CN117384442A - 一种电晕母料组合物及其制备方法与应用 - Google Patents
一种电晕母料组合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于高分子材料的技术领域,具体涉及一种电晕母料组合物及其制备方法与应用。所述的电晕母料组合物:是由以下原料按照重量份数制成的:聚乙烯,80‑90份;电晕助剂1,2‑4份;电晕助剂2,10‑20份;抗氧剂,2‑4.5份;分散剂,0.5‑1份;润滑剂,0.5‑1份;电晕助剂2是由以下原料按照重量份造粒制得的:MLPE‑8060,80‑90份;抗静电剂lrgastat P18,10‑20份;交联剂DCP,0.05‑0.10份;聚乙二醇二丙烯酸酯,1‑3份。本发明的电晕母料组合物应用于PO膜中,能够增加PO膜表面的粗糙度,增加涂覆液的牢固度。本发明还提供其制备方法,制备的PO膜的流滴效果好。
Description
技术领域
本发明属于高分子材料的技术领域,具体涉及一种电晕母料组合物及其制备方法与应用。
背景技术
PO(聚烯烃)膜是采用高级烯烃的原材料及其他助剂,采用外喷涂烘干工艺而生产的一种新型农膜,因其具有雾度低、透明度高的优点,因此被广泛应用。为了增加PO膜的消雾、流滴能力,一般是在PO膜成膜后进行电晕助剂的涂覆,但是涂覆的附着力是有限的,随着使用时间延长,便会带来流滴失效的问题。
中国专利CN107629298A公开了一种刺激响应型PO功能性母料的制备方法,其原料为:载体聚合物(LDPE、HDPE、LLDPE与POE的混合物),响应性功能成分(亚氯酸钠、氯酸钠、高氯酸钠、柠檬酸、硬脂酸、月桂酸、硬脂酸锌),填料(滑石粉、高岭土、碳酸钙、硅粉、二氧化钛),助剂(PE蜡、石蜡、邻苯二甲酸二辛酯、二甲基硅油),经过高速搅拌,双螺杆挤出机挤出,造粒制得。仅是一种普通功能母料,其中的硬脂酸和硬脂酸锌没有电晕母料的功能,作用是稳定剂和耐老化,捕捉自由基,防止其破坏分子结构导致分子链断裂,以防农膜过早老化。
中国专利CN107383549A公开了一种单面电晕消光膜,由以下原料制成:聚乙烯,均聚聚丙烯,镁砂,乌洛托品,聚氧乙烯,高岭土,聚四氟乙烯树脂,聚乙烯醇,消光母料,滑石粉,硬脂酸,油酸酰胺。这是一种普通母料,所用的油酸酰胺也有电晕效果,但是游离基少,效果差。
发明内容
本发明要解决的技术问题是克服现有技术存在的上述缺陷,提供一种电晕母料组合物,将其应用于PO膜中,增加PO膜表面的粗糙度,增加涂覆液的牢固度。本发明还提供其制备方法,制备的PO膜的流滴效果好。
本发明所述的电晕母料组合物:是由以下原料按照重量份数制成的:聚乙烯,80-90份;电晕助剂1,2-4份;电晕助剂2,10-20份;抗氧剂,2-4.5份;分散剂,0.5-1份;润滑剂,0.5-1份;
电晕助剂2是由以下原料按照重量份在140℃下造粒制得的:MLPE-8060,80-90份;抗静电剂lrgastat P18,10-20份;交联剂DCP,0.05-0.10份;聚乙二醇二丙烯酸酯,1-3份。抗静电剂lrgastat P18是一种基于聚酰胺/聚醚嵌段酰胺的聚合物,德国巴斯夫公司产品。交联剂DCP(过氧化二异丙苯)用量过高,会使得聚乙烯交联度高,从而引起吹塑的薄膜表面不平整,造成产品质量问题;交联剂用量过低,则起不到交联作用,不能将抗静电剂固定到聚乙烯分子内部,从而达不到永久性抗流滴效果,聚乙二醇二丙烯酸酯为助交联剂。
聚乙烯是由LDPE、MLLDPE按照质量比(30-50):1混合得到的,其中LDPE的型号为2420D,市售厂家为中海壳牌石油化工有限公司,MLLDPE型号为2005HH,市售厂家为美国埃克森美孚公司。其中的MLLDPE为茂金属聚乙烯,增加母料各项物理性能,包括拉伸强度和直角撕裂强度。
电晕助剂1为硬脂酸二乙醇胺硬脂酸酯,制备过程为:将硬脂酸二乙醇胺和硬脂酸按照1:1.6的质量比加入反应容器,升温至60~80℃,在高分子金属(钴)络合物催化下,融化搅拌1.5~2h,冷却至室温制得。
