CN109679186A - 一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料 - Google Patents
一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料 Download PDFInfo
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Abstract
本发明涉及功能性母料领域，具体的说是一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料。由如下质量份数的原料制成：聚乙烯树脂80～90份、改性树脂10～20份、复配光稳定剂0.5～5份、复配抗氧剂0.5～3份、润滑剂0.1～2份和颜料0.1～2份，所述复配光稳定剂选自2‑羟基‑4‑正辛氧基二苯甲酮、2‑（2’‑羟基‑3’，5’‑二茂基苯基）苯并三唑、2‑（2’‑羟基‑3’‑叔丁基‑5’‑甲基苯基）‑5‑氯代苯并三唑中的一种与癸二酸双（2,2,6,6,‑四甲基‑4‑哌啶酯）、4‑苯甲酰氧基‑2,2,6,6‑四甲哌啶、Tinuvin144、Tinuvin622、Chimassorb944中的一种复配而成。本发明同现有技术相比，具有长期抗紫外光老化、抗热氧老化作用，防止产品变色、发硬、发粘、变脆、鼓包、失去强度、分化的功能。
Description
技术领域
本发明涉及功能性母料领域，具体的说是一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料。
背景技术
太阳光中的紫外线是引起高分子材料发生老化的主要原因，高分子材料会吸收紫外线而引发自动氧化，导致聚合物降解，这一过程称为光氧化还原或光老化。紫外线虽然仅占阳光的5%左右，但是紫外线的能量足以破坏聚合物的化学键，使其分子键断裂、交联，从而使得其力学性能发生改变，同时颜色也会发生改变。
氧气存在于我们周围，高分子材料在制造、加工、储存及应用过程中不可避免地要与氧接触，氧会引起材料降解，在氧化降解过程中，高分子材料与氧的反映是一个自动催化过程，少量的氧就能使材料的强度、外观等性能发生变化。
中国专利2011102905461介绍了一种用于制造管材专用聚乙烯树脂的母料的制备方法，采用一种改进的组合光稳定剂，解决了非黑色PE 管材耐光老化性能较难以达到与黑色PE 管材相同水平，其抗紫外线的组合光稳定剂仅包含苯并三唑类和受阻胺类，只能起到吸收紫外光和捕获活性自由基，产生稳定的分子化合物的目的。并且，其主体是聚乙烯树脂，在颜料、助剂的添加量和母粒的制造浓度上存在缺陷。中国专利2011102905565介绍了一种用于制造管材专用聚乙烯树脂的母料，同样存在上述的缺陷。
发明内容
本发明为克服现有技术的不足，设计一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，具有长期抗紫外光老化、抗热氧老化作用，使聚乙烯添加该功能母料后避免在大气环境或太阳紫外线的照射下发生力学性能的恶化。
为实现上述目的，设计一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是由如下质量份数的原料制成：聚乙烯树脂80～90份、改性树脂10～20份、复配光稳定剂0.5～5份、复配抗氧剂0.5～3份、润滑剂0.1～2份和颜料0.1～2份，所述复配光稳定剂选自2-羟基-4-正辛氧基二苯甲酮、2-（2’-羟基-3’，5’-二茂基苯基）苯并三唑、2-（2’-羟基-3’-叔丁基-5’-甲基苯基）-5-氯代苯并三唑中的一种与癸二酸双（2,2,6,6,-四甲基-4-哌啶酯） 、4-苯甲酰氧基-2,2,6,6-四甲哌啶、Tinuvin144、Tinuvin622、Chimassorb944中的一种复配而成；所述复配抗氧剂选自四[3-(3’5’-二叔丁基-4’-羟基苯基)丙酸]季戊四醇、1,3,5-三甲基-2,4,6-三（3,5-二叔丁基-4-羟基苄基）苯的一种与β-（4-羟基-3,5-二叔丁基苯基）丙酸正十八碳醇酯、4,4’-硫代双(6-叔丁基-3-甲基苯酚)的一种复配而成；所述颜料选择炭黑、透橙、透红、铬黄中的任一种或多种和钛白粉。
