CN107286420A - 一种挤出吹塑小中空制品用高密度聚乙烯树脂 - Google Patents
一种挤出吹塑小中空制品用高密度聚乙烯树脂 Download PDFInfo
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Abstract
本发明涉及一种挤出吹塑小中空制品用高密度聚乙烯树脂，利用现有三井淤浆聚合装置两釜串联工艺，再串联一反应釜，第一反应釜仅加入乙烯，第二反应釜和第三反应釜加入乙烯和丁烯-1，通过第三反应釜的聚合来进一步拓宽HDPE的分子量分布，同时增加高分子量部分的共聚单体丁烯-1的含量，以达到挤出吹塑小中空制品用HDPE的要求。本发明的HDPE在力学性能上表现优异，拉伸屈服强度最高可达到28MPa，耐环境应力开裂性能超过200h，韧性显著提高，可广泛应用于小中空制品的成型加工。
Description
技术领域
本发明涉及一种高密度聚乙烯树脂，尤其是一种挤出吹塑小中空制品用高密度聚乙烯树脂。
背景技术
由于高密度聚乙烯(HDPE)其密度大，刚性、韧性好、加工性能好，因此常用于生产牛奶瓶、果汁瓶、化妆品瓶、药瓶、洗涤剂及食品容器、工业瓶等各类大中小型中空容器。HDPE小中空制品主要包括饮用水包装瓶、化妆品瓶和洗涤用品瓶、医药瓶等。HDPE小中空制品选择原料时需要进行两方面的考虑，首先是制品使用性能对材料的要求，包括力学性能、良好的强度、刚度、冲击韧性和抗蠕变性能可以保证制品的基本使用要求；耐化学腐蚀性，保证制品盛装各种液体不降解。
挤出-吹塑用的HDPE一般为中宽到宽的分子量分布范围，目前国内小中空制品用HDPE树脂有上海赛科HD5502FA、独山子石化HD5502GA、韩国大林5502HS、茂名石化HHM5502、上海金菲HHM5502、中沙天津5502XA等，但都存在韧性不够的问题，即拉伸屈服应力和耐环境应力开裂性能差的问题。
发明内容
本发明的目的是解决现有技术中HDPE树脂拉伸屈服应力和耐环境应力开裂性能差的问题，提供一种挤出吹塑小中空制品用高密度聚乙烯树脂，其具有优异的拉伸屈服应力和耐环境应力开裂性能。
技术方案
本发明利用现有三井淤浆聚合装置两釜串联工艺，再串联一反应釜，第一反应釜仅加入乙烯，第二反应釜和第三反应釜加入乙烯和丁烯-1，通过第三反应釜的聚合来进一步拓宽HDPE的分子量分布，同时增加高分子量部分的共聚单体丁烯-1的含量，以达到挤出吹塑小中空制品用HDPE的要求。
一种挤出吹塑小中空制品用高密度聚乙烯树脂，采用三釜串联的釜式淤浆聚合工艺，在第一反应釜中加入乙烯，在催化剂的作用下进行聚合，形成低分子量乙烯均聚物，在第二反应釜中加入乙烯和丁烯-1，共聚生成高分子量的乙烯共聚物，在第三反应釜中加入乙烯和丁烯-1；第一反应釜中氢气/乙烯体积比为2.0～8.0，反应釜温度为75～85℃，反应釜压力为0.55～0.75MPa；第二反应釜中氢气/乙烯体积比为0.08～0.5，反应釜温度为75～85℃，反应釜压力为0.3～0.5MPa；第三反应釜中氢气/乙烯体积比为0.06～0.4，反应釜温度为78～85℃，反应釜压力为0.3～0.4MPa，第二反应釜和第三反应釜中的1-丁烯的含量均为占各自加入乙烯的0.2～0.4wt％，往从第三反应釜出来的粉料加入复合加工助剂，然后经双螺杆挤出机挤出造粒，再经干燥、筛分后，得到产品。
本发明所述的催化剂中，主催化剂为本领域常用的Ziegler-Natta催化剂，例如北京化工研究院BCH或BCE催化剂、日本三井公司PZ或RZ催化剂，配制浓度为2.5～5mmolTi/LHX(1g催化剂含有55±10mgTi)；采用的助催化剂为三乙基铝，配制浓度为90～100mmolAl/LHX。
