纳米粒子的制备、表面修饰及PVC、纤维素的改性
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摘要
论文的工作主要分为四个部分进行：
第一部分，高分子网络法制备纳米粒子。采用羟丙基甲基纤维素作为空间分散剂制备纳米ZnO，和没加入空间分散剂制备的纳米ZnO相比，粒径小，不易团聚，并且在紫外-可见光范围内有较强的吸收，并还研究了在制备过程中添加不同量的羟丙基甲基纤维素对纳米ZnO粒径的影响。
第二部分，纤维素的接枝共聚物的合成。采用氧化-还原引发体系。引发甲基丙烯酸甲酯和羟丙基甲基纤维素发生接枝共聚反应。研究了接枝物在不同溶剂中溶解能力，同时比较了它们的热性能，发现接枝物的热分解温度比HPMC和PMMA有所提高，本论文还探讨了反应机理。
第三部分，纳米ZnO、TiO2的表面修饰、表征及机理探讨。采用非离子型表面活性剂或复合表面活性剂先对纳米粒子进行表面处理，然后在其表面接枝上MMA或MMA和BA，得到表面具有亲油性的纳米复合粒子。FT-IR和TEM表明在纳米ZnO、TiO2表面有接枝层存在。TG研究了复合粒子的热性能随包覆率的变化，同时还对复合粒子的紫外吸收能力进行了测定，表明复合粒子在紫外-可见区域具有较强的紫外吸收。可应用于涂料、化妆品等领域。运用正交设计法对纳米复合粒子制备过程中的各因素进行了规律性的研究。同时对纳米粒子表面修饰机理进行了探讨。
第四部分，PVC的填充改性。用表面改性的纳米ZnO、TiO2复合粒子填充PVC，使PVC的韧性和强度同时提高，并根据实验数据，建立数学模型，得出了实验最佳条件。
The paper is composed of the following four parts:
In the first part, nanopaticles were prepared by macromolecule network methods. Utilizing Hydroxypropyl methyl cellulose (HPMC) as steric stabilizer, the reaction precursors [Zn2(OH)2CO3·HPMC] were synthesized. Comparing to ZnO nanoparticles prepared in absence with HPMC, ZnO nanoparticles obtained by calcinating the precursor [Zn2(OH)2CO3·HPMC] have higher dispersibility, smaller size and are more difficult to agglomerate, and ZnO nanoparticles have a strong absorbance of UV wave. In addition, effect of different concentration of HPMC polymer on the nanoparticles diameters was studied during the synthesized procession.
In the second part, celluloses grafting copolymer were synthesized. Using K2S2O8-NaHSO3 initiation system, the graft copolymerization of methyl methacrylate and HPMC was carried out. Solution power of graft copolymer in the different solvents was studied. By comparing graft copolymer with HPMC and PMMA, graft copolymer decomposition temperature is higher than that of HPMC and PMMA. Reaction mechanisms were yet elucidated in the article.
In the third part, we investigated the different conditions, characterization and mechanism of nano-ZnO, TiO2 surface modification. First, nanoparticles surface was treated by nonionic surfactant or composite surfactant, and then, MMA or MMA and BA were grafted at the nanoparticle surface. We got hydrophobic property of nanocomposite particles surface. FT-IR spectrum and TEM photograph showed that MMA or MMA and BA had been grafted at the nanoprticle surface. Interrelation between thermal property and coating efficiency of nanocomposite particles were studied by TG, and its’ adsorbing ultraviolet ability detected by UV spectrophotometer showed that nanocomposite particles have a strong absorbance in the UV region. so, it can been applied in the cosmetics，coating, et al. Using orthogonal design method. The effects of different factors on the adsorption efficiency
and coating efficiency were studied. At the same time, the surface modification mechanism was preliminarily elucidated.
In the fourth part, mechanical properties of PVC were changed by filling. Surface modified nano- ZnO, TiO2 composite particles were added into PVC. The results showed that the reinforcing and toughening of PVC had all increased. We established the mathematics model on the basis of experiment data, and then, obtained the best experiment conditions.
