环保型热稳定剂的制备及其在PVC中的应用
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摘要
PVC是世界三大通用树脂之一,由于其具有良好的理化性能以及低廉的价格,在塑料制品中有着广泛的应用。但是PVC的热稳定性能较差,在加工过程中易发生降解,释放出HCl,导致PVC制品变色以及力学性能降低。因此在PVC的加工中必须加入热稳定剂来改善其加工性能。传统的热稳定剂一般含有铅、铬等重金属元素,会对环境造成污染。在环境问题日益突出的今天,研究新型的环保型热稳定剂已成为必然趋势。
本文首先以油酸、甲酸和双氧水为原料,合成出环氧油酸钙锌盐。将合成得到的环氧油酸钙锌盐以不同比例复配作为热稳定剂加入PVC中,通过刚果红法、电导率法、热烘箱试验法、热失重测试、红外测试以及力学性能测试等方法研究其热稳定性能和作用机理。结果表明环氧油酸锌是一种初期热稳定剂,有较好的初期着色性,它能够吸收PVC降解释放出的HCl,取代PVC上不稳定的氯原子,防止共轭烯烃链段的生成,但在这过程中会生成ZnCl2,从而产生“锌烧”现象。而环氧油酸钙是一种长期热稳定剂,可以吸收HCl,但是单独使用初期着色性不佳。而当环氧油酸钙锌盐复配使用时,环氧油酸钙会与ZnCl2反应,使其重新生成环氧油酸锌,延长稳定时间,同时改善初期着色性和延长黑化时间。两者复配使用,且环氧油酸锌/环氧油酸钙的质量份数比为1/3时,稳定时间达到了120min左右,为单独加入环氧油酸锌时的6倍;体系的初期着色性较好,同时黑化时间长达120min,说明在此比例下环氧油酸钙锌盐复配的热稳定效果最好。
进而将大豆分离蛋白(SPI)分别与硬脂酸锌(ZnSt2)、硬脂酸钙(CaSt2)、钙锌复合热稳定剂(Ca-Zn)以及环氧油酸钙锌盐以不同比例复配作为环保型热稳定剂加入PVC中。通过刚果红法,电导率法、热烘箱试验法、热失重测试,红外测试以及力学性能测试等方法研究其热稳定性能和作用机理。结果表明,SPI是一种性能优良的辅助热稳定剂,在有一定量主稳定剂Ca-Zn或者复配环氧油酸钙锌盐存在的条件下,能够与主稳定剂之间产生协同效应,显著提高热稳定效果,延长稳定时间和黑化时间。其中,以邻苯二甲酸二辛脂(DOP)为增塑剂,且Ca-Zn/SPI质量份数比为4/10时,稳定时间为172min,是只加入Ca-Zn时的2倍;黑化时间为180min,比只加入Ca-Zn时提高了60min;以环氧大豆油(ESO)为增塑剂,且环氧油酸锌/环氧油酸钙/SPI的质量份数比为1/3/10时,稳定时间达到了392.5min,是未加入SPI时的1.7倍;黑化时间长达400min,比未加入SPI时延长了160min。另外,SPI能够吸收PVC降解过程中释放出的HCl,属于长期热稳定剂。推测其热稳定机理在于SPI与HCl发生作用的过程中,分子链中的酰胺键(CONH)可能断开,生成部分酰氯键(COCl),起到热稳定的作用。
Poly(vinyl chloride) (PVC) is the world’s three general-purpose resin which is widely used due to its good performance in respect of mechanical behaviour as well as low price. However, PVC suffers from poor thermal stability, it undergoes extensive dehydrochlorination which results in severe discoloration and loss of mechanical properties. Therefore it is necessary to add thermal stabilizers in order to improve its thermal stability. However, the conventional thermal stabilizers generally contain lead, chromium and other toxic metals which will be environmental pollution. In recent years, the developments of environmentally friendly thermal stabilizers have become a necessity because environmental issues have become increasingly prominent.