抗氧剂为944,分子式为C35H69Cl3N8,提高母料组合物的耐老化能力。
润滑剂为PPA,市售厂家为上海鲁聚聚合物有限公司,属于高分子量润滑剂,作用是减少筒壁摩擦力,防止塑化过程糊料和结块。
分散剂是由聚乙烯蜡、芥酸酰胺按照质量比为(8-12):1混合得到的,其作用是使各种原料混合均匀,提高塑化效果。
所述的电晕母料组合物的制备方法,包括以下步骤:
(1)称取聚乙烯、电晕助剂1、电晕助剂2、抗氧剂、分散剂、润滑剂,加入到高速混合机中,混合5-10min,放出物料;
(2)将步骤(1)放出的物料加入到双螺杆挤出机中造粒,双螺杆温度设定为130-150℃,经水环冷却,切粒包装后,得到电晕母料组合物。
所述的电晕母料组合物的应用:将电晕母料组合物作为PO膜最外层原料,采用三层吹膜机吹塑薄膜,吹塑温度为175-195℃。
本发明的聚乙烯与抗静电剂在交联剂的作用下,通过聚乙二醇二丙烯酸酯紧密结合起来,形成轻微的三维网络交联结构。当电晕机放电时,产生低温等离子体,在塑料膜表面产生游离基相互交联,使表面粗糙,加入的电晕助剂含有大量的游离基,能有效增加PO膜表面的粗糙度,增加涂覆液的牢固度。
与现有技术相比,本发明具有的有益效果是:
(1)本发明制备的电晕母料组合物,以硬脂酸二乙醇胺硬脂酸酯为电晕助剂1,以聚乙烯与抗静电剂、交联剂DCP、聚乙二醇二丙烯酸酯为电晕助剂2,将其应用于PO膜吹塑过程中与聚乙烯相互交联使薄膜表面产生大量细微凸起,薄膜表面既光滑又有一定粗糙度,从而增加了涂覆液与薄膜之间的粘结牢固度。
(2)本发明制备的电晕母料组合物,加入的电晕助剂2作为表面活性剂,与电晕助剂1起到了较好的协同作用,不但增加了涂覆液与薄膜的结合牢固度,而且由于电晕助剂2中抗静电剂是通过微交联结合在聚乙烯树脂中,在薄膜使用过程中,抗静电剂不间断地析出表面,起到了较好的流滴效果,大大延长了流滴时间,起到永久性效果。
(3)本发明制备的电晕母料组合物,由于分散剂、抗氧剂的加入,有较好的分散效果,同时具有较好的热稳定效果和抗氧化效果。
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。
以下实施例和对比例所采用的原料或助剂均来自市售。,其来源如表1所示。
表1 原料来源
实施例1、实施例4、实施例5中的聚乙烯是由LDPE、MLLDPE按照质量比40:1混合得到;实施例2中的聚乙烯是由LDPE、MLLDPE按照质量比30:1混合得到;实施例3中的聚乙烯是由LDPE、MLLDPE按照质量比50:1混合得到。
电晕助剂1为硬脂酸二乙醇胺硬脂酸酯,制备过程为:将硬脂酸二乙醇胺和硬脂酸按照1:1.6的质量比加入反应容器,升温至70℃,加硬脂酸二乙醇胺和硬脂酸质量和的1%的2,2'-[1,2-乙二基双(次氮基次甲基)]双[6-甲氧基苯酚]钴络合物催化,搅拌2h,冷却至室温制得。所述的2,2'-[1,2-乙二基双(次氮基次甲基)]双[6-甲氧基苯酚]钴络合物为金锦乐(湖南)化学有限公司市售产品。
电晕助剂2为自制,实施例1、实施例4、实施例5中的电晕助剂2为MLPE-8060,80份;抗静电剂lrgastat P18,20份;交联剂DCP,0.10份;聚乙二醇二丙烯酸酯,2份,混合后在140℃造粒制得;实施例2和实施例3中的电晕助剂2为是由MLPE-8060,90份、抗静电剂lrgastatP18,10份、交联剂DCP,0.05份、聚乙二醇二丙烯酸酯,3份,混合后在140℃造粒制得。
润滑剂为PPA。抗氧剂为944。
实施例1、实施例4、实施例5中的分散剂为聚乙烯蜡与芥酸酰胺按质量比为10:1的复配物,实施例2的分散剂为聚乙烯蜡与芥酸酰胺按质量比为8:1的复配物,实施例3的分散剂为聚乙烯蜡与芥酸酰胺按质量比为12:1的复配物,其。
本发明的实施例的电晕母料组合物是由表2的原料按照重量份数制成的。
表2 实施例1-5的电晕母料组合物的原料
