氯化聚丙烯接枝马来酸酐部分水解物物性的研究
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摘要
随着汽车工业的快速发展,聚丙烯塑料的应用越来越广泛。为了拓宽聚丙烯的使用范围,提高其市场竞争能力,需要进行表面涂饰,使其制品在外观和性能上达到高一级的水平。通过研究人们将聚丙烯制成氯化聚丙烯(CPP),并且发现其与聚丙烯有较好的附着力。目前,世界对氯化聚丙烯的需求量逐年增长,消费结构大体为涂料,粘合剂占40%,油墨载色剂占40%,其他占20%。
由于氯化聚丙烯分子极性小,造成在极性溶剂中的溶解力低:用作底漆,在底漆和面漆层间的附着力、耐油性、耐水性不足;用作底面合一漆,和常用涂料树脂的混溶性不好,难以复配。为此人们采用接枝改性的方法调整氯化聚丙烯的分子极性。
本实验室即对氯化聚丙烯进行接枝改性并对其改性后的性质进行了研究。实验室的马向东硕士用CPP(广东)和马来酸酐等作原料,在CPP分子上接枝上马来酸酐基团,合成了五种不同接枝率的接枝物。并且范忠雷在其论文中提到,在对合成产物提纯的过程中接枝的马来酸酐存在微量水解。
为了研究水解后接枝产物的性质,本文首先沿用马的方法合成五种不同接枝率的接枝产物,采用回收丙酮对接枝产物进行提纯并真空干燥,采用酸碱滴定测定其接枝率,并采用红外表征确定马来酸酐及水解后形成的马来酸峰,计算了接枝马来酸酐的相对水解率(水解物和不水解物的红外面积比)范围:50.9%～56.1%。
由于水解率的改变其极性的大小也会随之发生改变,因此接下来用浊度滴定测定五种不同接枝产物的溶度参数,发现接枝产物发生水解后其溶度参数变大,对溶度参数与接枝率进行线性拟合发现溶度参数与接枝率成比较好的线性关系;采用Hansen标准对五种接枝物在27中溶剂中的溶解度进行研究,优化计算了其三维溶度参数,并与微量水解接枝产物的溶度参数进行了初步比较。
最后,对氯化聚丙烯及其接枝产物在溶液中的溶液性质进行了深入系统的研究,测定了不同温度、不同浓度下氯化聚丙烯-甲苯/四氢呋喃、部分水解的MAH-g-CPP-甲苯/四氢呋喃二元体系的密度、黏度、表面张力等溶液性质,并分别就其随浓度的变化关系作了具体分析。
这些工作为研究氯化聚丙烯并扩宽氯化聚丙烯的用途提供了基础数据,具有重要的学术理论意义和工程应用前景。
The application of chlorinated polypropylene gets more and more abroad with the rapid development of automobile industry, For the sake of widening range of uses and boosting the market competitiveness of polypropylene, it needs to be coated by covering materials so that its products reach more perfection.
It is found that chlorinated polypropylene(CPP) which is made from polypropylene has good adhesion to PP. The quantity demanded of CPP is increasing year by year. The consumption structures of CPP are that the bonds account for 40%, the printing ink vehicles account for 40% and the others account for 20%. So, studies on CPP and technical development in CPP are very important.
The weakly polar of CPP resulted in low dissolved in polar solvents. Used as primer, the performance of adhesion, oil resistance, water resistance were not good enough. Used as coating paint, it is difficult to compound due to the poor miscibility with the common resin coating. So malefic anhydride(MAH) was grafted to chlorinated polypropylene in order that the polarity of CPP becomes strong.
Previously, our laboratory was studying on the research of graft-modified chlorinated polypropylene, and MAH was grafted to CPP by master Ma Xiangdong in our lab, and five different synthetic products in grafting yield of MAH were made. And Dr. Fan Zhonglei mentioned, in his papers, that the hydrolysis is existent in the process of purification.
In order to study the properties of the partially hydrolyzed CPP-g-MAH, in this paper, firstly, five grafted product with different grafting yield were synthetic according to MA's methods, and drying in a vacuum drying oven. The acetone was recycled using in purification. The grafting yield was estimated by acid-base titration. Synthesis of malefic anhydride grafted chlorinated polypropylene was studied, and it is proved that malefic anhydride was partially hydrolyzed according to IR spectrum. The rate of relative hydrolysis is: 50.9%～56.1%.
Because the polarity was changed with the different of hydrolysis rate, next, the solubility parameter of five different products was estimated by the methods of turbidimetric titration, and found that the solubility parameter of grafted product became larger as a result of hydrolysis. Having a linear fit, we found the grafting rate into a better linear relationship with the solubility parameter. The solubility in 27 solvents was studied according the standard of Hansen. The three-dimensional solubility parameter was optimized and calculated, and a preliminary comparison with the results of FAN's was carrying on.
