CN106084294B - 一种β-二酮类有机锡PVC热稳定剂及其制备方法 - Google Patents
一种β-二酮类有机锡PVC热稳定剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种β‑二酮类有机锡PVC热稳定剂及其制备方法,属于PVC热稳定剂技术领域。本发明的技术方案要点为:一种β‑二酮类有机锡PVC热稳定剂,其结构式为:
Description
技术领域
本发明属于PVC热稳定剂技术领域,具体涉及一种β-二酮类有机锡PVC热稳定剂及其制备方法。
背景技术
聚氯乙烯(简称PVC)是五大通用塑料之一,以其低廉的价格和非常突出的均衡性能而成为十分理想的材料,也是塑料应用历史上古老而活跃的品种,其全球产量仅次于聚乙烯居第二位。我国是PVC树脂的生产大国之一,国内聚氯乙烯工业经过50多年的发展已取得长足进步,目前国内拥有聚氯乙烯生产企业100多家,生产能力在国内合成树脂中居于首位。
一般PVC通常加热到130℃以上时,便开始释放出HCl,这是因为在制造PVC的过程中,由于自动氧化反应、链终止反应与微量氧的共聚反应及一些尚未明确的副反应产生了不稳定的C-Cl键,进而受热分解释放出HCl,而HCl又会对PVC的继续分解起到催化作用,使PVC最后转变成含有不饱和的共轭双键结构(多烯序列),这样的连串反应,最后导致了大分子链上出现长的多烯序列,当大分子链上的双键数大于6时,PVC就会变色。
因此,作为PVC的热稳定剂应具备预防功能和钝化作用。其中预防功能包括两个方面,一方面是吸收PVC热降解释放出的HCl,另一方面是消除PVC不稳定的氯原子,从而防止HCl的产生;钝化作用是消除影响PVC性能的物质,其方法是热稳定剂与多烯序列化合物进行加成反应,使长的多烯序列化合物变短(使共轭双键数减少)。目前,市场上作用效果最好的是有机锡类热稳定剂,是最有发展前景的热稳定剂,尤其在透明PVC制备中的应用更为广泛。其主要包括二甲基锡、二正丁基锡和二正辛基锡的脂肪酸盐、马来酸盐、硫醇盐、硫醇基脂肪酸盐等类型。有机锡类热稳定剂有很好的热稳定性、相容性和透明性等优点,但是该类热稳定剂都为液体,在运输、储存等方面不是很方便。
β-二酮类化合物是一种重要的热塑性塑料用的光稳定剂和热稳定剂,广泛用于PVC塑料和ABS树脂中,主要用作聚氯乙烯制品的助热稳定剂。作为新型PVC辅助热稳定剂,β-二酮类化合物具有高效、无毒和多功能等优点。与固体或液体钙/锌、钡/锌等热稳定剂并用,能大大改善PVC初期着色、透明度、长期稳定性以及加工过程中的析出和“锌烧”等,广泛用于医疗、食品包装等无毒透明PVC制品。在欧美等发达国家都允许在食品包装领域内使用该产品。
发明内容
本发明解决的技术问题是提供了一种能够综合有机锡稳定剂和β-二酮类辅助稳定剂的优点,使PVC热稳定效果更佳的β-二酮类有机锡PVC热稳定剂。
本发明解决的另一个技术问题是提供了一种操作简单易行、原料廉价易得、反应效率较高且重复性好的固体的β-二酮类有机锡PVC热稳定剂的制备方法。
本发明为解决上述技术问题采用如下技术方案,一种β-二酮类有机锡PVC热稳定剂,其特征在于结构式为:其中R为苯基或十七烷基。
本发明所述的β-二酮类有机锡PVC热稳定剂的制备方法,其特征在于具体步骤为:向安装有搅拌装置的超声波反应容器中通入氮气,然后加入溶有β-二酮类化合物的二氯甲烷溶液和氨水,于0-50℃的反应温度下向超声波反应容器中滴加亚锡盐的甲醇溶液或亚锡盐的丙酮溶液,其中β-二酮类化合物与亚锡盐的投料摩尔比为1-2:1,滴加过程中开启搅拌装置和超声波发生装置,超声波发生装置的设定频率为20-100KHz,滴加完后停止搅拌,保持超声波发生装置继续工作,降温至0℃后打开超声波反应容器上的排气孔,保持通入的氮气从排气孔排出直至反应液析晶完全,抽滤反应液,滤饼用甲醇洗涤多次以洗去多余的亚锡盐,滤饼在室温下晾干后得到β-二酮类有机锡PVC热稳定剂。
进一步优选,所述的亚锡盐为氯化亚锡、硫酸亚锡或硝酸亚锡。
进一步优选,所述的反应温度为25℃。
进一步优选,所述的超声波发生装置的设定频率为80KHz。