First of all, oleic acid, formic acid and peroxide were used to synthesize epoxidized oleic acid. Afterward, epoxidized calcium (zinc) oleate was synthesized by double decomposition reaction. Investigation of thermal stability of epoxidized calcium (zinc) oleate was investigated by means of congo red test, conductivity test, visual color comparison, thermo gravimetric analysis (TGA) test, FTIR analysis and mechanical analysis. The results showed that epoxidized zinc oleic acid ester was an initial-term thermal stabilizer, which can absorb the released HCl, react with the labile chlorine atoms in PVC chain and prevent further dehydrochlorination. However, an undesirable effect of the stabilizing action of epoxidized zinc oleic acid ester was the production of ZnCl2, which can promote the sudden dehydrochlorination of PVC. There was a fast exchange reaction between ZnCl2 and epoxidized calcium oleic acid ester, where the active epoxidized zinc oleic acid ester was regenerated and the undesir able ZnCl2 was consumed. This effect can prolong stability time and blacking time. When the ratio of epoxidized zinc oleic acid ester/ epoxidized calcium oleic acid ester was 1/3, stability time reached to 120min. The stability time was incresed 5 times than the zinc oleic acid ester was added separately. At the same time, blacking time came to 120 min, indicating that in this ratio thermal stability was the best.
Moreover, soybean protein isolate (SPI) and its individual complex with zinc stearates (ZnSt2), calcium stearates (CaSt2), calcium/zinc compound thermal stabilizers (Ca-Zn), epoxidized calcium (zinc) oleate of various ratios as environmental friendly thermal stabilizer on the processing thermal stability of PVC were investgated by means of congo red test, conductivity test, visual color comparison, TGA test, FTIR analysis and mechanical analysis. The results showed that SPI was an auxiliary stabilizer. In the condition of a certain amount of primary Ca-Zn or epoxidized calcium (zinc) oleate, there was a synergistic effect between SPI and Ca-Zn stabilizers. When Dioctyl phthalate (DOP) was used as plasticizer, and Ca-Zn/SPI reached to 4/10, the stability time was 172min, twice as Ca-Zn was added separately, the blacking increased from 120min to 180min. When epoxidized soybean oil (ESO) was used as plasticizer, and epoxidized zinc oleic acid ester/epoxidized calcium oleic acid ester/SPI was 1/3/10, the stability time was 392.5min, 1.7 times as SPI was not added, the blacking increased from 240min to 400min. SPI was a long-term thermal stabilizer, which could reduce the release of HCl, the increase of the acid chloride carbonyl (COCl) stretching band in FTIR spectra suggested that amide(CONH)band may break and chloride carbonyl (COCl) band partly generated at the latter stages of degradation.
本文首先以油酸、甲酸和双氧水为原料,合成出环氧油酸钙锌盐。将合成得到的环氧油酸钙锌盐以不同比例复配作为热稳定剂加入PVC中,通过刚果红法、电导率法、热烘箱试验法、热失重测试、红外测试以及力学性能测试等方法研究其热稳定性能和作用机理。结果表明环氧油酸锌是一种初期热稳定剂,有较好的初期着色性,它能够吸收PVC降解释放出的HCl,取代PVC上不稳定的氯原子,防止共轭烯烃链段的生成,但在这过程中会生成ZnCl2,从而产生“锌烧”现象。而环氧油酸钙是一种长期热稳定剂,可以吸收HCl,但是单独使用初期着色性不佳。而当环氧油酸钙锌盐复配使用时,环氧油酸钙会与ZnCl2反应,使其重新生成环氧油酸锌,延长稳定时间,同时改善初期着色性和延长黑化时间。两者复配使用,且环氧油酸锌/环氧油酸钙的质量份数比为1/3时,稳定时间达到了120min左右,为单独加入环氧油酸锌时的6倍;体系的初期着色性较好,同时黑化时间长达120min,说明在此比例下环氧油酸钙锌盐复配的热稳定效果最好。
进而将大豆分离蛋白(SPI)分别与硬脂酸锌(ZnSt2)、硬脂酸钙(CaSt2)、钙锌复合热稳定剂(Ca-Zn)以及环氧油酸钙锌盐以不同比例复配作为环保型热稳定剂加入PVC中。通过刚果红法,电导率法、热烘箱试验法、热失重测试,红外测试以及力学性能测试等方法研究其热稳定性能和作用机理。结果表明,SPI是一种性能优良的辅助热稳定剂,在有一定量主稳定剂Ca-Zn或者复配环氧油酸钙锌盐存在的条件下,能够与主稳定剂之间产生协同效应,显著提高热稳定效果,延长稳定时间和黑化时间。其中,以邻苯二甲酸二辛脂(DOP)为增塑剂,且Ca-Zn/SPI质量份数比为4/10时,稳定时间为172min,是只加入Ca-Zn时的2倍;黑化时间为180min,比只加入Ca-Zn时提高了60min;以环氧大豆油(ESO)为增塑剂,且环氧油酸锌/环氧油酸钙/SPI的质量份数比为1/3/10时,稳定时间达到了392.5min,是未加入SPI时的1.7倍;黑化时间长达400min,比未加入SPI时延长了160min。另外,SPI能够吸收PVC降解过程中释放出的HCl,属于长期热稳定剂。推测其热稳定机理在于SPI与HCl发生作用的过程中,分子链中的酰胺键(CONH)可能断开,生成部分酰氯键(COCl),起到热稳定的作用。
