酯基锡合成及其对PVC热稳定性能研究
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摘要
自荷兰Akzo公司发明第一个酯基锡化合物以来,关于酯基锡及其中间体的合成方法和复配研究一直非常活跃。近年来,仍然不断有新型酯基锡产品涌现并应用于制备PVC环保和透明制品,开发新型酯基锡化合物和改进合成方法是该领域的研究热点。我国在该领域的研究起步于上世纪九十年代,并进行了小规模的仿效生产,因工艺路线不成熟、事故频发和产品质量不稳定而没有实现大规模的产业化。其中产品质量问题是瓶颈问题,主要体现在产品放置几周后易出现沉淀、变色及臭味较重三个方面。本论文提出了合成酯基锡的新方法,突破了这一瓶颈问题,通过复配研究,制备了低毒环保型复合酯基锡热稳定剂。
本文的研究内容主要由三部分组成：(1)混合溶剂法合成中间体酯基二氯化锡(丁酯)的合成路线研究,重点讨论合成条件对产物组份和性能的影响；(2)Na2CO3水溶液-有机溶剂混合溶剂法合成酯基锡热稳定剂的合成路线研究,考察产物的静、动态热稳定性和流变性能,并对NaHCO3法合成产物中产生沉淀的原因和种类进行分析；(3)对酯基锡(甲酯)与甲基硫醇锡、金属皂、抗氧剂双酚A和水滑石进行复配研究,制备酯基锡(甲酯)/甲基硫醇锡、酯基锡(甲酯)/双酚A/水滑石两种复合热稳定剂,并分析两种复合热稳定剂对PVC的热稳定机理。具体研究工作简要概括如下：
本文采用三氯甲烷和四氢呋喃混合溶剂代替易燃易爆的乙醚作为反应介质,以Sn粉、丙烯酸丁酯分别与HCl气体、HCl气体和浓盐酸混合物、浓盐酸反应合成中间体酯基二氯化锡(丁酯)。重点研究了合成条件对中间体中各组分比例的影响。
实验结果表明,反应温度和通入HC1的方式是影响反应的主要因素,所合成的中间体是(C4H9OCOCH2CH2)2SnCl2和(C4H9OCOCH2CH2)SnCl3的混合物,主要成份是(C4H9OCOCH2CH2)2SnCl2,其含量为88.97%,反应收率大于90%。
本文用Na2CO3混合溶剂法和相转移催化剂,以酯基二氯化锡(甲酯)和酯基二氯化锡(丁酯)为中间体,巯基乙酸异辛酯为原料合成酯基锡(甲酯)和酯基锡(丁酯)。考察了合成方法、Na2CO3水溶液的质量分数和反应温度对产物收率、Sn含量和热稳定性的影响；通过HPLC、IR和1H-NMR等方法,重点研究了Na2CO3混合溶剂法和NaHCO3法合成酯基锡(甲酯)和酯基锡(丁酯)的组成和结构,分析了酯基锡(甲酯)易出现沉淀的原因；通过与甲基硫醇锡对比,详细考察了两种热稳定剂的静、动态热稳定性、透明性和流变性能。
研究结果表明,NaHCO3法合成的酯基锡(甲酯)中的沉淀是酯基锡氢氧化物,是由中间体酯基二氯化锡与副产物水发生水解反应的副产物；采用Na2CO3混合溶剂法合成酯基锡(甲酯),由于反应体系是液相体系,在相转移催化剂的作用下,中间体酯基二氯化锡反应得更完全,因此减轻或消除了生成沉淀的可能性。所合成的产物放置3个月以上无沉淀,产物的静态热稳定时间好于NaHCO3法合成的产物；在影响酯基锡合成的反应条件中,Na2CO3水溶液的质量分数是最主要的,产物收率达到95%以上。在PVC加工温度下,酯基锡的加工稳定性、透明性和流变性能均能和甲基硫醇锡相媲美。
本文考察了酯基锡(甲酯)与甲基硫醇锡、金属皂、抗氧剂双酚A和水滑石之间的协同效应,制备了酯基锡(甲酯)/甲基硫醇锡(1：1)复合热稳定剂和酯基锡(甲酯)/抗氧剂双酚A/水滑石(2：0.7：2.5)环保型复合热稳定剂。分析了两种复合热稳定剂抑制PVC的降解过程,提出了复合酯基锡对PVC的热稳定机理,测试了复合酯基锡/PVC复合体系的动态加工稳定性、透明性和力学性能。
研究结果表明,酯基锡(甲酯)与甲基硫醇锡以1：1复配,其静态热稳定时间长于单独使用2份酯基锡(甲酯),比单独使用2份甲基硫醇锡静态热稳定时间短,两者复配,改善了酯基锡的初期着色性和加工安全性,透明性好；酯基锡与硬脂酸钙和硬脂酸钡的协同效应较好,硬脂酸锌与酯基锡不但没有协同效应,还会加速PVC的降解；环保、低毒的酯基锡(甲酯)/抗氧剂双酚A/水滑石(2：0.7：2.5)复合热稳定剂对PVC有良好的热稳定性和加工安全性。经钛酸酯改性的水滑石在PVC中有良好的分散性和相容性,进而提高了PVC复合体系的热稳定性和力学性能。分析结果表明,水滑石与酯基锡(甲酯)有较好的协同效应。
