【作者】 唐四叶；

【导师】 刘大壮； 王键吉；

【作者基本信息】 郑州大学 ， 化学工艺， 2006， 博士

【摘要】 聚丙烯具有优良的综合性能，在工业生产和日常生活中得到广泛应用。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具有优良的附着力，因此，聚丙烯的广泛应用就成为研究氯化聚丙烯的推动力。本文针对氯化聚丙烯理论研究欠缺的薄弱环节，对氯化聚丙烯在溶液中的体积性质、粘度性质、溶解度参数等热力学性质及超声降解动力学进行了深入系统地研究，具有重要的学术理论意义和工程应用前景。用沉淀分级方法对氯含量为30％的氯化聚丙烯进行分级，得到5种窄分子量的级分，测定了氯化聚丙烯的不同级分与不同溶剂组成的二元混合物溶液的密度，在溶剂一定、浓度一定、温度一定时，不同级分氯化聚丙烯溶液的密度是相同的，不受分子量及其分布的影响。在此基础上，计算了氯化聚丙烯链节在溶液中的表观摩尔体积、标准偏摩尔体积和偏摩尔体积，并与溶剂分子的体积进行对比，确定了氯化聚丙烯链节的组成为丙烯二聚体为母体，表达式为C₆H₁₁Cl。为Flory-Huggins晶格理论提供了极其宝贵的数据。实验测定了298.15K、308.15K和318.15K温度下，氯化聚丙烯与甲苯、四氢呋喃、氯仿、四氯化碳、二甲苯和丁酮组成的二元混合物6种浓度的密度。该系列数据为氯化聚丙烯工程设计和研究提供了基础数据。用乌氏粘度计测定了不同温度下，浓度在10％以下6种氯化聚丙烯溶液的粘度，证明所考察的氯化聚丙烯溶液均为牛顿流体。考察了浓度、温度和分子量对溶液粘度的影响，建立了相关数学模型，确定了模型参数。计算了实验温度范围内氯化聚丙烯溶液的流动活化能。为工程设计中混合和流动条件的选取提供了依据，为溶液中分子间相互作用的研究奠定了基础。分别对五种浓度氯化聚丙烯甲苯溶液进行超声辐照，得到了低分子量的氯化聚丙烯。降解前后氯化聚丙烯分子结构、氯含量及在溶液中的存在状态均没有发生改变，氯化聚丙烯分子断裂位置在C-C键。在此基础上，考察了降解后氯化聚丙烯的分子量和特性粘数，发现文献中的Mark-Houwink方程[η]=0.017M^0.6919也适用于超声降解后的氯化聚丙烯，扩大了该方程的使用范围。测定了超声降解得到的不同分子量的氯化聚丙烯的相对溶解度。进而提出了一个判断氯化聚丙烯可溶溶剂与不可溶溶剂的溶解度新标准：相对溶解度增加的溶剂为可溶溶剂；分子量降低后溶解度不变的溶剂为不可溶溶剂。对于氯化聚丙烯来说，这种判别方法所得结果与客观事实及Flory-Huggins高分子溶液理论和Hansen、Lieberman、Funasaka所用标准的结果是一致的。依据本文提出的新标准，计算了氯化聚丙烯的三维溶解度参数，并用浊度法进行了验证。从热力学角度详细讨论了温度、聚合物浓度和聚合物与溶剂之间的相互作用参数对聚合物溶解过程的影响。氯化聚丙烯三维溶解度参数的确定为氯化聚丙烯热力学数据增添了新的内容，也为氯化聚丙烯的溶剂选择提供了依据。用数据拟合方法求取了超声降解动力学方程中的极限分子量和速率常数，实验证明该方法是可行的。考察了常用超声降解动力学方程对氯化聚丙烯实验数据的处理结果，发现处理结果并不满意，于是提出了一个新的聚合物超声降解二级动力学方程式，1／(M_t-M_lim)-1／(M_o-M_lim)=kt，氯化聚丙烯甲苯溶液的超声降解服从该动力学方程。详细考察了浓度对氯化聚丙烯降解反应速率常数和极限分子量的影响。该方程为聚合物超声降解动力学作了新的补充。用收集到的41组聚合物超声降解文献数据验证了常用和新提出的动力学方程的普适性，发现所有数据均可用一级或新提出的二级动力学方程处理，进而对聚合物超声降解动力学进行了归纳，得出了一般化的表达式：-dM_t／dt=k(M_t-M_lim)ⁿ，n=1或=2。认为超声降解动力学可以用统一的GPLE方程式表示。更多还原

