新型PVC热稳定剂合成、应用及机理研究
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摘要
聚氯乙烯(PVC)是五大通用塑料之一,但其热稳定性差,在160～200℃温度下加工时,会发生剧烈的热降解,因此必须使用稳定剂。传统热稳定剂有铅盐、有机锡、钙锌复合稳定剂。铅类稳定剂毒性大,易造成环境污染等问题,有机锡成本较高,钙锌复合稳定剂在使用中易发生"锌烧"现象。随着全球环保要求越来越高,因此研究新型、高效、低毒性的热稳定剂具有重要意义和较好的应用前景。
稀土热稳定剂是近年来发展起来的新型热稳定剂,具有无毒、长期热稳定性好等优点,但其抗初期着色性差。在本文中作者合成了多种稀土盐,经测试、筛选,发现硬脂酸镧对PVC热稳定性能相对较好。并深入研究了硬脂酸镧对PVC热稳定作用机理,经一系列实验及分析测试表明:硬脂酸镧在PVC降解过程中对共轭双烯结构的形成,不能起到显著的抑制作用;硬脂酸镧能与PVC中的氯原子发生作用,使得C-Cl键趋于稳定,导致PVC在降解过程中1,3重排更为困难,因而明显抑制共轭多烯结构的形成;根据PVC降解的协同消除机理,能作出很好的解释。在理论上解释了稀土稳定剂抗初期着色性差的问题。
作者研究了环己二醇二缩水甘油醚作为辅助热稳定剂,与钙锌复合体系的协同作用及协同机理。实验结果表明:环己二醇二缩水甘油醚对Ca/Zn复合体系具有很好的协同作用,能有效地抑制Ca/Zn复合稳定剂在使用中的"锌烧"现象,与Ca/Zn稳定剂复配性能优于环氧大豆油。环己二醇二缩水甘油醚与Ca/Zn复合稳定剂协同作用机理有两个方面:一是通过环氧基团开环和醚键断裂与PVC降解产生的HCl反应,消除PVC降解产生的HCl;二是环己二醇二缩水甘油醚在ZnCl2作用下,环氧基团开环,其中氧与锌结合,避免了ZnCl2催化PVC降解。
将硬脂酸铅、硬脂酸镧、硬脂酸钙、硬脂酸锌、环己二醇二缩水甘油醚等经正交实验优化、筛选得一性能较优配方,制得铅-稀土-钙锌复合热稳定剂。经刚果红法热稳定测试及挤出造粒,结果表明其性能与铅盐稳定剂相近,但其铅盐含量只占复合稳定剂25%左右,可大大减轻铅盐在使用中造成的环境污染,具有很好的应用前景。
Polyvinyle chloride(PVC) is one of the five most popular plastics. Since it has poor thermal stabilization and will degrade at 160～200℃in its processing, thermal stabilizer is used. There are plumbum salts, organic stannum and Ca/Zn Composite Stabilizer in traditional thermal stabilizer. However, Plumbum salts thermal stabilizers pollute environment with toxicity, using organic stannum costs too much, and the phenomenon of "zinc burn" will easily occur during the process of using Ca/Zn Composite Stabilizer. As the demand for environmental protection is becoming stronger and stronger, it will be quite significant and promising to develop a new kind of thermal stabilizer with high efficiency and low toxicity.
Rare earth thermal stabilizer, with no toxicity and long stabilization, has been developed as a new type of thermal stabilizer in the past few years, but it can not protect PVC from discoloring at an early stage. In my research I synthesize several rare earth salts by testing and choosing, only to find that Lanthanum stearate is the best one. The mechanism of stabilization of lanthanum stearate is studied by a series of experiments and tests, which can also be well explained by concerted elimination mechanism. I find that lanthanum stearate can not restrain the increase of conjugated double bond effectively; however, it can interact with chlorine in PVC, so that it makes C-Cl bond more stabilized and 1,3 rearrangement of chlorine more difficult. Consequently, it can restrain the formation of conjugated polyene(-CH=CH-)n (n>2). This theory can explain well the reason why rare earth salts can not protect PVC from discoloring at an early stage.
In my research, cooperativity and cooperativity Mechanism of cylohexanediol diglycidyl ether and Ca/Zn Composite Stabilizer are studied.