Studies on synthesis method and composite of ester-tin are in progress actively, since the first ester-tin compound was produced by Akso company Holland in 1976. In recent years, new (ester-tin) products are manufactured ceaselessly and applied to produce environment friendly and transparent PVC products, and the intensive study was concentrated on developing new synthesis routes and new compounds. Studies on this field started in the early 1990s in china, and the patterned manufactures were in progressed on small scales. However, the products were not industrialized massively because of immature process routes, accidents and unstable quality that precipitation, colouration and strong smell may occur within several days after being synthesized. In this paper, in order to solve this problem a new ester-tin synthesis route was proposed so that novel composite ester-tins with low tin content and low toxicity were prepared.
Studies in this paper are comprised of three sections:studies on the synthesis of bis(β-butyloxycarbonylethyl) tin dichlorides intermediate by mixing solvents, which was focused on the effects of synthesis conditions to the components and quality of products; Studies on the synthesis methods of ester-tin thermal stabilizers synthesized by Na2CO3 mixing solvents, in which the static thermal stability, the dynamic stability and rheological behavior were tested; Studies on ester-tin, which composited with methyltin mercaptide, metal soap, antioxidant bisphenol a and HLDs were carried out. Two kinds of composite thermal stabilizers of ester-tin(methyl acralate)/methyltin mercaptide(1:1)and ester-tin(methyl acralate)/ antioxidant bisphenol a/HLDs (2:0.7:2.5)were prepared and the mechanisms to PVC were investigated by means of thermal analysis method.
In this paper, bis(β-butyloxycarbonylethyl) tin dichlorides intermediate was synthesized by Sn powder, butyl acrylate reacted with HCl, HCl/hydrochloric acid and hydrochloric acid separately, and the effects of the reaction conditions such as the ratio of raw materials, temperature and reaction time to the component ratio of intermediate were studied. Results showed that the reaction temperature and the way to pump in HCl were the key factors, and the yield was over 90%. The intermediate was the mixture of (C4H9OCOCH2CH2)2SnCl2 and (C4H9OCOCH2CH2)SnCl3, and (C4H9OCOCH2CH2)2SnCl2 which accounted for 88.97% was the main component.