以HDPE粉料的重量为1000‰计，本发明中所述的复合加工助剂包含：0.3～1.0‰的抗氧剂1010，0.5～1.0‰的抗氧剂168，0.2～0.8‰的抗氧剂DHT，0.5～1.2‰的稳定剂，0.3～1.0‰的爽滑剂。
本发明所述抗氧剂1010为四[B-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇，熔点为110-125℃，分解温度大于220℃；所述抗氧剂168为三(2,4-二特丁基苯基)亚磷酸盐，分子量为647，熔点为181-186℃，分解温度大于300℃；所述抗氧剂BHT为2,6-二特丁基对-甲酚，分子量为220，熔点为69-70℃。
本发明所述稳定剂为硬脂酸钙或硬脂酸锌中的任意一种。
本发明所述爽滑剂为芥酸酰胺或油酸酰胺中的任意一种。
本发明中造粒工序，双螺杆挤出机的一区温度为165±10℃，二区温度为210±10℃，三区温度为180±10℃，模板温度为175±10℃。
本发明中的干燥工序中，干燥温度为90-100℃。
本发明中的筛分，是指先后过10目和30目筛。
本发明所述的聚乙烯工艺为扬子石化聚乙烯淤浆聚合三釜串联工艺，三个串联工艺可以实现高分子量部分共聚单体含量的提高，其最终产品呈现出多峰分布：低分子量均聚物、高分子量共聚物、超高分子量共聚物，可使HDPE具有优异的耐环境应力开裂性能。
本发明通过控制丁烯-1、氢气加入量，确定主催化剂加入量、辅助催化剂加入量、浆液浓度，实现丁烯-1含量在3.0～7.0％(wt％)之间、熔融指数在1.0～3.0g/10min(190℃，2.16Kg负荷下)之间用于挤出吹塑小中空制品用HDPE的工业化生产。本发明的HDPE在力学性能上表现优异，拉伸屈服强度最高可达到28MPa，耐环境应力开裂性能超过200h，与现有小中空制品用HDPE树脂相比，本发明的HDPE树脂的拉伸屈服应力提高7％-20％，耐环境应力开裂性能提高100％-400％，韧性显著提高，可广泛应用于小中空制品的成型加工。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1
聚合工艺条件
本实施例中的复合加工助剂为：0.5wt‰的抗氧剂1010，0.6wt‰的抗氧剂168，0.3wt‰的抗氧剂DHT，1.0wt‰的硬脂酸钙，0.5wt‰的芥酸酰胺。双螺杆挤出机的一区温度为165℃，二区温度为210℃，三区温度为180℃，模板温度为175℃。
实施例2
聚合工艺条件
本实施例中的复合加工助剂为：0.5wt‰的抗氧剂1010，0.6wt‰的抗氧剂168，0.3wt‰的抗氧剂DHT，1.0wt‰的硬脂酸锌，0.5wt‰的油酸酰胺。双螺杆挤出机的一区温度为165℃，二区温度为210℃，三区温度为180℃，模板温度为175℃。
实施例3
聚合工艺条件
本实施例中的复合加工助剂为：0.3wt‰的抗氧剂1010，0.9wt‰的抗氧剂168，0.5wt‰的抗氧剂DHT，0.6wt‰的硬脂酸钙，0.5wt‰的芥酸酰胺。双螺杆挤出机的一区温度为170℃，二区温度为215℃，三区温度为175℃，模板温度为180℃。
性能测试
将实施例制得的高密度聚乙烯树脂进行熔融指数、拉伸屈服强度及耐环境应力开裂测试，并与市售的5200B、上海赛科HD5502FA、独山子石化HD5502GA进行对比，其中，熔融指数按照GB/T3682-2000标准测试，测试条件为190℃、2.16Kg；丁烯-1含量用傅立叶红外光谱法测定；所述拉伸性能按照GB/T2546.2-2003标准测试，拉伸速度为50mm/min；所述耐环境应力开裂性能按照GB 1842-1999标准测试。
