CN108299496B - 含有亚磷酸有机酯抗氧剂及合成方法 - Google Patents
含有亚磷酸有机酯抗氧剂及合成方法 Download PDFInfo
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Abstract
本发明一种新型的高性能含磷抗氧剂‑双季戊四醇三亚磷酸脂肪醇酯,主要用作聚乙烯、聚丙烯、聚氯乙烯、ABS树脂和聚酯等各种合成树脂的抗氧剂。它对防止氧化,改善色泽等具有突出的作用;其本身具有较高的热稳定性,耐侯性及耐水解稳定性,因此加工稳定性好。产品因具双季戊四醇结构与高分子量特性，十分适合要求高温加工的聚合材料应用，由于含三亚磷酸酯结构，烷基三价磷含量较高，从而使抗氧效果更突出与高效。产品在结构上不含烷基苯酚，安全无毒。主要适用ABS、PS、HIPS、NBR、SBS、PP、PE、LLDPE、PVC、PC、PA、PET、UP、酰胺纤维、聚酯纤维、粘合剂、涂料、油墨，复合用助剂生产加工；钙锌稳定剂复配。
Description
技术领域
本发明属于精细化工技术领域，具体是指一种含有亚磷酸有机酯抗氧剂-双季戊四醇三亚磷酸脂肪醇酯及其合成方法。
背景技术
亚磷酸酯类抗氧剂是抗氧剂品种内发展较快的一类产品，全球抗氧剂的年增长率在5%左右，而亚磷酸酯类抗氧化剂年增长率达到7%以上，其发展速度在整个抗氧化剂品种中具领先位置。由于塑料产能和产量的快速增长，刺激和拉动了抗氧剂的生产和消费的增长，现国内抗氧剂的增长保持在10%的增长率。国内亚磷酸酯类抗氧剂受到越来越多的关注，但现亚磷酸酯类抗氧剂大多都是受阻酚类，双酚类和含苯类的亚磷酸酯抗氧剂，这类产品虽有好的抗氧性能，但因含有酚和苯的成份，严格地讲都是有毒的产品。而无毒环保的亚磷酸酯现在还很少，无法满足日益增长的橡塑工业发展对无毒抗氧剂的需求。加上现这类产品大多是液体产品，有刺鼻的亚磷酸味，分子量不大，在使用中会发生抽出和迁移的缺陷，从而影响了产品的推广使用。本产品的开发就是为了弥补这些不足，充分利用产品中双季戊四醇的多元醇的结构特性优势，开发出较大分子量的树枝型的无苯，无酚，环保无毒的无味的固体的亚磷酸酯类的抗氧剂。以适应人们对产品无毒，环保的要求。
发明内容
本发明的目的在于克服现有技术中存在的上述不足，而提供一种具有较高的热稳定性,耐侯性及耐水解稳定性，主要用作聚乙烯、聚丙烯、聚氯乙烯、ABS树脂和聚酯等各种合成树脂的亚磷酸酯类的抗氧剂。
本发明一种含有亚磷酸有机酯抗氧剂，其特征是名称为：双季戊四醇三亚磷酸脂肪醇酯，其分子结构式是：
亚磷酸-脂肪醇酯
║
双季戊四醇 ═亚磷酸-脂肪醇酯
║
亚磷酸-脂肪醇酯
分子量为：1148；
含磷量为：8.1%。
本发明含有亚磷酸有机酯抗氧剂的合成方法分为二步合成：第一步是双季戊四醇与亚磷酸三乙酯的酯化合成，制取双季戊四醇三亚磷酸乙酯。其化学反应方程式：
双季戊四醇 + 3亚磷酸三乙酯 —→ 双季戊四醇三亚磷酸乙酯 + 6乙醇；