Poly(vinyl chloride) (PVC) is the world’s three general-purpose resin which is widely used due to its good performance in respect of mechanical behaviour as well as low price. However, PVC suffers from poor thermal stability, it undergoes extensive dehydrochlorination which results in severe discoloration and loss of mechanical properties. Therefore it is necessary to add thermal stabilizers in order to improve its thermal stability. However, the conventional thermal stabilizers generally contain lead, chromium and other toxic metals which will be environmental pollution. In recent years, the developments of environmentally friendly thermal stabilizers have become a necessity because environmental issues have become increasingly prominent.
First of all, oleic acid, formic acid and peroxide were used to synthesize epoxidized oleic acid. Afterward, epoxidized calcium (zinc) oleate was synthesized by double decomposition reaction. Investigation of thermal stability of epoxidized calcium (zinc) oleate was investigated by means of congo red test, conductivity test, visual color comparison, thermo gravimetric analysis (TGA) test, FTIR analysis and mechanical analysis. The results showed that epoxidized zinc oleic acid ester was an initial-term thermal stabilizer, which can absorb the released HCl, react with the labile chlorine atoms in PVC chain and prevent further dehydrochlorination. However, an undesirable effect of the stabilizing action of epoxidized zinc oleic acid ester was the production of ZnCl2, which can promote the sudden dehydrochlorination of PVC. There was a fast exchange reaction between ZnCl2 and epoxidized calcium oleic acid ester, where the active epoxidized zinc oleic acid ester was regenerated and the undesir able ZnCl2 was consumed. This effect can prolong stability time and blacking time. When the ratio of epoxidized zinc oleic acid ester/ epoxidized calcium oleic acid ester was 1/3, stability time reached to 120min. The stability time was incresed 5 times than the zinc oleic acid ester was added separately. At the same time, blacking time came to 120 min, indicating that in this ratio thermal stability was the best.
Moreover, soybean protein isolate (SPI) and its individual complex with zinc stearates (ZnSt2), calcium stearates (CaSt2), calcium/zinc compound thermal stabilizers (Ca-Zn), epoxidized calcium (zinc) oleate of various ratios as environmental friendly thermal stabilizer on the processing thermal stability of PVC were investgated by means of congo red test, conductivity test, visual color comparison, TGA test, FTIR analysis and mechanical analysis. The results showed that SPI was an auxiliary stabilizer. In the condition of a certain amount of primary Ca-Zn or epoxidized calcium (zinc) oleate, there was a synergistic effect between SPI and Ca-Zn stabilizers. When Dioctyl phthalate (DOP) was used as plasticizer, and Ca-Zn/SPI reached to 4/10, the stability time was 172min, twice as Ca-Zn was added separately, the blacking increased from 120min to 180min. When epoxidized soybean oil (ESO) was used as plasticizer, and epoxidized zinc oleic acid ester/epoxidized calcium oleic acid ester/SPI was 1/3/10, the stability time was 392.5min, 1.7 times as SPI was not added, the blacking increased from 240min to 400min. SPI was a long-term thermal stabilizer, which could reduce the release of HCl, the increase of the acid chloride carbonyl (COCl) stretching band in FTIR spectra suggested that amide(CONH)band may break and chloride carbonyl (COCl) band partly generated at the latter stages of degradation.
引文
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