Ester-tin(methyl acrylate) and ester-tin(butyl acrylate) were synthesized with Na2CO3 mixing solvents and transfer catalyst. The effects of synthesis methods, reaction temperature, reaction time, catalyst dosages and concentration of Na2CO3 aq. to the yield, Sn content and thermal stability were investgated. The components and structures of two products that produced by means of Na2CO3 aq. and NaHCO3 analyzed by HPLC, IR, and 1-NMR, and the reason of appearing precipitation was proposed. Static and dynamic thermal stability, transparency, rheologic properties of two products were investigated, and the mechanism to suppress PVC degredation was also analyzed by comparing with methyltin mercaptide.
Results showed that the precipitation in ester-tin (methyl acrylate) synthesized by NaHCO3 was ester-tin hydroxide which was formed by the byproducts from the hydrolysis of bis(β-butyloxycarbonylethyl) tin dichlorides. Ester-tin (methyl acrylate) synthesized by Na2CO3 aq. was clear over 3 months, because in this reaction system, bis(β-butyloxycarbonylethyl) tin dichlorides reacted fully with mercaptoester catalyzed under transfer catalysist without ester-tin hydroxide was not formed in products. Thermal stability of the products made by Na2CO3 mixing solvents was better than that of making by NaHCO3. Ester-tin(butyl acrylate) synthesized by Na2CO3 mixing solvents was clear over 1 year, the concentration of Na2CO3 aq. was the most important of all the factors. The processing stability, transparency and flowing properties of two kinds of ester-tin were similar with methyltin mercaptide under PVC processing conditions.
The synergism between ester-tin(methyl acrylate) with methyltin mercaptide, metal soaps, antioxidant bisphenol a and HLDs were investigated. How ester-tin (methyl acrylate)/methyltin mercaptide, ester-tin(methyl acrylate)/antioxidant bisphenol a/HLDs compound stabilizers to suppress the degradation process of PVC were analyzed. The dynamic thermal stability, transparency, and dynamic properties of compound ester-tin/PVC were also tested.
Experimental results indicated that there was little synergism between ester-tin(methyl acrylate) and methyltin mercaptide, but the first stage pigmentation processing safety and transparency were improved; There were synergisms among barium stearate, calcium stearate and ester-tin(methyl acrylate), but zinc stearate not only had no synergistic effect but also could accelerate the degradation of PVC; Ester-tin(methyl acrylate)/bisphenol a/ HLDs modified by titanate (2:1:2.5) environmental compound stabilizers exhibited a better thermal stability, HLDs modified by titanate had not only a famous synergistic effect but also a better dispersity and consistency in PVC as well, so the thermal stability and mechanical properties of PVC composites were improved.
