纳米SiO_2/苯丙含氟核壳无皂乳液的制备及其性能研究
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摘要
本文论述了乳液聚合、苯丙乳液及纳米SiO2粒子的特点,概括了最近乳液聚合改性研究的现状,研究了含氟苯丙核壳无皂乳液有关的制备、性能和纳米SiO2对其的改性,并进行了表征,试图研制性能优良的纳米SiO2改性含氟苯丙核壳无皂乳液。
以烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵(SE-10N)为反应性乳化剂,甲基丙烯酸六氟丁酯(F6MBA)为助稳定剂,通过控制聚合工艺,进行预乳化种子乳液核壳无皂聚合,合成了一种以苯乙烯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸共聚为核,苯乙烯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸六氟丁酯共聚为壳的硬核软壳型含氟苯丙无皂乳液。研究了聚合工艺、核壳质量比及软硬单体配比对单体转化率和乳液综合性能的影响,反应性乳化剂SE-10N用量对乳胶膜耐水性的影响,通过比较所制备的含氟苯丙核壳无皂乳液与普通乳液的胶膜的耐水性知：本实验所研制的含氟苯丙核壳无皂乳液的耐水性明显高于普通乳液。研究结果还表明：反应性乳化剂SE-10N的质量分数为2.0%,F6MBA的量为0.2g,聚合温度80～85℃,反应时间4～6h,制备的乳液综合性能较好。用IR表征了其结构,并用TEM观察到乳胶粒子的形态为比较均匀的球形核壳结构,DSC的分析也证明了核壳结构的形成。
采用溶胶-凝胶法,以正硅酸乙酯(TEOS)为制备无机纳米SiO2的前躯体,对以阴离子反应性乳化剂SE-10N与苯丙乳液聚合的乳液改性,讨论了纳米SiO2含量对材料力学性能的影响。在纳米SiO2和SE-10N的质量分数分别为5.0%和2.0%,聚合温度85～90℃,反应时间4～6h条件下,研制出一种壳含氟、核含纳米Si02的纳米水性壳软核硬型无皂氟碳聚合物／无机纳米复合乳液。通过IR、TEM及DSC对聚合物的结构和形态进行了表征。其与常规乳液相比,各项性能均有明显提高,本工作为研究开发新型复合材料提供了一定的实验基础与理论借鉴。
The features of emulsion polymerization, polystyrene acrylic emulsion and namo-silica, and recent progress on modification of polystyrene acrylic emulsion were reviewed in this thesis. The preparation and properties of core-shell emulsion-free polystyrene-acrylic emulsion were discussed, It is expected that the excellent namo-SiO2 contenting fluorine core-shell emulsion-free polystyrene-acrylate composites emulsion can be synthesized.The present studies could be divided into the following two parts.
First, a fluorine contented emulsion-free polystyrene-acrylate emulsion was synthesized by per-emulsified technology with SE-10N as the emulsifier, the fluorine containing methyl acrylate as modifier. The core-shell emulsion-free polystyrene acrylate emulsion with (St+MAM+BA+MAA) as the core and (St+BA+MAA+F) as the shell was synthesized. The effect of factors such as polymerization process, temperature, the effect of the mass ratio of core-shell, the ratio of soft and hard monomer, and the amount of reactive emulsifier on the multiple properties of the latex film were studied. The water resistance of soap-free core-shell emulsion was better compared with the general core-shell emulsion. It was shown that the comprehensive properties of the emulsion and its film were better when the amount of fluorine-containing methyl acrylate was 0.2g, the quality of reactive emulsifier was 2.0%, the polymerization temperature at 80～85℃and the reaction time was 4～6 hours. The structure of the copolymer was characterized by IR. The positive core-shell structure was observed by TEM, DSC analysis also shows the core-shell structure was formed.
Second, the namo-SiO2/polystyrene acrylic emulsion composites were successfully synthesized by a sol-gel method using tetraethylorthosilicate (TEOS) as the silica precursor, the non-soap copolymer emulsion of namo-silica and styrene-acrylate was synthesized by per-emulsified technology.with namo-silica, styrene, methyl acrylate monomers, APS as the initiator, SE-10N as the emulsifier. The model and amount of reactive emulsifier as well as the namo-silica amount on the comprehensive properties of the emulsion and its film were investigated. The structure of the copolymer was characterized by IR, TEM and DSC. The suitable polymerization process as follows:by pre-emulsification process, the quality score of reactive emulsifier and namo-silica was 2.0% and 5.0% respectively, the reaction temperature was 85～90℃, the reaction time was 4～6 hours. Under this condition, the comprehensive properties of the emulsion and its film were better.
以烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵(SE-10N)为反应性乳化剂,甲基丙烯酸六氟丁酯(F6MBA)为助稳定剂,通过控制聚合工艺,进行预乳化种子乳液核壳无皂聚合,合成了一种以苯乙烯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸共聚为核,苯乙烯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸六氟丁酯共聚为壳的硬核软壳型含氟苯丙无皂乳液。研究了聚合工艺、核壳质量比及软硬单体配比对单体转化率和乳液综合性能的影响,反应性乳化剂SE-10N用量对乳胶膜耐水性的影响,通过比较所制备的含氟苯丙核壳无皂乳液与普通乳液的胶膜的耐水性知：本实验所研制的含氟苯丙核壳无皂乳液的耐水性明显高于普通乳液。研究结果还表明：反应性乳化剂SE-10N的质量分数为2.0%,F6MBA的量为0.2g,聚合温度80～85℃,反应时间4～6h,制备的乳液综合性能较好。用IR表征了其结构,并用TEM观察到乳胶粒子的形态为比较均匀的球形核壳结构,DSC的分析也证明了核壳结构的形成。
采用溶胶-凝胶法,以正硅酸乙酯(TEOS)为制备无机纳米SiO2的前躯体,对以阴离子反应性乳化剂SE-10N与苯丙乳液聚合的乳液改性,讨论了纳米SiO2含量对材料力学性能的影响。在纳米SiO2和SE-10N的质量分数分别为5.0%和2.0%,聚合温度85～90℃,反应时间4～6h条件下,研制出一种壳含氟、核含纳米Si02的纳米水性壳软核硬型无皂氟碳聚合物／无机纳米复合乳液。通过IR、TEM及DSC对聚合物的结构和形态进行了表征。其与常规乳液相比,各项性能均有明显提高,本工作为研究开发新型复合材料提供了一定的实验基础与理论借鉴。
The features of emulsion polymerization, polystyrene acrylic emulsion and namo-silica, and recent progress on modification of polystyrene acrylic emulsion were reviewed in this thesis. The preparation and properties of core-shell emulsion-free polystyrene-acrylic emulsion were discussed, It is expected that the excellent namo-SiO2 contenting fluorine core-shell emulsion-free polystyrene-acrylate composites emulsion can be synthesized.The present studies could be divided into the following two parts.
First, a fluorine contented emulsion-free polystyrene-acrylate emulsion was synthesized by per-emulsified technology with SE-10N as the emulsifier, the fluorine containing methyl acrylate as modifier. The core-shell emulsion-free polystyrene acrylate emulsion with (St+MAM+BA+MAA) as the core and (St+BA+MAA+F) as the shell was synthesized. The effect of factors such as polymerization process, temperature, the effect of the mass ratio of core-shell, the ratio of soft and hard monomer, and the amount of reactive emulsifier on the multiple properties of the latex film were studied. The water resistance of soap-free core-shell emulsion was better compared with the general core-shell emulsion. It was shown that the comprehensive properties of the emulsion and its film were better when the amount of fluorine-containing methyl acrylate was 0.2g, the quality of reactive emulsifier was 2.0%, the polymerization temperature at 80～85℃and the reaction time was 4～6 hours. The structure of the copolymer was characterized by IR. The positive core-shell structure was observed by TEM, DSC analysis also shows the core-shell structure was formed.
Second, the namo-SiO2/polystyrene acrylic emulsion composites were successfully synthesized by a sol-gel method using tetraethylorthosilicate (TEOS) as the silica precursor, the non-soap copolymer emulsion of namo-silica and styrene-acrylate was synthesized by per-emulsified technology.with namo-silica, styrene, methyl acrylate monomers, APS as the initiator, SE-10N as the emulsifier. The model and amount of reactive emulsifier as well as the namo-silica amount on the comprehensive properties of the emulsion and its film were investigated. The structure of the copolymer was characterized by IR, TEM and DSC. The suitable polymerization process as follows:by pre-emulsification process, the quality score of reactive emulsifier and namo-silica was 2.0% and 5.0% respectively, the reaction temperature was 85～90℃, the reaction time was 4～6 hours. Under this condition, the comprehensive properties of the emulsion and its film were better.
引文
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[5]Rui,Z.;Yuan,H.;Jia,Y.X.Polymer Degradation and Stability.2004,85,583.
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[17]刘国军,张桂霞,曾汉民.聚丙烯酸酯纳米SiO2有机-无机复合压敏胶乳液的制备[J].高分子材料科学与工程,2007,23(2)：54-57.
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[19]Castel V V,Vitaa C D.anostructured hybrid materials from aqueous polymer dispersions [J]. Advances in Colloid and Interface Science,2004,108～109:167-185.
[20]Zhang S W,Zhou S X,Weng Y M, et al. Synthesis of SiO2/Polystyrene Nanocomposite Particles via Miniemulsion Polymerization [J]. Langmuir,2005,21: 2124-2128.
[21]周诗彪,张维庆,郝爱平等,MA／AA无皂乳液聚合改性纳米Si02,湖南文理学院学报(自然科学版),2008,20(2)：41-44
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