所述复配光稳定剂中，2-羟基-4-正辛氧基二苯甲酮、2-（2’-羟基-3’，5’-二茂基苯基）苯并三唑、2-（2’-羟基-3’-叔丁基-5’-甲基苯基）-5-氯代苯并三唑的含量为50～70%wt，癸二酸双（2,2,6,6,-四甲基-4-哌啶酯） 、4-苯甲酰氧基-2,2,6,6-四甲哌啶、Tinuvin144、Tinuvin622、Chimassorb944的含量为30～50%wt；所述复配抗氧剂中，四[3-(3’5’-二叔丁基-4’-羟基苯基)丙酸]季戊四醇、1,3,5-三甲基-2,4,6-三（3,5-二叔丁基-4-羟基苄基）苯的含量为40～60%wt，β-（4-羟基-3,5-二叔丁基苯基）丙酸正十八碳醇酯、4,4’-硫代双(6-叔丁基-3-甲基苯酚)的含量为40～60%wt。
所述聚乙烯树脂的相对密度为0.920～0.960之间，选用的聚乙烯树脂在190℃的温度下和2160g条件下测得的熔指为0.01-2.5g/10min。
所述改性树脂选自聚烯烃弹性体和乙烯醋酸乙烯共聚物中的任一种，所述聚烯烃弹性体的相对密度为0.860～0.900，在190℃的温度下和2160g条件下测得的熔指为0.5～5g/10min；所述乙烯醋酸乙烯共聚物中醋酸乙烯含量为10～40%，在190℃的温度下和2160g条件下测得的熔指为0.5～5g/10min。
所述润滑剂选自聚乙烯蜡、氧化聚乙烯蜡、硅氧烷、硅酮、氟弹性体中的一种或几种。
包括如下制备步骤：S1，将聚乙烯树脂、改性树脂、复配光稳定剂、复配抗氧剂、润滑剂和颜料按照上述配比充分混合得到混合物；S2，将混合物放入到双螺杆挤出机挤出造粒；S3，将造粒后得到的成品干燥至水分含量低于0.1%；S4，将干燥后的产品贮存在聚乙烯包装袋中。
所述步骤S2中双螺杆挤出机分为十个加热区，其中第一加热区的温度为50～70℃，第二加热区的温度为150～170℃第三加热区和第四加热区的温度均为180～220℃，第五加热区、第六加热区、第七加热区、第八加热区、第九加热区和挤出机机头的温度均为180～200℃，喂料时的频率为150～200HZ，挤出机的转速为300～400rpm。
所述步骤S3中干燥采用的方法为沸腾法干燥，沸腾的温度为50～60℃。
本发明同现有技术相比，具有长期抗紫外光老化、抗热氧老化作用，防止产品变色、发硬、发粘、变脆、鼓包、失去强度、分化的功能。
具体实施方式
本发明中颜料可以选用杜邦钛白粉、卡博特炭黑、汽巴固美透橙、汽巴固美透红、康纳铬黄等中任一种或多种混合。
本发明中聚乙烯树脂的相对密度为0.920～0.960之间，选用的聚乙烯树脂在190℃的温度下和2160g条件下测得的熔指为0.01-2.5g/10min。
本发明中树脂选自聚烯烃弹性体和乙烯醋酸乙烯共聚物中的任一种，所述聚烯烃弹性体的相对密度为0.860～0.900，在190℃的温度下和2160g条件下测得的熔指为0.5～5g/10min；所述乙烯醋酸乙烯共聚物中醋酸乙烯含量为10～40%，在190℃的温度下和2160g条件下测得的熔指为0.5～5g/10min。
实施例一：
称取聚乙烯树脂80份，改性树脂20份，2-羟基-4-正辛氧基二苯甲酮3.0份和癸二酸双（2,2,6,6,-四甲基-4-哌啶酯）2.0份作为复配光稳定剂5.0份，四[3-(3’5’-二叔丁基-4’-羟基苯基)丙酸]季戊四醇1.5份和4,4’-硫代双(6-叔丁基-3-甲基苯酚)1.5份作为复配抗氧剂3.0份，聚乙烯蜡作为润滑剂2.0份和颜料2.0份。
其中颜料可以选用杜邦钛白粉、卡博特炭黑、汽巴固美透橙、汽巴固美透红、康纳铬黄等中任一种或多种混合。
