CN110183364B - 一种硫醚类双酚丙烯酸酯多效抗氧剂及其制备方法 - Google Patents
一种硫醚类双酚丙烯酸酯多效抗氧剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种硫醚类双酚丙烯酸酯多效抗氧剂，具有如下式所示的分子结构：
本发明硫醚类双酚丙烯酸酯多效抗氧剂分子中既含有作为主抗氧剂的受阻酚官能团和辅助抗氧剂的硫醚键，同时也含有具有碳自由基捕捉功能的丙烯酸酚酯结构，在高分子材料加工及使用过程中可以起到三效合一的抗氧化作用，可以更好地保护高分子材料，避免制品的降解及老化，解决了单一功能抗氧剂对高分子材料抗氧化作用效果差的问题，并且对应的制备工艺反应温度低，能耗低，副产物过滤即可除去，不产生废水，溶剂可回收，绿色环保。
Description
技术领域
本发明涉及塑料助剂，尤其涉及一种硫醚类双酚丙烯酸酯多效抗氧剂及其制备方法。
背景技术
抗氧剂抗是一类聚合物助剂，当其在聚合物体系中仅少量存在时，就可延缓或抑制聚合物氧化过程的进行，从而阻止聚合物的老化并延长其使用寿命，又被称为防老剂。有机化合物的热氧化过程是一系列的自由基链式反应，在热或光的作用下，分子的化学键发生断裂，生成活泼的自由基，这些自由基可以引发一系列的自由基链式反应，导致有机化合物的结构和性质发生根本变化，抗氧剂的作用机理就是消除刚刚产生的自由基，阻止链式反应的进行，从而起到防止老化的作用。常见的受阻酚类抗氧剂防老化机理就是其官能团和自由基结合，但功能比较单一，防老化效果一般。
发明内容
本发明针对现有受阻酚类抗氧剂防老化效果单一的问题，提供一种硫醚类双酚丙烯酸酯多效抗氧剂及其制备方法。
本发明解决上述技术问题的技术方案如下：一种硫醚类双酚丙烯酸酯多效抗氧剂，其特征在于，其具有如式Ⅰ所示的分子结构：
其中，R1为C1-C5的直链或带有支链的烷基，R2为C1-C5的直链或带有支链的烷基。
具体地，所述硫醚类双酚丙烯酸酯多效抗氧剂具有如式a-e所示的分子结构：
本发明还涉及上述硫醚类双酚丙烯酸酯多效抗氧剂的制备方法，其步骤为：将硫醚类双酚化合物溶解于溶剂中，加入催化剂三乙胺和丙烯酸，控制温度为20℃-50℃，搅拌混合0.5-1.5h，向反应体系中滴加三氯氧磷，控制滴加时间为50-90min，滴加完成后升温至60℃-90℃，搅拌下反应1-4h，将反应液抽滤，将滤饼用正庚烷淋洗，对淋洗液减压蒸馏，将蒸馏残液在0-5℃下搅拌析晶，再次抽滤，收集滤饼，即得。涉及的主要反应为：
其中，所述硫醚类双酚化合物与丙烯酸、三氯氧磷的物质的量比为1:(1.1-1.4):(1.1-1.5)；所述硫醚类双酚化合物与所述三乙胺的物质的量比为1:(4-6)；所述溶剂为甲苯、二甲苯、三甲苯、苯、正庚烷或正壬烷中的一种。
本发明的有益效果是：本发明硫醚类双酚丙烯酸酯多效抗氧剂分子中既含有作为主抗氧剂的受阻酚官能团和辅助抗氧剂的硫醚键，同时也含有具有碳自由基捕捉功能的丙烯酸酚酯结构，在高分子材料加工及使用过程中可以起到三效合一的抗氧化作用，可以更好地保护高分子材料，避免制品的降解及老化，解决了单一功能抗氧剂对高分子材料抗氧化作用效果差的问题，并且对应的制备工艺反应温度低，能耗低，副产物过滤即可除去，不产生废水，溶剂可回收，绿色环保。
附图说明
图1为为实施例1化合物a的核磁共振图谱；图2为实施例1化合物a的液相色谱图。
具体实施方式
以下结合实例对本发明进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1化合物a的合成
将2,2’-硫代双(4-甲基-6-叔丁基苯酚)358.5g(1mol)加入到3L三口瓶中，再加入正庚烷1000ml，三乙胺404g(4mol)，丙烯酸86.5g(1.2mol)，搅拌升温至60℃，开始滴加三氯氧磷199g(1.3mol)，滴加时控温60～80℃，滴加时间1h，滴加完升温至85℃保温1.5h。反应结束后，待反应液稍冷却抽滤，滤饼为三乙胺盐，用正庚烷500ml淋洗，将有机相合并，减压蒸馏出正庚烷1200ml，将剩余残留液搅拌降温析晶，0到5℃下析晶，抽滤，得到产品338.3g，收率82％。
实施例2化合物b的合成
将2,2’-硫代双(4-乙基-6-叔丁基苯酚)386.5g(1mol)加入到3L三口瓶中，再加入正庚烷1100ml，三乙胺505g(5mol)，丙烯酸93.7g(1.3mol)，搅拌升温至65℃，开始滴加三氯氧磷199g(1.3mol)，滴加时控温65～80℃，滴加时间1h，滴加完升温至85℃保温1.5h。反应结束后，待反应液稍冷却抽滤，滤饼为三乙胺盐，用正庚烷500ml淋洗，将有机相合并，减压蒸馏出正庚烷1300ml，将剩余残留液搅拌降温析晶，2到5℃下析晶，得到产品373g，收率84.6％。
实施案例3化合物c的合成
将2,2’-硫代双(4，6-二叔丁基苯酚)414.5g(1mol)加入到3L三口瓶中，再加入甲苯1100ml，三乙胺535g(5.3mol)，丙烯酸93.7g(1.3mol)，搅拌升温至60℃，开始滴加三氯氧磷207g(1.35mol)，滴加时控温65～85℃，滴加时间1h，滴加完升温至90℃保温1.5h。反应结束后，待反应液稍冷却抽滤，滤饼为三乙胺盐，用甲苯600ml淋洗，将有机相合并，减压蒸馏出甲苯1200ml，将剩余残留液搅拌降温析晶，5到10℃下析晶，得到产品414.6g，收率88.5％。
