CN109054186B - 一种功能性聚烯烃固体降解剂 - Google Patents
一种功能性聚烯烃固体降解剂 Download PDFInfo
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Abstract
本发明涉及一种功能性聚烯烃固体降解剂，属于降解剂技术领域。本发明所述功能性聚烯烃固体降解剂，按重量份，由下述组份组成：聚丙烯30‑70份、过氧化物5‑20份、抗氧剂10‑30份、爽滑剂/抗静电剂5‑15份、酸清除剂5‑15份；其中：所述过氧化物为二叔戊基过氧化物、2,5‑二甲基‑2,5双(叔丁基过氧基)己烷和过氧化二异丙苯中的至少一种。使用本发明所述功能性聚烯烃固体降解剂生产的高熔指聚丙烯产品分子量分布窄，同时，具有优异的抗氧化性能，在200℃时，制品的氧化诱导期大于8min。
Description
技术领域
本发明涉及一种功能性聚烯烃固体降解剂，属于降解剂技术领域。
背景技术
高质量的聚丙烯纤维要求聚丙烯产品有较高的熔融指数且分子量分布窄。通常生产符合该要求的聚丙烯产品需要用降解法，即通过在宽分子量低熔融指数的聚丙烯产品的挤出造粒过程中加入降解剂来实现生产分子量分布窄而熔融指数高的聚丙烯产品。
在降解法生产的高熔指聚丙烯工艺中，常用液态的有机过氧化物作为降解剂。由于液体过氧化物在添加时浓度较高，添加量小，要使降解剂均匀的分散在聚合物中比较困难。如果分散不均匀，可能造成产品的熔融指数不稳定、均一性差，影响连续化生产和产品质量的稳定性，由于分散不均造成的局部过度降解会使制品产生气味，另外也提过氧化物由于其较高的化学活性使其在运输、仓储和使用的过程中存在较高的危险性，极易燃烧甚至发生***。
发明内容
本发明通过提供一种新的固体降解剂，解决了上述问题。
本发明提供了一种功能性聚烯烃固体降解剂，所述功能性聚烯烃固体降解剂，按重量份，由下述组份组成：
其中：所述过氧化物为二叔戊基过氧化物、2,5-二甲基-2,5双(叔丁基过氧基)己烷和过氧化二异丙苯中的至少一种。
本发明所述过氧化物最优选为2,5-二甲基-2,5双(叔丁基过氧基)己烷。
本发明优选为所述抗氧剂为抗氧剂3114、抗氧剂330、抗氧剂1010、抗氧剂168、抗氧剂1076和抗氧剂264中的至少一种。
本发明优选为所述抗氧剂为抗氧剂3114、抗氧剂330和抗氧剂168。
本发明优选为所述抗氧剂3114、抗氧剂330和抗氧剂168的重量比为1：1：0.2-5。
本发明所述抗氧剂3114、抗氧剂330和抗氧剂168的重量比最优选为1：1：1。
本发明优选为所述爽滑剂/抗静电剂为单甘酯、芥酸酰胺或油酸酰胺。
本发明所述爽滑剂/抗静电剂最优选为单甘酯。
本发明优选为所述酸清除剂为硬脂酸钙或硬脂酸锌。
本发明所述酸清除剂最优选为硬脂酸钙。
本发明优选为所述聚丙烯在温度230℃，压力2.16kg下，熔融指数为1-10g/10min。。
本发明优选为所述功能性聚烯烃固体降解剂的形状为圆柱形，圆柱的底面直径为1-5mm，圆柱的高度为1-10mm。
本发明优选为所述功能性聚烯烃固体降解剂添加量为聚丙烯的0.1-8wt.％。
本发明有益效果为：
本发明所述功能性聚烯烃固体降解剂可以在挤出机中均匀分散在聚合物中，使聚合物的降解过程更加均一，同时，产生的小分子少、气味小，降解后的产品熔融指数更加稳定。
使用本发明所述功能性聚烯烃固体降解剂生产的高熔指聚丙烯产品分子量分布窄，同时，具有优异的抗氧化性能，在200℃时，制品的氧化诱导期大于8min。
本发明所述功能性聚烯烃固体降解剂不限于在生产高熔指聚丙烯产品中的应用，亦适用于其他使用降解法生产的热塑性制品的生产过程中。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
下述聚丙烯在温度230℃，压力2.16kg下，熔融指数为3g/10min。
下述过氧化物为2,5-二甲基-2,5双(叔丁基过氧基)己烷。
下述抗氧剂为抗氧剂3114、抗氧剂330和抗氧剂168，所述抗氧剂3114、抗氧剂330和抗氧剂168的重量比为1：1：1。