所述聚乙烯树脂的相对密度为0.940，190℃和2160g条件下的熔指为2.0g/10min。所述改性树脂选用聚烯烃弹性体，相对密度为0.880，190℃和2160g条件下的熔指为1.0 g/10min。
制备时，将称取的原料进行充分混合后，放入双螺杆挤出机内，进行造粒。依次经过九个加热区，温度分别为50℃、150℃、180℃、180℃、180℃、190℃、190℃、190℃、190℃，挤出机的机头温度保持在200℃，喂料的频率为200Hz，挤出机的转速为350rpm。
物料挤出后，将物料干燥至水分含量小于0.1%，干燥采用沸腾法干燥，干燥温度为50℃。然后将干燥好的物料放入到聚乙烯包装袋中。
实施例二：
称取聚乙烯树脂90份，改性树脂10份，2-羟基-4-正辛氧基二苯甲酮2.0份和Chimassorb944 2.0份作为复配光稳定剂4.0份，四[3-(3’5’-二叔丁基-4’-羟基苯基)丙酸]季戊四醇1.8份和4,4’-硫代双(6-叔丁基-3-甲基苯酚)1.2份作为复配抗氧剂3.0份，硅氧烷作为润滑剂1.0份和颜料2.0份。
其中颜料可以选用杜邦钛白粉、卡博特炭黑、汽巴固美透橙、汽巴固美透红、康纳铬黄等中任一种或多种混合。
所述聚乙烯树脂的相对密度为0.950，190℃和2160g条件下的熔指为1.8g/10min。所述改性树脂选用乙烯醋酸乙烯共聚物，醋酸乙烯含量为25%,相对密度为0.942，190℃和2160g条件下的熔指为3.0 g/10min。
制备时，将称取的原料进行充分混合后，放入双螺杆挤出机内，进行造粒。依次经过九个加热区，温度分别为50℃、150℃、190℃、190℃、190℃、200℃、200℃、200℃、190℃，挤出机的机头温度保持在190℃，喂料的频率为180Hz，挤出机的转速为300rpm。
物料挤出后，将物料干燥至水分含量小于0.1%，干燥采用沸腾法干燥，干燥温度为50℃。然后将干燥好的物料放入到聚乙烯包装袋中。
本发明中的颜料中，钛白粉采用的二氧化钛是光屏蔽剂，能够反射紫外光，犹如在聚合物和光辐射之间设立了一道屏障，使光不能直射到聚合物内部，从而有效的抑制光老化。其次，二苯甲酮类和苯并三唑类属于紫外光吸收剂，能够强烈的吸收紫外光，并将能量转化为无害的热能形式出去。第三，受阻胺类属于自由基捕获剂，一旦聚合物吸收了紫外线并分解产生出导致自动氧化反应的活性自由基后，为了阻止链式氧化反应蔓延下去，捕获剂将活性自由基抓获，使其形成稳定的分子化合物。通过此三道防线，大大提高抗紫外老化，使材料能够达到25年以上的户外使用寿命。
Claims (8)
1.一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是由如下质量份数的原料制成：聚乙烯树脂80～90份、改性树脂10～20份、复配光稳定剂0.5～5份、复配抗氧剂0.5～3份、润滑剂0.1～2份和颜料0.1～2份，所述复配光稳定剂选自2-羟基-4-正辛氧基二苯甲酮、2-（2’-羟基3’，5’-二茂基苯基）苯并三唑、2-（2’-羟基-3’-叔丁基-5’-甲基苯基）-5-氯代苯并三唑中的一种与癸二酸双（2,2,6,6,-四甲基-4-哌啶酯） 、4-苯甲酰氧基-2,2,6,6-四甲哌啶、Tinuvin144、Tinuvin622、Chimassorb944中的一种复配而成；所述复配抗氧剂选自四[3-(3’5’-二叔丁基-4’-羟基苯基)丙酸]季戊四醇、1,3,5-三甲基-2,4,6-三（3,5-二叔丁基-4-羟基苄基）苯的一种与β-（4-羟基-3,5-二叔丁基苯基）丙酸正十八碳醇酯、4,4’-硫代双(6-叔丁基-3-甲基苯酚)的一种复配而成；所述颜料选择炭黑、透橙、透红、铬黄中的任一种或多种和钛白粉。
