellence indicators.

Claims (5)

1.一种复合纳米材料改性的乳液,它是用无机纳米材料改性丙烯酸酯类乳液,其特征在于:无机纳米材料是纳米氧化铝粉体和纳米硅溶胶的复配物,用量为250~2500重量份,纳米氧化铝粉体占纳米硅溶胶固体含量的5~30%;丙烯酸酯类乳液用量为2500重量份,乳液的固体含量为40±5%,上述百分数为重量百分数。 A modified nanocomposite emulsion, which is modified with an inorganic nanomaterials acrylate emulsion, wherein: the inorganic nanomaterial is a nano-alumina powder and the nano-silica complex was in an amount of 250 to 2500 parts by weight, nano-alumina powder from 5 to 30 percent solids silica sol nanometers; acrylate emulsion in an amount of 2500 parts by weight, the solid content of the emulsion was 40 ± 5%, the above percentages are by weight.
2.根据权利要求1所述的乳液,其特征在于:所述纳米氧化铝粉体粒径为5~50纳米;所述纳米硅溶胶的颗粒粒度为5~30纳米,固体含量为20~40%。 2. The emulsion according to claim 1, characterized in that: the nano-alumina powder particle diameter of 5 to 50 nanometers; nano particle size of the silica sol is 5 to 30 nm, solids content of 20 to 40 %.
3.根据权利要求1所述的乳液,其特征在于:所述丙烯酸酯类乳液为丙烯酸酯乳液、苯丙乳液、醋丙乳液中的一种或几种。 3. The emulsion according to claim 1, wherein: the acrylic emulsion as acrylic emulsion, styrene-acrylic latex, acrylic emulsion vinegar of one or more.
4.一种权利要求1乳液的制备方法,其特征在于:首先按配方比例将纳米氧化铝粉体和纳米硅溶胶混合,再进一步用超声波分散至分散体粒度为100~200nm得到复配物,然后按配方比例用复配物对丙烯酸酯类乳液进行改性即可。 Preparation of emulsion 1 4. A method as claimed in claim, wherein: the first by formula ratio nano-alumina and nano-powder silica sol, and then further dispersed using an ultrasonic dispersion particle size of 100 ~ 200nm was obtained compound, then modified according to the formula ratio of acrylate emulsion formulations were used.
5.根据权利要求4所述的制备方法,其特征在于:所述用复配物改性丙烯酸酯类乳液的方法是,在搅拌下将复配物加到已合成的丙烯酸酯类乳液中混拼完成改性,或者是将复配物加到反应器中,与组成丙烯酸酯类乳液的各组分,一起进行乳液聚合完成改性。 The production method as claimed in claim 4, wherein: the complex method was modified acrylic emulsion is under agitation was added to the compound synthesized acrylate emulsion mixed fight completed modification, or the complex was added to the reactor, with the components of the composition of the acrylic-based emulsion, the emulsion polymerization is completed with the modification.
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