下述爽滑剂/抗静电剂为单甘酯。
下述酸清除剂为硬脂酸钙。
下述传统固体降解剂为申请公布号CN 102358791A公开的固体降解剂。
下述均聚聚丙烯T30S在温度230℃，压力2.16kg下，熔融指数为2.9g/10min。
下述无规共聚聚丙烯L6D20在温度230℃，压力2.16kg下，熔融指数为1.9g/10min。
下述嵌段共聚聚丙烯EPS30R在温度230℃，压力2.16kg下，熔融指数为2g/10min。
下述熔融指数测试参考GB/T 3682-2000。
下述氧化诱导期测试参考GB/T 19466.6-2009。
实施例1
一种功能性聚烯烃固体降解剂的制备方法，所述制备方法为：按重量份，将70份聚丙烯、10份过氧化物、20份抗氧剂、5份爽滑剂/抗静电剂与5份酸清除剂在挤压机中挤出造粒，得到圆柱形功能性聚烯烃固体降解剂颗粒，圆柱底面的直径为2-4mm，圆柱的高度为2-4mm。
应用例1
均聚高熔指聚丙烯的制备
将传统固体降解剂、抗氧剂、爽滑剂/抗静电剂、酸清除剂与均聚聚丙烯料T30S混合，所述传统固体降解剂的添加量为0.5wt.％，所述抗氧剂的添加量为0.24wt.％，所述爽滑剂/抗静电剂的添加量为0.05wt.％，所述酸清除剂的添加量为0.05wt.％，在挤出机中熔融造粒，得到均聚高熔指聚丙烯(对比品1)，抽取11个样品进行熔融指数测试，其结果见表1。
应用例2
均聚高熔指聚丙烯的制备
与应用例1的区别为：所述传统固体降解剂的添加量为0.6wt.％，得到均聚高熔指聚丙烯(对比品2)。
应用例3
均聚高熔指聚丙烯的制备
与应用例1的区别为：所述传统固体降解剂的添加量为0.7wt.％得到均聚高熔指聚丙烯(对比品3)。
应用例4
均聚高熔指聚丙烯的制备
将实施例1制备的功能性聚烯烃固体降解剂与均聚聚丙烯料T30S混合，所述功能性聚烯烃固体降解剂的添加量为1.2wt.％，在挤出机中熔融造粒，得到均聚高熔指聚丙烯(样品1)，抽取11个样品进行熔融指数测试，其结果见表1。
应用例5
均聚高熔指聚丙烯的制备
与应用例4的区别为：所述功能性聚烯烃固体降解剂的添加量为1.3wt.％，得到均聚高熔指聚丙烯(样品2)。
应用例6
均聚高熔指聚丙烯的制备
与应用例4的区别为：所述功能性聚烯烃固体降解剂的添加量为1.4wt.％，得到均聚高熔指聚丙烯(样品3)。
表1均聚高熔指聚丙烯的熔融指数测试结果
应用例7
无规共聚高熔指聚丙烯的制备
将传统固体降解剂、抗氧剂、爽滑剂/抗静电剂、酸清除剂与无规共聚聚丙烯料L6D20混合，所述传统固体降解剂的添加量为0.5wt.％，所述抗氧剂的添加量为0.24wt.％，所述爽滑剂/抗静电剂的添加量为0.05wt.％，所述酸清除剂的添加量为0.05wt.％，在挤出机中熔融造粒，得到无规共聚高熔指聚丙烯(对比品4)，抽取11个样品进行熔融指数测试，其结果见表2。
应用例8
无规共聚高熔指聚丙烯的制备
与应用例7的区别为：所述传统固体降解剂的添加量为0.6wt.％，得到无规共聚高熔指聚丙烯(对比品5)。
应用例9
无规共聚高熔指聚丙烯的制备
与应用例7的区别为：所述传统固体降解剂的添加量为0.7wt.％，得到无规共聚高熔指聚丙烯(对比品6)。
应用例10
无规共聚高熔指聚丙烯的制备
将实施例1制备的功能性聚烯烃固体降解剂与无规共聚聚丙烯料L6D20混合，所述功能性聚烯烃固体降解剂的添加量为1.2wt.％，在挤出机中熔融造粒，得到无规共聚高熔指聚丙烯(样品4)，抽取11个样品进行熔融指数测试，其结果见表2。
应用例11
无规共聚高熔指聚丙烯的制备
与应用例10的区别为：所述功能性聚烯烃固体降解剂的添加量为1.3wt.％，得到无规共聚高熔指聚丙烯(样品5)。
应用例12
无规共聚高熔指聚丙烯的制备
与应用例10的区别为：所述功能性聚烯烃固体降解剂的添加量为1.4wt.％，得到无规共聚高熔指聚丙烯(样品6)。
表2共聚高熔指聚丙烯的熔融指数测试结果
应用例13
嵌段共聚高熔指聚丙烯的制备