2.根据权利要求1所述的一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是：所述复配光稳定剂中，2-羟基-4-正辛氧基二苯甲酮、2-（2’-羟基3’，5’-二茂基苯基）苯并三唑、2-（2’-羟基-3’-叔丁基-5’-甲基苯基）-5-氯代苯并三唑的含量为50～70%wt，癸二酸双（2,2,6,6,-四甲基-4-哌啶酯） 、4-苯甲酰氧基-2,2,6,6-四甲哌啶、Tinuvin144、Tinuvin622、Chimassorb944的含量为30～50%wt；所述复配抗氧剂中，四[3-(3’5’-二叔丁基-4’-羟基苯基)丙酸]季戊四醇、1,3,5-三甲基-2,4,6-三（3,5-二叔丁基-4-羟基苄基）苯的含量为40～60%wt，β-（4-羟基-3,5-二叔丁基苯基）丙酸正十八碳醇酯、4,4’-硫代双(6-叔丁基-3-甲基苯酚)的含量为40～60%wt。
3.根据权利要求1所述的一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是：所述聚乙烯树脂的相对密度为0.920～0.960之间，选用的聚乙烯树脂在190℃的温度下和2160g条件下测得的熔指为0.01-2.5g/10min。
4.根据权利要求1所述的一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是：所述改性树脂选自聚烯烃弹性体和乙烯醋酸乙烯共聚物中的任一种，所述聚烯烃弹性体的相对密度为0.860～0.900，在190℃的温度下和2160g条件下测得的熔指为0.5～5g/10min；所述乙烯醋酸乙烯共聚物中醋酸乙烯含量为10～40%，在190℃的温度下和2160g条件下测得的熔指为0.5～5g/10min。
5.根据权利要求1所述的一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是：所述润滑剂选自聚乙烯蜡、氧化聚乙烯蜡、硅氧烷、硅酮、氟弹性体中的一种或几种。
6.根据权利要求1所述的一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是包括如下制备步骤：S1，将聚乙烯树脂、改性树脂、复配光稳定剂、复配抗氧剂、润滑剂和颜料按照上述配比充分混合得到混合物；S2，将混合物放入到双螺杆挤出机挤出造粒；S3，将造粒后得到的成品干燥至水分含量低于0.1%；S4，将干燥后的产品贮存在聚乙烯包装袋中。
7.根据权利要求6所述的一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是：所述步骤S2中双螺杆挤出机分为十个加热区，其中第一加热区的温度为50～70℃，第二加热区的温度为150～170℃第三加热区和第四加热区的温度均为180～220℃，第五加热区、第六加热区、第七加热区、第八加热区、第九加热区和挤出机机头的温度均为180～200℃，喂料时的频率为150～200HZ，挤出机的转速为300～400rpm。
8.根据权利要求6所述的一种含有复配光稳定剂和复配抗氧剂的聚乙烯母料，其特征是：所述步骤S3中干燥采用的方法为沸腾法干燥，沸腾的温度为50～60℃。
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| CN113563661B (zh) * | 2020-04-28 | 2023-05-23 | 宿迁联盛科技股份有限公司 | 一种长效耐候的农膜用母料及其制备方法和应用 |
| CN114058077A (zh) * | 2020-08-03 | 2022-02-18 | 中国石油化工股份有限公司 | Sbs热塑性弹性体及其制备方法和防老剂及其应用 |
| CN114058077B (zh) * | 2020-08-03 | 2023-10-13 | 中国石油化工股份有限公司 | Sbs热塑性弹性体及其制备方法和防老剂及其应用 |
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