第一步的反应过程是：在装有电动搅拌、电加热、回流冷凝器、测温系统的反应瓶中，将双季戊四醇与亚磷酸三乙酯按摩尔比1：3配比加入反应瓶中进行酯化反应，催化剂用量0.3-1.0%，反应温度100-160℃，反应时间60-180分钟，反应结束后冷却至100℃以下，得到产物双季戊四醇三亚磷酸乙酯；
第二步是双季戊四醇三亚磷酸乙酯与脂肪醇合成，制取双季戊四醇三亚磷酸脂肪醇酯。其化学反应方程式：
双季戊四醇三亚磷酸乙酯 + 3脂肪醇酯
—→双季戊四醇三亚磷酸脂肪醇酯+3乙醇；
第二步的反应过程是：在装有电动搅拌、电加热、回流冷凝器、测温系统的反应瓶中，在第一步反应得到的产物双季戊四醇三亚磷酸乙酯与脂肪醇按摩尔比1：3配比，将脂肪醇加入到第一步反应产物的反应瓶中进行酯化反应，催化剂用量0.3-1.0%，反应温度140-220℃，反应时间120-210分钟，反应结束后冷却至100℃以下，经恒温烘箱保温过滤，得到亚磷酸有机酯抗氧剂产物—双季戊四醇三亚磷酸脂肪醇酯；第一步的反应过程是用磷酸作催化剂，用量为物料总量的0.4-0.6% ；第二步的反应过程是用钛酸四丁酯作催化剂，用量为物料总量的0.3-0.6% 。
作为优选，所述的催化剂还包括：氢氧化钠、磷酸、硫酸氢钠、酞酸四丁酯、酞酸异丙酯、氯化亚锡、氧化亚锡。
作为优选，所述的脂肪醇还包括：丁醇、异丁醇、辛醇、异辛醇、月桂醇、十六醇、十八醇、十二羟基硬脂醇。不同碳链的脂肪醇，得到液体或固体的产品。
作为优选，所述的原料配比按摩尔比来计算，1摩尔的量就是指该化合物的分子量。如十八醇分子量为270，则1摩尔十八醇即为270。双季戊四醇分子量为254，则1摩尔双季戊四醇即为254。亚磷酸三乙酯分子量为166，则1摩尔亚磷酸三乙酯即为166。不同的脂肪醇可用其分子量来进行计量。
本发明可作为橡塑制品加工的抗氧化剂、辅助稳定剂及润滑剂使用。
本发明与现有技术相比，具有以下优点和效果：1、本发明主要用作聚乙烯、聚丙烯、聚氯乙烯、ABS树脂和聚酯等各种合成树脂的辅助抗氧剂，它对防止氧化,改善色泽等具有突出的作用;其本身具有较高的热稳定性,耐侯性及耐水解稳定性,因此加工稳定性好；2、产品因具双季戊四醇结构与高分子量特性，十分适合要求高温加工的聚合材料应用，由于含三亚磷酸酯结构，烷基三价磷含量较高，从而使抗氧效果更突出与高效；3、产品在结构上不含烷基苯、酚，安全无毒。主要适用ABS、PS、HIPS、NBR、SBS、PP、PE、LLDPE、PVC、PC、PA、PET、UP、酰胺纤维、聚酯纤维、粘合剂、涂料、油墨，复合用助剂生产加工；钙锌稳定剂复配。
具体实施方式
下面通过实施例对本发明作进一步的描述。
实例一。
在装有电动搅拌、电加热、回流冷凝器、测温系统、通氮气装置的反应瓶中，分别加入双季戊四醇84克，亚磷酸三乙酯163克，催化剂磷酸1克，加到反应瓶中，通入氮气进行酯化反应，控制反应温度100-180℃，反应时间180分钟，反应结束后冷却至100℃以下。然后加入硬脂醇（即十八醇）253克，加入催化剂钛酸四丁酯3.6克，通入氮气进行第二步酯化反应，反应温度150-210℃，反应时间180分钟，反应结束后冷却至100℃以下，经恒温烘箱80-100℃左右保温过滤，得到固体的亚磷酸有机酯抗氧剂产物—双季戊四醇三亚磷酸硬脂醇酯。