【Abstract】 Due to good integrate properties, polypropylene（PP） has been widely used in industry and our daily life. The adhesion property of chlorinated polypropylene（CPP） to PP is better than other coating resins. Therefore, the abroad application of PP turns into the impetuses to study the properties of CPP.Aim at the weakness of CPP property research at present, systemic studies to volume properties, viscosity properties, solubility parameter and other thermodynamic properties as well as ultrasonic degradation kinetics of CPP were carried through in the thesis. These studies have a great science and applied significance for CPP.The CPP was separated into five fractions using fractional precipitations by solvent/nonsolvent technique. Densities for binary mixtures of five fractionated and unfractionated CPP which contains a mass fraction of 30 % chlorine with solvents were determined. At a fixed temperature, concentration and solvent, the densities for binary mixtures of fractionated and unfractionated CPP with solvents have the same value. The width of molecular weight distribution of CPP does not affect the densities of these mixtures. Based on this, the apparent molar volumes, standard partial molar volumes and partial molar volumes of CPP repeat unit have been calculated. Comparing with the molecular volumes of solvents, the repeat unit structure of CPP, C₆H₁₁Cl, has been determined. This result supplies valuable data for Flory-Huggins lattice theory.Densities for binary mixtures of CPP which contains a mass fraction of 30 % chlorine with toluene, tetrahydrofuran, chloroform, carbon tetrachloride, xylene and 2-butanone were determined at temperatures from （298.15 to 318.15） K. This systemic data supply basic data for project design and research of CPP.The viscosities of binary mixtures of CPP with solvents at 1%, 2%, 3%, 4%, 5% and 10% concentrations were measured using Ubbelohde capillary viscometer. It was found that all mixtures showed Newtonian flow. The effects of concentration, temperature, and molecular weight on viscosity have been studied. Flow activation energy of CPP solution was calculated in the experimental temperature range. These results offer references for selection of flow conditions and study of interaction between molecules.Ultrasonic irradiation was carried out for CPP toluene solutions at five concentrations. CPP with low molecular weight was obtained. The molecule structure, the chlorine content and the configuration of molecules in toluene solution don’t change. This indicates that the molecules of CPP break at carbon-carbon bond. Molecular weight and intrinsic viscosity of degraded CPP were measured. It is found that the Mark-Houwink equation,[η]=0.017M^0.6919, is also suitable for degraded CPP. Its application range is enlarged.Relative solubilities of CPP with different molecular weights were determined by weighing method at 298.15K. A new standard for judging good and poor solvents of CPP was proposed. The results obtained by the proposed standard are consistent with reality, the standard of complete miscibility suggested by Flory-Huggins and the standard proposed by Hansen, Lieberman,Funasaka. According to the standard proposed here, the three-dimensional solubility parameters and the total solubility parameter of CPP acquired by optimization calculation were calculated. They were verified by the turbidity method. The effects of temperature, concentration, interaction parameter between polymer and its solvents on dissolution of polymer were discussed from thermodynamic point. The three-dimensional solubility parameters add a new content for thermodynamic data of CPP and offer reference for selection of its solvents.The limiting molecular weight and rate coefficient under ultrasonic irradiation could be obtained by data fitting technique. It was proved that the method was feasible by experiment. The fitting accuracy of common kinetic equations of polymers under ultrasonic irradiation for experimental data of chlorinated polypropylene was evaluated. It was found that the fitting results of these kinetic equations for experimental data of chlorinated polypropylene were not satisfactory. Therefore, a new second order kinetic equation for ultrasonic degradation was proposed: 1/(M_t-M_lim)-1/(M_o-M_lim)=kt. Ultrasonic degradation of CPP toluene solution obeys this equation. The effect of concentration on rate coefficient and limiting molecular weights was investigated. This equation is a new complement for ultrasonic degradation kinetics of polymers.General applicability of the common and new kinetic equations kinetic equations were verified by the 41 sets of available original ultrasonic degradation data of polymers collected from previous reports. It was found that the general applicability of the first and second order kinetic equation proposed in this work were wider than other equations. They can substitute the other equations completely. Then a general power law expression（GPLE）of ultrasonic degradation,-dM_t／dt=k(M_t-M_lim)ⁿ n=1 or 2, was suggested. The kinetic equations can be united by the GPLE.更多还原