对比例的电晕母料组合物是由表3的原料按照重量份数制成的,其中的聚乙烯与电晕助剂2、分散剂均与实施例4相同。
表3 对比例1-7的电晕母料组合物的原料
将以上实施例1-5和对比例1-7用于制备PO膜,包括以下步骤:
(1)称取聚乙烯、电晕助剂1、电晕助剂2、抗氧剂、分散剂、润滑剂,加入到高速混合机中,混合5-10min,放出物料;
(2)将步骤(1)放出的物料加入到双螺杆挤出机中造粒,双螺杆温度设定为130-150℃,经水环冷却,切粒包装后,得到电晕母料组合物;
(3)将制得的电晕母料组合物作为PO膜最外层原料,采用三层吹膜机吹塑薄膜,吹塑温度175-195℃。
其中,实施例1-5的电晕母料组合物用于制备PO膜的工艺参数,如表4所示,其中对比例1-7的工艺参数均与实施例4相同。
表4 工艺参数
将以上实施例1-5和对比例1-7制备PO膜后,根据企业标准Q/ZBKL001-2022进行性能检测(外涂覆型厚度δ=0.10mm),检测结果如表5所示。摩擦牢度测试采用瑞士TESTEX检测公司TF411 Electronic Crockmeter,对照GB/T 3920-2008,摩擦牢度分为5级,5级最好。
表5 检测结果
从表5可以看出,本发明电晕母料制备的PO膜,具有较好的流滴效果,流滴失效时间都大于等于30d,超过标准要求,拉伸强度和直角撕裂强度高,均能符合标准要求,摩擦牢度均达到5级,人工加速老化后纵向断裂伸长率都大于400%,满足标准要求。实施例所有性能均优于对比例。对比例1由于只采用了电晕助剂1,其流滴失效时间明显减少,且摩擦牢度降低到3级;对比例2只采用了电晕助剂2,其流滴失效时间亦明显减少,摩擦牢度降低到3级;对比例3将电晕助剂1和2替换为油酸酰胺,流滴效果大幅降低,在第8天就失效了,不能满足标准;对比例4聚乙烯全部采用LDPE后,其撕裂强度明显较低;对比例5的不采用自制的电晕助剂2,只采用抗静电剂,没有微交联,进行普通共混,电晕助剂不能长时间固定在聚乙烯中,导致消耗较快,其流滴失效时间较实施例少三分之一,且力学性能及撕裂强度有所降低,对比例6只采用了油酸酰胺和抗氧剂,导致分散效果变差,导致PO膜的强度有所降低。对比例7只采用抗氧剂和润滑剂,导致PO膜的强度有所降低。
Claims (8)
1.一种电晕母料组合物,其特征在于:是由以下原料按照重量份数制成的:聚乙烯,80-90份;电晕助剂1,2-4份;电晕助剂2,10-20份;抗氧剂,2-4.5份;分散剂,0.5-1份;润滑剂,0.5-1份;
电晕助剂2是由以下原料按照重量份造粒制得的:MLPE-8060,80-90份;抗静电剂lrgastat P18,10-20份;交联剂DCP,0.05-0.10份;聚乙二醇二丙烯酸酯,1-3份。
2.根据权利要求1所述的电晕母料组合物,其特征在于:聚乙烯是由LDPE、MLLDPE按照质量比(30-50):1混合得到的。
3.根据权利要求1所述的电晕母料组合物,其特征在于:电晕助剂1为硬脂酸二乙醇胺硬脂酸酯。
4.根据权利要求1所述的电晕母料组合物,其特征在于:抗氧剂为944。
5.根据权利要求1所述的电晕母料组合物,其特征在于:润滑剂为PPA。
6.根据权利要求1所述的电晕母料组合物,其特征在于:分散剂是由聚乙烯蜡、芥酸酰胺按照质量比为(8-12):1混合得到的。
7.一种权利要求1-6任一项所述的电晕母料组合物的制备方法,其特征在于:包括以下步骤:
(1)称取聚乙烯、电晕助剂1、电晕助剂2、抗氧剂、分散剂、润滑剂,加入到高速混合机中,混合5-10min,放出物料;
(2)将步骤(1)放出的物料加入到双螺杆挤出机中造粒,双螺杆温度设定为130-150℃,经水环冷却,切粒包装后,得到电晕母料组合物。
8.一种权利要求1-6任一项所述的电晕母料组合物的应用,其特征在于:将电晕母料组合物作为PO膜最外层原料,采用三层吹膜机吹塑薄膜,吹塑温度为175-195℃。
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