【作者】 范忠雷；

【导师】 刘大壮； 王键吉；

【作者基本信息】 郑州大学 ， 化学工艺， 2003， 博士

【摘要】 聚丙烯具有优良的综合性能和独特的性价比，使其在生产和应用中得到了很大的发展。1995年聚丙烯产量仅次于聚乙烯和聚氯乙烯，居第三位，2000年聚丙烯产量达2820万吨，超过聚氯乙烯位居第二。聚丙烯广泛用于薄膜、纤维和注塑制品，尤其随着汽车工业的快速发展，使得对聚丙烯制品的表面性能和外观提出了更高的要求，但是由于一般涂料树脂对聚丙烯附着力很差，而氯化聚丙烯对聚丙烯塑料具有优良的附着力，因此汽车工业的需要就成为研究氯化聚丙烯的重要推动力之一。 本文针对氯化聚丙烯目前研究的薄弱环节，对氯化聚丙烯结构与性能关系进行了系统研究，用激光光散射法测定了氯化聚丙烯和CPP-g-MAH接枝物的分子量，Z均方根旋转半径和第二维利系数等基本物性参数。通过窄级分氯化聚丙烯的分子量和特性粘数的测定，得到了氯化聚丙烯在甲苯溶液中、298.15K条件下的Mark-Houwink方程为[η]=0.0174M^0.6919。在此基础上，进一步拟合出Z均方根旋转半径和重均分子量的关系式，计算了氯化聚丙烯在甲苯溶液中的均方根末端距和分子的柔性参数，得到氯化聚丙烯在甲苯溶液中是柔性分子，以无规线团的形式存在。 建立了一套精确测定聚合物溶解度参数的实验装置。用此装置可以准确测定高聚物在指定温度下的溶解度参数，并且可以动态追踪整个实验过程，形象地给出聚合物溶解度参数范围。在此基础上，研究了氯化聚丙烯分子量、温度和马来酸酐接枝率对溶解度参数的影响。测定结果表明分子量对氯化聚丙烯分级样品的溶解度参数影响不大。随温度的升高，可以显著改善氯化聚丙烯对非溶剂的容忍度，表现在溶解度参数上为氯化聚丙烯的溶解度参数范围扩大。随接枝率增加，CPP-g-MAH接枝物对极性溶剂的容忍度逐渐增大，表明通过接枝马来酸酐可以提高氯化聚丙烯的极性，改善与短油度醇酸树脂的混容性。 用称重法测定了氯化等规聚丙烯和其接枝物在298.15K下，不同溶剂中的溶解度。氯化聚丙烯溶解性能实验表明：氯化聚丙烯属于弱极性物质。在溶度参数接近时，一般弱极性溶剂为良溶剂，中等极性溶剂为微溶溶剂。用溶解度结果对CPP-g-MAH接枝物的极性进行分析，认为随着马来酸酐的引入，氯化聚丙烯的极性逐渐增强。并用一维溶解度参数、三维溶解度参数和类溶解度参数对氯化聚丙 郑州大学博士学位论文烯和接校物的溶解性能进行了研究，得到聚合物的溶解性能图，为其选择合适溶剂或配制混合溶剂提供依据。 用不同方法研究了氯化聚丙烯及其接校物与常用涂料树脂的相容性。稀溶液粘度法（a判据和p判据）预测结果是氯化聚丙烯和石油树脂相容，和丙烯酸树脂不相容性，和短油度醇酸树脂的相容性与配比有关。对氯化聚丙烯和短油度醇酸树脂的相容性进行判别，发现344“短油度醇酸树脂在树脂中的含量小于0．5时，a川，p川，表示M者相容；含量大于0．5时，um，p们，表示M者不相容。用红外光谱法考察了该类共混物的羟基位移情况，认为短油度醇酸树脂的羟基和氯化聚丙烯链上氯原子的相互作用促进了两种树脂间的相容性。 在此基础上，用涂膜光泽度和透光度法研究了一系列氯化聚丙烯和醇酸树脂混合物涂膜的性能，发现涂膜的光泽度和透光度可用来表征聚合物之间的相容程度。所得的宏观结果与稀溶液粘度法预测的结果相当一致。 用正交实验考察了石油树脂与CPP的比例，G漆在总量中的百分含量，烘干温度三个因素对氯化聚丙烯涂膜光泽度的影响，实验结果表明烘干温度对氯化聚丙烯涂膜的光泽度有显著影响，当烘干温度达到CPP的软化点时，涂膜光泽度显著改善，因此，该涂膜的适宜烘干温度在333K～353K之间。这个结果对于聚丙烯涂料的工艺条件优化具有一定的意义。更多还原