进一步优选,所述的β-二酮类化合物与亚锡盐的投料摩尔比为1.5:1。
本发明与现有技术相比具有以下有益效果:
1、综合了目前已有的月桂酸酯类和硫醇类有机锡稳定剂和β-二酮类化合物辅助热稳定剂的优势,达到了同时使用两种物质的效果,使用更加方便;
2、β-二酮类有机锡PVC使用亚锡盐作为原料,避免了已有的月桂酸酯类和硫醇类有机锡稳定剂,在生产过程中需要使用含有烷基基团的有机锡化合物,如二甲基锡、四丁基锡和四辛基锡等甲酯锡或丁酯锡衍生物中间体,该类中间体生产过程中具有毒性大,有臭味(特别是硫醇类有机锡热稳定剂),产品稳定性不好等缺点;本发明使用的亚锡盐不但使用方便,而且无毒,做到了绿色环保;并且该稳定剂为固体,使用、运输、储存都很方便。
3、本发明的β-二酮类有机锡PVC热稳定剂的制备方法中,使用超声波能够有效避免反应生成的氯化铵包杂在产品中影响产品的质量,使用氮气伴随整个反应,在0℃条件下,溶剂不易挥发,通过氮气伴随溶剂挥发,不仅能够促进析晶,而且能够避免氧气影响β-二酮类化合物与亚锡离子结合,有效的得到很纯净的产品。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
向安装有搅拌装置的超声波反应容器中通入氮气,然后加入溶有1,3-二苯基-1,3-丙二酮22.5g(0.1mol)的二氯甲烷溶液300mL,加入氨水100mL后,于25℃的反应温度下向超声波反应容器中缓慢滴加溶有二水合氯化亚锡22.5g(0.1mol)的甲醇溶液300mL,滴加过程中开启搅拌装置和超声波发生装置,超声波发生装置的设定频率为20KHz,滴加完后,溶液此时为澄清状态,停止搅拌,保持超声波发生装置继续工作,缓慢降温至0℃,反应液静止,打开超声波反应容器上的排气孔,保持通入的氮气从排气孔排出,使氮气伴随一定量的反应溶剂排出超声波反应容器,逐渐有无色或淡黄色晶体析出,5h后析晶完全,抽滤反应液,滤饼用甲醇洗涤多次以洗去多余的亚锡盐,滤饼在室温下晾干后得到1,3-二苯基-1,3-丙二酮有机锡PVC热稳定剂27g。
实施例2
向安装有搅拌装置的超声波反应容器中通入氮气,然后加入溶有1,3-二苯基-1,3-丙二酮22.5g(0.1mol)的二氯甲烷溶液300mL,加入氨水100mL后,于0℃的反应温度下向超声波反应容器中缓慢滴加溶有二水合氯化亚锡12g(0.05mol)的甲醇溶液300mL,滴加过程中开启搅拌装置和超声波发生装置,超声波发生装置的设定频率为100KHz,滴加完后,溶液此时为澄清状态,停止搅拌,保持超声波发生装置继续工作,缓慢降温至0℃,反应液静止,打开超声波反应容器上的排气孔,保持通入的氮气从排气孔排出,使氮气伴随一定量的反应溶剂排出超声波反应容器,逐渐有无色或淡黄色晶体析出,5h后析晶完全,抽滤反应液,滤饼用甲醇洗涤多次以洗去多余的亚锡盐,滤饼在室温下晾干后得到1,3-二苯基-1,3-丙二酮有机锡PVC热稳定剂22g。
实施例3
向安装有搅拌装置的超声波反应容器中通入氮气,然后加入溶有1,3-二苯基-1,3-丙二酮22.5g(0.1mol)的二氯甲烷溶液300mL,加入氨水100mL后,于50℃的反应温度下向超声波反应容器中缓慢滴加溶有二水合氯化亚锡16g(0.066mol)的甲醇溶液300mL,滴加过程中开启搅拌装置和超声波发生装置,超声波发生装置的设定频率为80KHz,滴加完后,溶液此时为澄清状态,停止搅拌,保持超声波发生装置继续工作,缓慢降温至0℃,反应液静止,打开超声波反应容器上的排气孔,保持通入的氮气从排气孔排出,使氮气伴随一定量的反应溶剂排出超声波反应容器,逐渐有无色或淡黄色晶体析出,5h后析晶完全,抽滤反应液,滤饼用甲醇洗涤多次以洗去多余的亚锡盐,滤饼在室温下晾干后得到1,3-二苯基-1,3-丙二酮有机锡PVC热稳定剂28g。
实施例4
