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使用两性离子表面活性剂通过乳液聚合合成聚(甲基丙烯酸甲酯)纳米复合材料。

Synthesis of poly(methyl methacrylate) nanocomposites via emulsion polymerization using a zwitterionic surfactant.

作者信息

Meneghetti Paulo, Qutubuddin Syed

机构信息

Department of Chemical Engineering, Case Western Reserve University, University Circle, Cleveland, Ohio 44106, USA.

出版信息

Langmuir. 2004 Apr 13;20(8):3424-30. doi: 10.1021/la0357099.

Abstract

The synthesis of nanocomposites via emulsion polymerization was investigated using methyl methacrylate (MMA) monomer, 10 wt % montmorillonite (MMT) clay, and a zwitterionic surfactant octadecyl dimethyl betaine (C18DMB). The particle size of the diluted polymer emulsion was about 550 nm, as determined by light scattering, while the sample without clay had a diameter of about 350 nm. The increase in the droplet size suggests that clay was present in the emulsion droplets. X-ray diffraction indicated no peak in the nanocomposites. Transmission electron microscopy showed that emulsion polymerization of MMA in the presence of C18DMB and MMT formed partially exfoliated nanocomposites. Differential scanning calorimetry showed an increase of 18 degrees C in the glass transition temperature (Tg) of the nanocomposites. A dynamic mechanical thermal analyzer also verified a similar Tg increase, 16 degrees C, for the partially exfoliated nanocomposites over poly(methyl methacrylate) (PMMA). Thermogravimetric analysis indicated a 37 degrees C increase in the decomposition temperature for a 20 wt % loss. A PMMA nanocomposite with 10 wt % C18DMB-MMT was also synthesized via in situ polymerization. This nanocomposite was intercalated and had a Tg 10 degrees lower than the emulsion nanocomposite. The storage modulus of the partially exfoliated emulsion nanocomposite was superior to the intercalated structure at higher temperatures and to the pure polymer. The rubbery plateau modulus was over 30 times higher for the emulsion product versus pure PMMA. The emulsion technique produced nanocomposites of the highest molecular weight with a bimodal distribution. This reinstates that exfoliated structures have enhanced thermal and mechanical properties over intercalated hybrids.

摘要

采用甲基丙烯酸甲酯(MMA)单体、10 wt%蒙脱石(MMT)黏土和两性离子表面活性剂十八烷基二甲基甜菜碱(C18DMB),通过乳液聚合研究了纳米复合材料的合成。通过光散射测定,稀释后的聚合物乳液粒径约为550 nm,而不含黏土的样品直径约为350 nm。液滴尺寸的增加表明乳液滴中存在黏土。X射线衍射表明纳米复合材料中没有峰。透射电子显微镜显示,在C18DMB和MMT存在下MMA的乳液聚合形成了部分剥离的纳米复合材料。差示扫描量热法表明,纳米复合材料的玻璃化转变温度(Tg)升高了18℃。动态机械热分析仪也证实,部分剥离的纳米复合材料比聚甲基丙烯酸甲酯(PMMA)的Tg有类似的升高,为16℃。热重分析表明,在失重20 wt%时,分解温度升高了37℃。还通过原位聚合法合成了含有10 wt% C18DMB-MMT的PMMA纳米复合材料。该纳米复合材料是插层型的,其Tg比乳液纳米复合材料低10℃。在较高温度下,部分剥离的乳液纳米复合材料的储能模量优于插层结构和纯聚合物。乳液产物的橡胶态平台模量比纯PMMA高30倍以上。乳液技术制备出了具有双峰分布的最高分子量的纳米复合材料。这再次表明,与插层杂化物相比,剥离结构具有增强的热性能和机械性能。

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