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The Influence of Oxide Nanoparticles on the Kinetics of Free Radical Methyl Methacrylate Polymerization in Bulk

机译:氧化物纳米颗粒对自由基甲基丙烯酸甲酯聚合反应动力学的影响

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A series of poly(methyl methacrylate) (PMMA) nano-composites were synthesized using free radical polymerization in bulk, by addition of 1 vol% of oxide nanoparticles (silica, alumina, and titania), differing in the nature and type. The influence of nanofiller presence on the kinetics of methyl methacrylate (MMA) free radical polymerization was investigated. For this purpose, the kinetic model that includes the contribution from the first-order reaction and the autoaccelera-tion was applied on data obtained following the isothermal polymerization at 70°C by differential scanning calorimetry (DSC). The effect of the size and the surface nature of nanofillers on the interfacial layer thickness (d), as well as the influence of d on the glass transition temperature (T_g) of PMMA hybrid materials was studied. It was found that hydrophilic particles accelerated the initiator decomposition and affected the monomer polymerization on the surface, which caused the formation of thicker interfacial layer compared to the one around hydrophobic fillers. The addition of smaller nanoparticles size decreased the glass transition temperature of pure poly(methyl metacry-late). The linear increase of PMMA T_g value with increasing the polymeric interfacial layer was determined. The T_g values of pure PMMA and PMMA nano-composite with d of 1.4 nm were estimated to be the same.
机译:通过自由基聚合,通过添加性质和类型不同的1%(体积)的氧化物纳米颗粒(二氧化硅,氧化铝和二氧化钛),合成了一系列的聚甲基丙烯酸甲酯(PMMA)纳米复合材料。研究了纳米填料的存在对甲基丙烯酸甲酯(MMA)自由基聚合动力学的影响。为此,将包括一级反应和自加速作用的动力学模型应用于通过差示扫描量热法(DSC)在70°C等温聚合后获得的数据。研究了纳米填料的尺寸和表面性质对界面层厚度(d)的影响,以及d对PMMA杂化材料的玻璃化转变温度(T_g)的影响。发现亲水性颗粒加速了引发剂分解并影响了表面上的单体聚合,与疏水性填料周围的一层相比,亲水性颗粒导致了较厚的界面层的形成。较小纳米颗粒尺寸的添加降低了纯聚甲基丙烯酸甲酯的玻璃化转变温度。确定了PMMA T_g值随聚合物界面层的增加而线性增加。 d值为1.4 nm的纯PMMA和PMMA纳米复合材料的T_g值估计相同。

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