第一部分，高分子网络法制备纳米粒子。采用羟丙基甲基纤维素作为空间分散剂制备纳米ZnO，和没加入空间分散剂制备的纳米ZnO相比，粒径小，不易团聚，并且在紫外-可见光范围内有较强的吸收，并还研究了在制备过程中添加不同量的羟丙基甲基纤维素对纳米ZnO粒径的影响。
第二部分，纤维素的接枝共聚物的合成。采用氧化-还原引发体系。引发甲基丙烯酸甲酯和羟丙基甲基纤维素发生接枝共聚反应。研究了接枝物在不同溶剂中溶解能力，同时比较了它们的热性能，发现接枝物的热分解温度比HPMC和PMMA有所提高，本论文还探讨了反应机理。
第三部分，纳米ZnO、TiO2的表面修饰、表征及机理探讨。采用非离子型表面活性剂或复合表面活性剂先对纳米粒子进行表面处理，然后在其表面接枝上MMA或MMA和BA，得到表面具有亲油性的纳米复合粒子。FT-IR和TEM表明在纳米ZnO、TiO2表面有接枝层存在。TG研究了复合粒子的热性能随包覆率的变化，同时还对复合粒子的紫外吸收能力进行了测定，表明复合粒子在紫外-可见区域具有较强的紫外吸收。可应用于涂料、化妆品等领域。运用正交设计法对纳米复合粒子制备过程中的各因素进行了规律性的研究。同时对纳米粒子表面修饰机理进行了探讨。
第四部分，PVC的填充改性。用表面改性的纳米ZnO、TiO2复合粒子填充PVC，使PVC的韧性和强度同时提高，并根据实验数据，建立数学模型，得出了实验最佳条件。
The paper is composed of the following four parts:
In the first part, nanopaticles were prepared by macromolecule network methods. Utilizing Hydroxypropyl methyl cellulose (HPMC) as steric stabilizer, the reaction precursors [Zn2(OH)2CO3·HPMC] were synthesized. Comparing to ZnO nanoparticles prepared in absence with HPMC, ZnO nanoparticles obtained by calcinating the precursor [Zn2(OH)2CO3·HPMC] have higher dispersibility, smaller size and are more difficult to agglomerate, and ZnO nanoparticles have a strong absorbance of UV wave. In addition, effect of different concentration of HPMC polymer on the nanoparticles diameters was studied during the synthesized procession.
In the second part, celluloses grafting copolymer were synthesized. Using K2S2O8-NaHSO3 initiation system, the graft copolymerization of methyl methacrylate and HPMC was carried out. Solution power of graft copolymer in the different solvents was studied. By comparing graft copolymer with HPMC and PMMA, graft copolymer decomposition temperature is higher than that of HPMC and PMMA. Reaction mechanisms were yet elucidated in the article.
In the third part, we investigated the different conditions, characterization and mechanism of nano-ZnO, TiO2 surface modification. First, nanoparticles surface was treated by nonionic surfactant or composite surfactant, and then, MMA or MMA and BA were grafted at the nanoparticle surface. We got hydrophobic property of nanocomposite particles surface. FT-IR spectrum and TEM photograph showed that MMA or MMA and BA had been grafted at the nanoprticle surface. Interrelation between thermal property and coating efficiency of nanocomposite particles were studied by TG, and its’ adsorbing ultraviolet ability detected by UV spectrophotometer showed that nanocomposite particles have a strong absorbance in the UV region. so, it can been applied in the cosmetics，coating, et al. Using orthogonal design method. The effects of different factors on the adsorption efficiency
and coating efficiency were studied. At the same time, the surface modification mechanism was preliminarily elucidated.
In the fourth part, mechanical properties of PVC were changed by filling. Surface modified nano- ZnO, TiO2 composite particles were added into PVC. The results showed that the reinforcing and toughening of PVC had all increased. We established the mathematics model on the basis of experiment data, and then, obtained the best experiment conditions.
引文
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