Aim at the weakness of CPP property research at present, systemic studies to volume properties, viscosity properties, solubility parameter and surface tension properties were carried through in the thesis. The densities, viscosity, surface tension for binary mixtures of CPP and MAH-g-CPP with toluene, tetrahydrofuran were determined at temperatures 293.15K and 298.15K.
This systemic data supply basic data for project design and research of CPP.
由于氯化聚丙烯分子极性小,造成在极性溶剂中的溶解力低:用作底漆,在底漆和面漆层间的附着力、耐油性、耐水性不足;用作底面合一漆,和常用涂料树脂的混溶性不好,难以复配。为此人们采用接枝改性的方法调整氯化聚丙烯的分子极性。
本实验室即对氯化聚丙烯进行接枝改性并对其改性后的性质进行了研究。实验室的马向东硕士用CPP(广东)和马来酸酐等作原料,在CPP分子上接枝上马来酸酐基团,合成了五种不同接枝率的接枝物。并且范忠雷在其论文中提到,在对合成产物提纯的过程中接枝的马来酸酐存在微量水解。
为了研究水解后接枝产物的性质,本文首先沿用马的方法合成五种不同接枝率的接枝产物,采用回收丙酮对接枝产物进行提纯并真空干燥,采用酸碱滴定测定其接枝率,并采用红外表征确定马来酸酐及水解后形成的马来酸峰,计算了接枝马来酸酐的相对水解率(水解物和不水解物的红外面积比)范围:50.9%～56.1%。
由于水解率的改变其极性的大小也会随之发生改变,因此接下来用浊度滴定测定五种不同接枝产物的溶度参数,发现接枝产物发生水解后其溶度参数变大,对溶度参数与接枝率进行线性拟合发现溶度参数与接枝率成比较好的线性关系;采用Hansen标准对五种接枝物在27中溶剂中的溶解度进行研究,优化计算了其三维溶度参数,并与微量水解接枝产物的溶度参数进行了初步比较。
最后,对氯化聚丙烯及其接枝产物在溶液中的溶液性质进行了深入系统的研究,测定了不同温度、不同浓度下氯化聚丙烯-甲苯/四氢呋喃、部分水解的MAH-g-CPP-甲苯/四氢呋喃二元体系的密度、黏度、表面张力等溶液性质,并分别就其随浓度的变化关系作了具体分析。
这些工作为研究氯化聚丙烯并扩宽氯化聚丙烯的用途提供了基础数据,具有重要的学术理论意义和工程应用前景。
The application of chlorinated polypropylene gets more and more abroad with the rapid development of automobile industry, For the sake of widening range of uses and boosting the market competitiveness of polypropylene, it needs to be coated by covering materials so that its products reach more perfection.
It is found that chlorinated polypropylene(CPP) which is made from polypropylene has good adhesion to PP. The quantity demanded of CPP is increasing year by year. The consumption structures of CPP are that the bonds account for 40%, the printing ink vehicles account for 40% and the others account for 20%. So, studies on CPP and technical development in CPP are very important.
The weakly polar of CPP resulted in low dissolved in polar solvents. Used as primer, the performance of adhesion, oil resistance, water resistance were not good enough. Used as coating paint, it is difficult to compound due to the poor miscibility with the common resin coating. So malefic anhydride(MAH) was grafted to chlorinated polypropylene in order that the polarity of CPP becomes strong.
Previously, our laboratory was studying on the research of graft-modified chlorinated polypropylene, and MAH was grafted to CPP by master Ma Xiangdong in our lab, and five different synthetic products in grafting yield of MAH were made. And Dr. Fan Zhonglei mentioned, in his papers, that the hydrolysis is existent in the process of purification.
In order to study the properties of the partially hydrolyzed CPP-g-MAH, in this paper, firstly, five grafted product with different grafting yield were synthetic according to MA's methods, and drying in a vacuum drying oven. The acetone was recycled using in purification. The grafting yield was estimated by acid-base titration. Synthesis of malefic anhydride grafted chlorinated polypropylene was studied, and it is proved that malefic anhydride was partially hydrolyzed according to IR spectrum. The rate of relative hydrolysis is: 50.9%～56.1%.
Because the polarity was changed with the different of hydrolysis rate, next, the solubility parameter of five different products was estimated by the methods of turbidimetric titration, and found that the solubility parameter of grafted product became larger as a result of hydrolysis. Having a linear fit, we found the grafting rate into a better linear relationship with the solubility parameter. The solubility in 27 solvents was studied according the standard of Hansen. The three-dimensional solubility parameter was optimized and calculated, and a preliminary comparison with the results of FAN's was carrying on.
Aim at the weakness of CPP property research at present, systemic studies to volume properties, viscosity properties, solubility parameter and surface tension properties were carried through in the thesis. The densities, viscosity, surface tension for binary mixtures of CPP and MAH-g-CPP with toluene, tetrahydrofuran were determined at temperatures 293.15K and 298.15K.
This systemic data supply basic data for project design and research of CPP.
引文
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