将传统固体降解剂、抗氧剂、爽滑剂/抗静电剂、酸清除剂与嵌段共聚聚丙烯料EPS30R混合，所述传统固体降解剂的添加量为0.5wt.％，所述抗氧剂的添加量为0.24wt.％，所述爽滑剂/抗静电剂的添加量为0.05wt.％，所述酸清除剂的添加量为0.05wt.％，在挤出机中熔融造粒，得到嵌段共聚高熔指聚丙烯(对比品7)，抽取11个样品进行熔融指数测试，其结果见表3。
应用例14
嵌段共聚高熔指聚丙烯的制备
与应用例13的区别为：所述传统固体降解剂的添加量为0.6wt.％，得到嵌段共聚高熔指聚丙烯(对比品8)。
应用例15
嵌段共聚高熔指聚丙烯的制备
与应用例13的区别为：所述传统固体降解剂的添加量为0.7wt.％，得到嵌段共聚高熔指聚丙烯(对比品9)。
应用例16
嵌段共聚高熔指聚丙烯的制备
将实施例1制备的功能性聚烯烃固体降解剂与嵌段共聚聚丙烯料EPS30R混合，所述功能性聚烯烃固体降解剂的添加量为1.2wt.％，在挤出机中熔融造粒，得到嵌段共聚高熔指聚丙烯(样品7)，抽取11个样品进行熔融指数测试，其结果见表3。
应用例17
嵌段共聚高熔指聚丙烯的制备
与应用例16的区别为：所述功能性聚烯烃固体降解剂的添加量为1.3wt.％，得到嵌段共聚高熔指聚丙烯(样品8)。
应用例18
嵌段共聚高熔指聚丙烯的制备
与应用例16的区别为：所述功能性聚烯烃固体降解剂的添加量为1.4wt.％，得到嵌段共聚高熔指聚丙烯(样品9)。
表3嵌段共聚高熔指聚丙烯的熔融指数测试结果
应用例1-18制备的产品在200℃时，测试其氧化诱导期，结果见表4。
表4应用例1-18制备的产品在200℃时的氧化诱导时间
Claims (6)
1.一种功能性聚烯烃固体降解剂，其特征在于：所述功能性聚烯烃固体降解剂，按重量份，由下述组份组成：
其中：
所述过氧化物为二叔戊基过氧化物和2,5-二甲基-2,5双(叔丁基过氧基)己烷中的至少一种；
所述抗氧剂3114、抗氧剂330和抗氧剂168的重量比为1：1：1。
2.根据权利要求1所述的功能性聚烯烃固体降解剂，其特征在于：所述爽滑剂/抗静电剂为单甘酯、芥酸酰胺或油酸酰胺。
3.根据权利要求2所述的功能性聚烯烃固体降解剂，其特征在于：所述酸清除剂为硬脂酸钙或硬脂酸锌。
4.根据权利要求3所述的功能性聚烯烃固体降解剂，其特征在于：所述聚丙烯在温度230℃，压力2.16kg下，熔融指数为1-10g/10min。
5.根据权利要求4所述的功能性聚烯烃固体降解剂，其特征在于：所述功能性聚烯烃固体降解剂的形状为圆柱形，圆柱的底面直径为1-5mm，圆柱的高度为1-10mm。
6.根据权利要求5所述的功能性聚烯烃固体降解剂，其特征在于：所述功能性聚烯烃固体降解剂添加量为聚丙烯的0.1-8wt.％。
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| EP0185434A2 (en) * | 1984-12-19 | 1986-06-25 | Shell Internationale Researchmaatschappij B.V. | Controlled cracking of alpha-olefin polymers |
| CN1451689A (zh) * | 2003-05-09 | 2003-10-29 | 东华大学 | 超高熔融指数聚丙烯及其制备方法 |
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| EP0185434A2 (en) * | 1984-12-19 | 1986-06-25 | Shell Internationale Researchmaatschappij B.V. | Controlled cracking of alpha-olefin polymers |
| CN1451689A (zh) * | 2003-05-09 | 2003-10-29 | 东华大学 | 超高熔融指数聚丙烯及其制备方法 |
| CN101429308A (zh) * | 2007-11-08 | 2009-05-13 | 中国石油天然气股份有限公司 | 一种聚丙烯降解母粒的制造方法 |
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