CN112358673A - 一种辐照交联发泡聚乙烯制品及其制备方法 - Google Patents

一种辐照交联发泡聚乙烯制品及其制备方法 Download PDF

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CN112358673A
CN112358673A CN202011398352.9A CN202011398352A CN112358673A CN 112358673 A CN112358673 A CN 112358673A CN 202011398352 A CN202011398352 A CN 202011398352A CN 112358673 A CN112358673 A CN 112358673A
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foaming
density polyethylene
parts
sheet
polyethylene
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黄志杰
史丛丛
邹惠忠
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Shanghai Branch Of Cgn Hi Tech Nuclear Material Technology Suzhou Co ltd
Zhongguanghe Nuclear Technology Development Co ltd
Cgn Delta Jiangsu Plastics Co ltd
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Shanghai Branch Of Cgn Hi Tech Nuclear Material Technology Suzhou Co ltd
Zhongguanghe Nuclear Technology Development Co ltd
Cgn Delta Jiangsu Plastics Co ltd
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Abstract

本发明公开了一种辐照交联聚乙烯发泡制品及其制备方法，所述辐照交联聚乙烯发泡制品的原料包括以质量份计的线性低密度聚乙烯40‑70份、低密度聚乙烯20‑40份、乙烯‑醋酸乙烯酯5‑20份、发泡剂5‑30份、交联剂1‑10份、抗氧剂0.1‑1份和发泡助剂3‑25份，本发明的制备方法是将制得的母片片材首先经过辐照交联，使材料形成具有不溶不熔特点的三维交联网络结构，然后再经过高温发泡形成发泡材料。通过辐照提高了熔体强度，使得制品在高温发泡过程中可以很好的保持尺寸各项均一性，并且形成的泡孔尺寸小，具有均匀、致密的特点。通过添加交联剂可以大幅度降低辐照所需剂量，降低生产成本。