We find that cylohexanediol diglycidyl ether turns out to possess the feature of harmonious cooperativity with Ca/Zn composite stabilizer. It restrains the phenomenon of "zinc burn" effectively during the process of using Ca/Zn composite stabilizer, and it has an advantage over epoxidized soybean oil after being remixed with Ca/Zn composite stabilizer. There are two aspects for the cooperativity mechanism compounded by cylohexanediol diglycidyl ether and Ca/Zn composite stabilizer: One is to remove HCl during the degradation of PVC by the reactions that epoxidized groups and ether bonds react with HCl; The other is that the oxide atom in the epoxidized group can combine with zinc in the presence of ZnCl2, making ZnCl2
稀土热稳定剂是近年来发展起来的新型热稳定剂,具有无毒、长期热稳定性好等优点,但其抗初期着色性差。在本文中作者合成了多种稀土盐,经测试、筛选,发现硬脂酸镧对PVC热稳定性能相对较好。并深入研究了硬脂酸镧对PVC热稳定作用机理,经一系列实验及分析测试表明:硬脂酸镧在PVC降解过程中对共轭双烯结构的形成,不能起到显著的抑制作用;硬脂酸镧能与PVC中的氯原子发生作用,使得C-Cl键趋于稳定,导致PVC在降解过程中1,3重排更为困难,因而明显抑制共轭多烯结构的形成;根据PVC降解的协同消除机理,能作出很好的解释。在理论上解释了稀土稳定剂抗初期着色性差的问题。
作者研究了环己二醇二缩水甘油醚作为辅助热稳定剂,与钙锌复合体系的协同作用及协同机理。实验结果表明:环己二醇二缩水甘油醚对Ca/Zn复合体系具有很好的协同作用,能有效地抑制Ca/Zn复合稳定剂在使用中的"锌烧"现象,与Ca/Zn稳定剂复配性能优于环氧大豆油。环己二醇二缩水甘油醚与Ca/Zn复合稳定剂协同作用机理有两个方面:一是通过环氧基团开环和醚键断裂与PVC降解产生的HCl反应,消除PVC降解产生的HCl;二是环己二醇二缩水甘油醚在ZnCl2作用下,环氧基团开环,其中氧与锌结合,避免了ZnCl2催化PVC降解。
将硬脂酸铅、硬脂酸镧、硬脂酸钙、硬脂酸锌、环己二醇二缩水甘油醚等经正交实验优化、筛选得一性能较优配方,制得铅-稀土-钙锌复合热稳定剂。经刚果红法热稳定测试及挤出造粒,结果表明其性能与铅盐稳定剂相近,但其铅盐含量只占复合稳定剂25%左右,可大大减轻铅盐在使用中造成的环境污染,具有很好的应用前景。
Polyvinyle chloride(PVC) is one of the five most popular plastics. Since it has poor thermal stabilization and will degrade at 160～200℃in its processing, thermal stabilizer is used. There are plumbum salts, organic stannum and Ca/Zn Composite Stabilizer in traditional thermal stabilizer. However, Plumbum salts thermal stabilizers pollute environment with toxicity, using organic stannum costs too much, and the phenomenon of "zinc burn" will easily occur during the process of using Ca/Zn Composite Stabilizer. As the demand for environmental protection is becoming stronger and stronger, it will be quite significant and promising to develop a new kind of thermal stabilizer with high efficiency and low toxicity.
Rare earth thermal stabilizer, with no toxicity and long stabilization, has been developed as a new type of thermal stabilizer in the past few years, but it can not protect PVC from discoloring at an early stage. In my research I synthesize several rare earth salts by testing and choosing, only to find that Lanthanum stearate is the best one. The mechanism of stabilization of lanthanum stearate is studied by a series of experiments and tests, which can also be well explained by concerted elimination mechanism. I find that lanthanum stearate can not restrain the increase of conjugated double bond effectively; however, it can interact with chlorine in PVC, so that it makes C-Cl bond more stabilized and 1,3 rearrangement of chlorine more difficult. Consequently, it can restrain the formation of conjugated polyene(-CH=CH-)n (n>2). This theory can explain well the reason why rare earth salts can not protect PVC from discoloring at an early stage.
In my research, cooperativity and cooperativity Mechanism of cylohexanediol diglycidyl ether and Ca/Zn Composite Stabilizer are studied.
We find that cylohexanediol diglycidyl ether turns out to possess the feature of harmonious cooperativity with Ca/Zn composite stabilizer. It restrains the phenomenon of "zinc burn" effectively during the process of using Ca/Zn composite stabilizer, and it has an advantage over epoxidized soybean oil after being remixed with Ca/Zn composite stabilizer. There are two aspects for the cooperativity mechanism compounded by cylohexanediol diglycidyl ether and Ca/Zn composite stabilizer: One is to remove HCl during the degradation of PVC by the reactions that epoxidized groups and ether bonds react with HCl; The other is that the oxide atom in the epoxidized group can combine with zinc in the presence of ZnCl2, making ZnCl2
引文
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