本文的研究内容主要由三部分组成：(1)混合溶剂法合成中间体酯基二氯化锡(丁酯)的合成路线研究,重点讨论合成条件对产物组份和性能的影响；(2)Na2CO3水溶液-有机溶剂混合溶剂法合成酯基锡热稳定剂的合成路线研究,考察产物的静、动态热稳定性和流变性能,并对NaHCO3法合成产物中产生沉淀的原因和种类进行分析；(3)对酯基锡(甲酯)与甲基硫醇锡、金属皂、抗氧剂双酚A和水滑石进行复配研究,制备酯基锡(甲酯)/甲基硫醇锡、酯基锡(甲酯)/双酚A/水滑石两种复合热稳定剂,并分析两种复合热稳定剂对PVC的热稳定机理。具体研究工作简要概括如下：
本文采用三氯甲烷和四氢呋喃混合溶剂代替易燃易爆的乙醚作为反应介质,以Sn粉、丙烯酸丁酯分别与HCl气体、HCl气体和浓盐酸混合物、浓盐酸反应合成中间体酯基二氯化锡(丁酯)。重点研究了合成条件对中间体中各组分比例的影响。
实验结果表明,反应温度和通入HC1的方式是影响反应的主要因素,所合成的中间体是(C4H9OCOCH2CH2)2SnCl2和(C4H9OCOCH2CH2)SnCl3的混合物,主要成份是(C4H9OCOCH2CH2)2SnCl2,其含量为88.97%,反应收率大于90%。
本文用Na2CO3混合溶剂法和相转移催化剂,以酯基二氯化锡(甲酯)和酯基二氯化锡(丁酯)为中间体,巯基乙酸异辛酯为原料合成酯基锡(甲酯)和酯基锡(丁酯)。考察了合成方法、Na2CO3水溶液的质量分数和反应温度对产物收率、Sn含量和热稳定性的影响；通过HPLC、IR和1H-NMR等方法,重点研究了Na2CO3混合溶剂法和NaHCO3法合成酯基锡(甲酯)和酯基锡(丁酯)的组成和结构,分析了酯基锡(甲酯)易出现沉淀的原因；通过与甲基硫醇锡对比,详细考察了两种热稳定剂的静、动态热稳定性、透明性和流变性能。
研究结果表明,NaHCO3法合成的酯基锡(甲酯)中的沉淀是酯基锡氢氧化物,是由中间体酯基二氯化锡与副产物水发生水解反应的副产物；采用Na2CO3混合溶剂法合成酯基锡(甲酯),由于反应体系是液相体系,在相转移催化剂的作用下,中间体酯基二氯化锡反应得更完全,因此减轻或消除了生成沉淀的可能性。所合成的产物放置3个月以上无沉淀,产物的静态热稳定时间好于NaHCO3法合成的产物；在影响酯基锡合成的反应条件中,Na2CO3水溶液的质量分数是最主要的,产物收率达到95%以上。在PVC加工温度下,酯基锡的加工稳定性、透明性和流变性能均能和甲基硫醇锡相媲美。
本文考察了酯基锡(甲酯)与甲基硫醇锡、金属皂、抗氧剂双酚A和水滑石之间的协同效应,制备了酯基锡(甲酯)/甲基硫醇锡(1：1)复合热稳定剂和酯基锡(甲酯)/抗氧剂双酚A/水滑石(2：0.7：2.5)环保型复合热稳定剂。分析了两种复合热稳定剂抑制PVC的降解过程,提出了复合酯基锡对PVC的热稳定机理,测试了复合酯基锡/PVC复合体系的动态加工稳定性、透明性和力学性能。
研究结果表明,酯基锡(甲酯)与甲基硫醇锡以1：1复配,其静态热稳定时间长于单独使用2份酯基锡(甲酯),比单独使用2份甲基硫醇锡静态热稳定时间短,两者复配,改善了酯基锡的初期着色性和加工安全性,透明性好；酯基锡与硬脂酸钙和硬脂酸钡的协同效应较好,硬脂酸锌与酯基锡不但没有协同效应,还会加速PVC的降解；环保、低毒的酯基锡(甲酯)/抗氧剂双酚A/水滑石(2：0.7：2.5)复合热稳定剂对PVC有良好的热稳定性和加工安全性。经钛酸酯改性的水滑石在PVC中有良好的分散性和相容性,进而提高了PVC复合体系的热稳定性和力学性能。分析结果表明,水滑石与酯基锡(甲酯)有较好的协同效应。
Studies on synthesis method and composite of ester-tin are in progress actively, since the first ester-tin compound was produced by Akso company Holland in 1976. In recent years, new (ester-tin) products are manufactured ceaselessly and applied to produce environment friendly and transparent PVC products, and the intensive study was concentrated on developing new synthesis routes and new compounds. Studies on this field started in the early 1990s in china, and the patterned manufactures were in progressed on small scales. However, the products were not industrialized massively because of immature process routes, accidents and unstable quality that precipitation, colouration and strong smell may occur within several days after being synthesized. In this paper, in order to solve this problem a new ester-tin synthesis route was proposed so that novel composite ester-tins with low tin content and low toxicity were prepared.