实施案例4化合物d的合成
将2,2’-硫代双(4-叔戊基-6-叔丁基苯酚)430g(1mol)加入到3L三口瓶中，再加入甲苯1100ml，三乙胺550g(5.5mol)，丙烯酸96g(1.4mol)，搅拌升温至60℃，开始滴加三氯氧磷207g(1.35mol)，滴加时控温65-85℃，滴加时间1h，滴加完升温至50℃保温3h。反应结束后，待反应液稍冷却抽滤，滤饼为三乙胺盐，用甲苯600ml淋洗，将有机相合并，减压蒸馏出甲苯1200ml，将剩余残留液搅拌降温析晶，5-10℃下析晶，抽滤，得到产品414.6g，收率90.5％。
实施案例5化合物e的合成
将2,2’-硫代双(4，6-二丁基苯酚)430g(1mol)加入到3L三口瓶中，再加入甲苯1100ml，三乙胺550g(5.5mol)，丙烯酸96g(1.4mol)，搅拌升温至60℃，开始滴加三氯氧磷207g(1.35mol)，滴加时控温65-85℃，滴加时间1h，滴加完升温至50℃保温3h。反应结束后，待反应液稍冷却抽滤，滤饼为三乙胺盐，用甲苯600ml淋洗，将有机相合并，减压蒸馏出甲苯1200ml，将剩余残留液搅拌降温析晶，5-10℃下析晶，抽滤，得到产品414.6g，收率91.5％。
将上述实施例1-5制备抗氧剂和对比例1抗氧剂1010+DLTP以及对比例2抗氧剂1010+168分别应用于PP制品中，参照国家标准GB/T1727-92，进行制样，制样完成后长期热氧老化实验(LTTS，参照GB/T7141-2008)，实验结束后进行性能对比，如表1所示。从表中数据对比结果表明，添加0.5％本发明产物的样品的长期热氧老化性能是空白样的约10倍，是对比例1传统受阻酚类加硫代酯类抗氧剂的约1.3倍，是对比例2传统受阻酚类加亚磷酸酯类抗氧剂的约4倍，具有较好的抗氧化性能。
表1.实施例与对比例抗氧剂抗老化性能对比
将实施例1化合物a进行核磁共振检测，图谱如图1所示，具体解析如下：δ1.35-9.44(D，9H，3CH3)；δ1.41-9.11(D，9H，3CH3)；δ2.20-3.00(T，3H，CH3)；δ2.26-2.99(T，3H，CH3)；δ3.70-1.83(S，2H，＝CH2)；δ6.1-0.98(D，H，＝CH)；δ6.45-0.97(M，H，Ar-OH)；δ6.71-1.56(D，H，Ar-H)；δ6.81-1.00(D，H，Ar-H)；δ7.11-0.99(D，H，Ar-H)；δ7.20-1.02(D，H，Ar-H)。根据上述数据可以确定产物的分子结构与目标化合物一致。
将实施例1化合物a进行液相色谱检测，图谱如图2所示，化合物的出峰保留时间为10.434min，且通过归一法计算，纯度为99.574％，纯度较高，具体数据参见表2。
表2.实施例1化合物a的液相色谱浓度数据
| 峰号 | 保留时间 | 面积 | 高度 | 浓度 |
| 1 | 2.673 | 1496 | 197 | 0.006 |
| 2 | 3.137 | 2942 | 713 | 0.012 |
| 3 | 3.247 | 8738 | 755 | 0.037 |
| 4 | 3.625 | 12794 | 1552 | 0.054 |
| 5 | 3.825 | 2746 | 398 | 0.012 |
| 6 | 4.581 | 3017 | 269 | 0.013 |
| 7 | 5.019 | 5626 | 255 | 0.024 |
| 8 | 7.239 | 48152 | 2742 | 0.203 |
| 9 | 8.145 | 6417 | 311 | 0.027 |
| 10 | 9.343 | 9030 | 461 | 0.038 |
| 11 | 10.434 | 23610885 | 1165433 | 99.574 |
| 总计 | 23711842 | 1173086 |
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (2)
1.一种硫醚类双酚丙烯酸酯多效抗氧剂，其特征在于，其具有如式c-e所示的分子结构：
2.一种如权利要求1所述的硫醚类双酚丙烯酸酯多效抗氧剂的制备方法，其特征在于，其步骤为：将硫醚类双酚化合物溶解于溶剂中，加入催化剂三乙胺和丙烯酸，控制温度为20℃-50℃，搅拌混合0.5-1.5h，向反应体系中滴加三氯氧磷，控制滴加时间为50-90min，滴加完成后升温至60℃-90℃，搅拌下反应1-4h，将反应液抽滤，将滤饼用正庚烷淋洗，对淋洗液减压蒸馏，将蒸馏残液在0-5℃下搅拌析晶，再次抽滤，收集滤饼，即得；
所述硫醚类双酚化合物与丙烯酸、三氯氧磷的物质的量比为1:(1.1-1.4):(1.1-1.5)；
所述硫醚类双酚化合物与所述三乙胺的物质的量比为1:(4-6)；
所述溶剂为甲苯、二甲苯、三甲苯、苯、正庚烷或正壬烷中的一种。
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