测试结果见下表：
Claims (7)
1.一种挤出吹塑小中空制品用高密度聚乙烯树脂，其特征在于，采用三釜串联的釜式淤浆聚合工艺，在第一反应釜中加入乙烯，在催化剂的作用下进行聚合，形成低分子量乙烯均聚物，在第二反应釜中加入乙烯和丁烯-1，共聚生成高分子量的乙烯共聚物，在第三反应釜中加入乙烯和丁烯-1；第一反应釜中氢气/乙烯体积比为2.0～8.0，反应釜温度为75～85℃，反应釜压力为0.55～0.75MPa；第二反应釜中氢气/乙烯体积比为0.08～0.5，反应釜温度为75～85℃，反应釜压力为0.3～0.5MPa；第三反应釜中氢气/乙烯体积比为0.06～0.4，反应釜温度为78～85℃，反应釜压力为0.3～0.4MPa，第二反应釜和第三反应釜中的1-丁烯的含量均为占各自加入乙烯的0.2～0.4wt％，往从第三反应釜出来的粉料加入复合加工助剂，然后经双螺杆挤出机挤出造粒，再经干燥、筛分后，得到产品。
2.如权利要求1所述的挤出吹塑小中空制品用高密度聚乙烯树脂，其特征在于，以HDPE粉料的重量为1000‰计，所述复合加工助剂包含：0.3～1.0‰的抗氧剂1010，0.5～1.0‰的抗氧剂168，0.2～0.8‰的抗氧剂DHT，0.5～1.2‰的稳定剂，0.3～1.0‰的爽滑剂。
3.如权利要求2所述的挤出吹塑小中空制品用高密度聚乙烯树脂，其特征在于，所述稳定剂为硬脂酸钙或硬脂酸锌中的任意一种。
4.如权利要求2所述的挤出吹塑小中空制品用高密度聚乙烯树脂，其特征在于，所述爽滑剂为芥酸酰胺或油酸酰胺中的任意一种。
5.如权利要求1所述的挤出吹塑小中空制品用高密度聚乙烯树脂，其特征在于，造粒工序中，所述双螺杆挤出机的一区温度为165±10℃，二区温度为210±10℃，三区温度为180±10℃，模板温度为175±10℃。
6.如权利要求1所述的挤出吹塑小中空制品用高密度聚乙烯树脂，其特征在于，所述干燥温度为90-100℃。
7.如权利要求1至6任一项所述的挤出吹塑小中空制品用高密度聚乙烯树脂，其特征在于，所述筛分是指先后过10目和30目筛。
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| CN112679641A (zh) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | 中空制品用聚乙烯树脂及其组合物和制备方法 |
| CN117488428A (zh) * | 2023-11-02 | 2024-02-02 | 连云港石化有限公司 | 一种三釜串联连续生产窄分子量分布聚乙烯纤维的工艺 |
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| CN106317546A (zh) * | 2015-07-01 | 2017-01-11 | 中国石油化工股份有限公司 | 一种大型中空容器用高密度聚乙烯树脂 |
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| CN112679641B (zh) * | 2019-10-18 | 2023-01-20 | 中国石油化工股份有限公司 | 中空制品用聚乙烯树脂及其组合物和制备方法 |
| CN117488428A (zh) * | 2023-11-02 | 2024-02-02 | 连云港石化有限公司 | 一种三釜串联连续生产窄分子量分布聚乙烯纤维的工艺 |
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