【Abstract】 Due to good integrate properties and special ratio of its properties to price, polypropylene(PP) has gained great development in the production and application. Its total output stand the third only behind polyethylene and PVC in 1995, and the second in 2000 which output, up to 28.2million tons, exceed PVC yield. Polypropylene was wildly used in the field of film, fibre and plastic produce. Because of its good adhesion properties to PP, Chlorinated polypropylene application gets more and more abroad with the rapid development of polypropylene in the fields, especially in automobile industry. Therefore, the need of the automobile industry to chlorinated polypropylene (CPP) turn into one of important impetuses to study the properties of CPP.Aim at the weakness of CPP property research at present, systemic research about the relation between the structure and properties of CPP was carried through in the thesis. Molecular weight, the mean square radius of gyration and the second Virial coefficient for CPP and maleic anhydride grafted chlorinated polypropylene (CPP-g-MAH) have been obtained by laser-light scattering. The Mark-Houwink Equation of CPP in the toluene at 298.15K was obtained, which isas follow: [r]] = 0.0174M ?919 At the base of data of the mean square radius of Z gyration andthe actual values of Mw, the relationships between the molecular parameters were imitated and the mean square end distance and molecule flexible parameter of CPP were calculated, which show molecule of CPP in the toluene is flexible and exists in the form of random coil.Laser monitoring observation system was set up to exactly determine the solubility parameters of polymer in the special temperature. In comparison with the classical method of turbidity, the method is better and worth getting applications wildly because of its precision, dynamic pursuing the process of the whole experiment and getting visually range of solubility parameter. The effects of molecular weight, temperature and the maleic content of CPP-g-MAH on the solubility parameters were researched by the laser-turbidity method. The results show that the upper limit of the solubility parameter of CPP gets big gradually and the lower limit falls down with the increasing temperature, the solubility parameter of CPP keeps constant with the increasing molecular weight and the solubility parameter and polarity of CPP-g-MAH are increasing by grafting maleic anhydride to CPP and compatibility of chlorinated polypropylene with alkyd resin is improved with the grafting yield of maleic anhydride increasing.The solubility of CPP and five CPP-g-MAH materials with different maleic content at 298.15K were determined by the weighing method. The studies of the dissolving properties of CPP in various solvents show that CPP is weakly polar material, and the dissolving abilities of the weakly polar solvents are good to CPP and ones of the moderately polar solvents are slightly dissolving at the case of the similar solubility parameters. At the same time, the dissolving properties of CPP were also discussed with three dimensions of the solubility parameter and a new two-dimensional solubility parameter. Also, the result that polarity of CPP-g-MAH is increasing by grafting maleic anhydride to CPP is proved by the solubility.Miscibility of CPP with other common coating resins was researched by means of several methods. The miscibility of 344# Acrylic resin/CPP. Petroleum resm/CPP and 344# alkyd resin/CPP systems in the specified mixing ratios was investigated by the dilute solution viscometry. The criteria a and P show that Petroleum resin/CPP blends are miscible, Acrylic Resin/CPP blends are immiscible, and the 344 alkyd resin/CPP blends are miscible when the weight percentage of 344* alkyd resin to CPP is less 50%(w%), and immiscible within the ranges of greater than 50%(w%), which is consistent with the results of the stability of the mixtures, the clarity and the glossiness of filmsMiscibility of CPP with 344" alkyd resin in the specified mixing ratios has a更多还原