Studies in this paper are comprised of three sections:studies on the synthesis of bis(β-butyloxycarbonylethyl) tin dichlorides intermediate by mixing solvents, which was focused on the effects of synthesis conditions to the components and quality of products; Studies on the synthesis methods of ester-tin thermal stabilizers synthesized by Na2CO3 mixing solvents, in which the static thermal stability, the dynamic stability and rheological behavior were tested; Studies on ester-tin, which composited with methyltin mercaptide, metal soap, antioxidant bisphenol a and HLDs were carried out. Two kinds of composite thermal stabilizers of ester-tin(methyl acralate)/methyltin mercaptide(1:1)and ester-tin(methyl acralate)/ antioxidant bisphenol a/HLDs (2:0.7:2.5)were prepared and the mechanisms to PVC were investigated by means of thermal analysis method.
In this paper, bis(β-butyloxycarbonylethyl) tin dichlorides intermediate was synthesized by Sn powder, butyl acrylate reacted with HCl, HCl/hydrochloric acid and hydrochloric acid separately, and the effects of the reaction conditions such as the ratio of raw materials, temperature and reaction time to the component ratio of intermediate were studied. Results showed that the reaction temperature and the way to pump in HCl were the key factors, and the yield was over 90%. The intermediate was the mixture of (C4H9OCOCH2CH2)2SnCl2 and (C4H9OCOCH2CH2)SnCl3, and (C4H9OCOCH2CH2)2SnCl2 which accounted for 88.97% was the main component.
Ester-tin(methyl acrylate) and ester-tin(butyl acrylate) were synthesized with Na2CO3 mixing solvents and transfer catalyst. The effects of synthesis methods, reaction temperature, reaction time, catalyst dosages and concentration of Na2CO3 aq. to the yield, Sn content and thermal stability were investgated. The components and structures of two products that produced by means of Na2CO3 aq. and NaHCO3 analyzed by HPLC, IR, and 1-NMR, and the reason of appearing precipitation was proposed. Static and dynamic thermal stability, transparency, rheologic properties of two products were investigated, and the mechanism to suppress PVC degredation was also analyzed by comparing with methyltin mercaptide.
Results showed that the precipitation in ester-tin (methyl acrylate) synthesized by NaHCO3 was ester-tin hydroxide which was formed by the byproducts from the hydrolysis of bis(β-butyloxycarbonylethyl) tin dichlorides. Ester-tin (methyl acrylate) synthesized by Na2CO3 aq. was clear over 3 months, because in this reaction system, bis(β-butyloxycarbonylethyl) tin dichlorides reacted fully with mercaptoester catalyzed under transfer catalysist without ester-tin hydroxide was not formed in products. Thermal stability of the products made by Na2CO3 mixing solvents was better than that of making by NaHCO3. Ester-tin(butyl acrylate) synthesized by Na2CO3 mixing solvents was clear over 1 year, the concentration of Na2CO3 aq. was the most important of all the factors. The processing stability, transparency and flowing properties of two kinds of ester-tin were similar with methyltin mercaptide under PVC processing conditions.
The synergism between ester-tin(methyl acrylate) with methyltin mercaptide, metal soaps, antioxidant bisphenol a and HLDs were investigated. How ester-tin (methyl acrylate)/methyltin mercaptide, ester-tin(methyl acrylate)/antioxidant bisphenol a/HLDs compound stabilizers to suppress the degradation process of PVC were analyzed. The dynamic thermal stability, transparency, and dynamic properties of compound ester-tin/PVC were also tested.
Experimental results indicated that there was little synergism between ester-tin(methyl acrylate) and methyltin mercaptide, but the first stage pigmentation processing safety and transparency were improved; There were synergisms among barium stearate, calcium stearate and ester-tin(methyl acrylate), but zinc stearate not only had no synergistic effect but also could accelerate the degradation of PVC; Ester-tin(methyl acrylate)/bisphenol a/ HLDs modified by titanate (2:1:2.5) environmental compound stabilizers exhibited a better thermal stability, HLDs modified by titanate had not only a famous synergistic effect but also a better dispersity and consistency in PVC as well, so the thermal stability and mechanical properties of PVC composites were improved.
引文
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