实例二。
在装有电动搅拌、电加热、回流冷凝器、测温系统、通氮气装置的反应瓶中，将双季戊四醇90克，亚磷酸三乙酯272克到反应瓶中，催化剂磷酸1.8克，通入氮气进行酯化反应，反应温度100-180℃，反应时间约180分钟，反应结束后冷却至100℃以下。然后加入辛醇138克，加入催化剂氯化亚锡0.7克，通入氮气进行第二步酯化反应，反应温度140-200℃，回流反应时间180分钟，反应结束后冷却至100℃以下，经恒温烘箱80℃左右保温过滤，得到液体亚磷酸有机酯抗氧剂产物—双季戊四醇三亚磷酸辛醇酯。
实例三。
在装有电动搅拌、电加热、回流冷凝器、测温系统、通氮气装置的反应瓶中，将双季戊四醇81克，亚磷酸三乙酯159克，催化剂磷酸3克，到反应瓶中，通入氮气进行酯化反应，反应温度100-180℃，反应时间约180分钟，反应结束后冷却至100℃以下。然后加入十二羟基硬脂醇260克，通入氮气进行第二步酯化反应，控制反应温度150-200℃，反应时间150分钟，然后在200℃拉真空30分钟，结束反应后冷却至100℃以下，经恒温烘箱100℃左右保温过滤，得到固体的亚磷酸有机酯抗氧剂产物—双季戊四醇三亚磷酸十二羟基硬脂醇酯。
Claims (2)
1.一种含有亚磷酸有机酯抗氧剂的合成方法，其特征是，所述含有亚磷酸有机酯抗氧剂名称为：双季戊四醇三亚磷酸脂肪醇酯，其分子结构式是：
分子量为：1148；
含磷量为：8.1％；
所述合成方法分为二步合成：第一步是双季戊四醇与亚磷酸三乙酯的酯化合成，制取双季戊四醇三亚磷酸乙酯，其化学反应方程式：
双季戊四醇+3亚磷酸三乙酯—→双季戊四醇三亚磷酸乙酯+6乙醇
第一步的反应过程是：在装有电动搅拌、电加热、回流冷凝器、测温系统的反应瓶中，将双季戊四醇与亚磷酸三乙酯按摩尔比1：3配比加入反应瓶中进行酯化反应，用量为物料总量0.4-0.6％的催化剂磷酸，反应温度100-160℃，反应时间60-180分钟，反应结束后冷却至100℃以下，得到产物双季戊四醇三亚磷酸乙酯；
第二步是双季戊四醇三亚磷酸乙酯与脂肪醇合成，制取双季戊四醇三亚磷酸脂肪醇酯，其化学反应方程式：
双季戊四醇三亚磷酸乙酯+3脂肪醇酯
—→双季戊四醇三亚磷酸脂肪醇酯+3乙醇
第二步的反应过程是：在装有电动搅拌、电加热、回流冷凝器、测温系统的反应瓶中，在第一步反应得到的产物双季戊四醇三亚磷酸乙酯与脂肪醇按摩尔比1：3配比，将脂肪醇加入到第一步反应产物的反应瓶中进行酯化反应，用量为物料总量0.3-0.6％的催化剂钛酸四丁酯，反应温度140-220℃，反应时间120-210分钟，反应结束后冷却至100℃以下，经恒温烘箱保温过滤，得到亚磷酸有机酯抗氧剂产物—双季戊四醇三亚磷酸脂肪醇酯。
2.根据权利要求1所述的含有亚磷酸有机酯抗氧剂的合成方法，其特征是所述的脂肪醇还可以是：丁醇、异丁醇、辛醇、异辛醇、月桂醇、十六醇、十二羟基硬脂醇。
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