向安装有搅拌装置的超声波反应容器中通入氮气,然后加入溶有1,3-二苯基-1,3-丙二酮22.5g(0.1mol)的二氯甲烷溶液300mL,加入氨水100mL后,于25℃的反应温度下向超声波反应容器中缓慢滴加溶有二十水合硝酸亚锡40g(0.066mol)的甲醇溶液300mL,滴加过程中开启搅拌装置和超声波发生装置,超声波发生装置的设定频率为80KHz,滴加完后,溶液此时为澄清状态,停止搅拌,保持超声波发生装置继续工作,缓慢降温至0℃,反应液静止,打开超声波反应容器上的排气孔,保持通入的氮气从排气孔排出,使氮气伴随一定量的反应溶剂排出超声波反应容器,逐渐有无色或淡黄色晶体析出,5h后析晶完全,抽滤反应液,滤饼用甲醇洗涤多次以洗去多余的亚锡盐,滤饼在室温下晾干后得到1,3-二苯基-1,3-丙二酮有机锡PVC热稳定剂21g。
实施例5
向安装有搅拌装置的超声波反应容器中通入氮气,然后加入溶有1-苯基-3-17烷基-1,3-丙二酮38.5g(0.1mol)的二氯甲烷溶液300mL,加入氨水100mL后,于25℃的反应温度下向超声波反应容器中缓慢滴加溶有二水合氯化亚锡16g(0.066mol)的甲醇溶液300mL,滴加过程中开启搅拌装置和超声波发生装置,超声波发生装置的设定频率为80KHz,滴加完后,溶液此时为澄清状态,停止搅拌,保持超声波发生装置继续工作,缓慢降温至0℃,反应液静止,打开超声波反应容器上的排气孔,保持通入的氮气从排气孔排出,使氮气伴随一定量的反应溶剂排出超声波反应容器,逐渐有无色或淡黄色晶体析出,5h后析晶完全,抽滤反应液,滤饼用甲醇洗涤多次以洗去多余的亚锡盐,滤饼在室温下晾干后得到1-苯基-3-17烷基-1,3-丙二酮有机锡PVC热稳定剂46g。
实施例6
热稳定性测试
检测所需的PVC材料配方组成为:100重量的PVC材料、5重量份的增塑剂邻苯二甲酸二辛酯、3重量份的二氧化钛和一定量的热稳定剂,在180℃条件下在双辊炼胶机中塑炼至变色,观察颜色改变时所经历的时间的长短(时间越长说明稳定剂效果越好),上述每一份PVC材料所使用的稳定剂加入量如下表所示。
5% | 10% | 15% | |
传统铅复合稳定剂 | 10min | 18min | 21min |
钙锌复合稳定剂 | 12min | 20min | 24min |
传统有机锡稳定剂 | 15min | 24min | 32min |
1,3-二苯基-1,3-丙二酮有机锡稳定剂 | 13min | 21min | 27min |
1-苯基3-十七烷基-1,3-丙二酮有机锡稳定剂 | 16min | 22min | 30min |
由上表可以看出,本发明所得到的1,3-二苯基-1,3-丙二酮有机锡稳定剂和1-苯基3-十七烷基-1,3-丙二酮有机锡稳定剂作用效果超过了传统铅复合稳定剂,达到了传统有机锡稳定剂水平。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (5)
1.一种β-二酮类有机锡PVC热稳定剂的制备方法,其特征在于:所述的β-二酮类有机锡PVC热稳定剂的结构式为:,其中R为苯基或十七烷基;具体合成步骤为:向安装有搅拌装置的超声波反应容器中通入氮气,然后加入溶有β-二酮类化合物的二氯甲烷溶液和氨水,于0-50℃的反应温度下向超声波反应容器中滴加亚锡盐的甲醇溶液或亚锡盐的丙酮溶液,其中β-二酮类化合物与亚锡盐的投料摩尔比为1-2:1,滴加过程中开启搅拌装置和超声波发生装置,超声波发生装置的设定频率为20-100KHz,滴加完后停止搅拌,保持超声波发生装置继续工作,降温至0℃后打开超声波反应容器上的排气孔,保持通入的氮气从排气孔排出直至反应液析晶完全,抽滤反应液,滤饼用甲醇洗涤多次以洗去多余的亚锡盐,滤饼在室温下晾干后得到β-二酮类有机锡PVC热稳定剂。
2.根据权利要求1所述的β-二酮类有机锡PVC热稳定剂的制备方法,其特征在于:所述的亚锡盐为氯化亚锡、硫酸亚锡或硝酸亚锡。
3.根据权利要求1所述的β-二酮类有机锡PVC热稳定剂的制备方法,其特征在于:所述的反应温度为25℃。
4.根据权利要求1所述的β-二酮类有机锡PVC热稳定剂的制备方法,其特征在于:所述的超声波发生装置的设定频率为80KHz。
5.根据权利要求1所述的β-二酮类有机锡PVC热稳定剂的制备方法,其特征在于:所述的β-二酮类化合物与亚锡盐的投料摩尔比为1.5:1。
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