Description

一种辐照交联发泡聚乙烯制品及其制备方法
技术领域
本发明涉及一种辐照交联发泡聚乙烯制品及其制备方法，属于化工材料技术领域。
背景技术
发泡聚乙烯材料在包装上广泛用于精密仪器仪表、家用电器、玻璃和陶瓷制品、工艺品、贵重物品等的缓冲包装；可制成缓冲衬垫，作为包装内衬材料；也可制成缓冲袋、缓冲板箱等包装容器；还可制成冷冻食品和热食品的绝热容器等。
发泡聚乙烯材料还可用作通信电缆的材料，专利CN111704763A公开了一种化学发泡聚乙烯组合物及其制备方法和应用，此专利是对未交联的PE进行发泡，存在以下缺点：(1)未交联的PE在发泡过程中存在高温发泡时熔体容易流动变形等，造成泡孔不均匀，不致密；(2)因为受发泡气体冲击，制品尺寸容易产生各向异性的变化；导致最终制品尺寸均一性较难控制；(3)对比技术中是高密度聚乙烯和高密度聚丙烯的混合物，并不是纯的聚乙烯发泡材料。
发明内容
本发明解决的技术问题是：现有技术中的发泡聚乙烯制品的尺寸稳定性差，泡孔不均匀、不致密的问题。
为了解决上述技术问题，本发明提供了一种辐照交联发泡聚乙烯制品，原料包括以质量份计的线性低密度聚乙烯40-70份、低密度聚乙烯20-40份、乙烯-醋酸乙烯酯5-20份、发泡剂5-30份、交联剂1-10份、抗氧剂0.1-1份和发泡助剂3-25份。
优选地，所述发泡剂为偶氮二甲酰胺、偶氮二甲酸二异丙酯和偶氮二异丁氰中的一种；所述交联剂为三烯丙基异氰酸酯、三烯丙基氰酸酯和三羟甲基丙烷三甲基丙烯酸酯中的一种或其分子量低于1500的均聚物；所述抗氧剂为N，N’-双[β-(3，5-二叔丁基-4-羟基苯基)丙酰]肼；所述发泡助剂为金属脂肪酸盐和/或金属氧化物。
优选地，所述线性低密度聚乙烯的质量份为50-65份，所述低密度聚乙烯的质量份为25-30份。
更优选地，所述发泡剂为偶氮二甲酰胺，其质量份为10-20份。
更优选地，所述交联剂为三烯丙基异氰酸酯，其质量份为2-5份。
更优选地，所述发泡助剂为硬脂酸锌和氧化锌，其中，硬脂酸锌的质量份为2-10份，氧化锌的质量份为1-5份。
本发明还提供了一种上述辐照交联发泡聚乙烯制品的制备方法，包括以下步骤：
步骤1：将原料制成发泡母片片材；
步骤2：将上述母片片材进行辐照，得到交联后的片材；
步骤3：将上述交联后的片材进行加热发泡，得到最终的发泡聚乙烯制品。
优选地，所述步骤1中制备发泡母片片材的方法为：将原料中的发泡剂以线性低密度聚乙烯或低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到发泡母粒，将交联剂、抗氧剂和发泡助剂混合，以线性低密度聚乙烯或低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到添加剂母粒；然后将两种母粒与线性低密度聚乙烯、低密度聚乙烯和乙烯-醋酸乙烯酯在高混机中混合均匀后，用单螺杆或双螺杆挤出机挤出母片片材。
优选地，所述步骤2中辐照的剂量为5-15Mrad。
优选地，所述步骤3中加热发泡的温度为160-250℃，时间为5min。
更优选地，所述挤出母片片材的方法为采用双螺杆挤出机挤出母片片材。
优选地，所述双螺杆挤出机的工艺参数为：长径比30:1，加工温度150-180℃，螺杆转速50r/min。
本发明与现有技术相比，具有如下有益效果：
1.本发明提供的一种辐照交联发泡聚乙烯制品的制备方法通过辐照提高了熔体强度，使得制品在高温发泡过程中可以很好的保持尺寸各项均一性，并且形成的泡孔尺寸小，具有均匀、致密的特点。
2.本发明通过在配方中添加交联剂，可以大幅度降低辐照所需剂量，降低了生产成本。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，作详细说明如下。
实施例1
一种辐照交联发泡聚乙烯制品的制备方法，具体步骤为：
(1)将原料(如表1所示)中的发泡剂以一半量的线性低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到发泡母粒，将交联剂、抗氧剂和发泡助剂混合，以一半量的低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到添加剂母粒；然后将两种母粒与乙烯-醋酸乙烯酯和余下的线性低密度聚乙烯、低密度聚乙烯在高混机中混合10分钟，混合均匀后通过双螺杆挤出机挤出片材，双螺杆挤出机的长径比为30:1，加工温度为150-180℃，螺杆转速为50r/min，挤出的片材的厚度为0.45mm，长度为100m，宽度为600mm。
(2)将得到的片材用8Mrad的辐照剂量进行辐照交联，得到交联后的片材；
(3)将交联后的片材在220℃下发泡5min，得到厚度为2mm左右的发泡聚乙烯制品，将其剪裁为长、宽各为1m的片材。
实施例2
一种辐照交联发泡聚乙烯制品的制备方法，具体步骤为：
(1)将原料(如表1所示)中的发泡剂以一半量的低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到发泡母粒，将交联剂、抗氧剂和发泡助剂混合，以一半量的线性低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到添加剂母粒；然后将两种母粒与乙烯-醋酸乙烯酯和余下的线性低密度聚乙烯、低密度聚乙烯在高混机中混合10分钟，混合均匀后通过双螺杆挤出机挤出片材，双螺杆挤出机的长径比为30:1，加工温度为150-180℃，螺杆转速为50r/min，挤出的片材的厚度为0.5mm，长度为100m，宽度为600mm。
(2)将得到的片材用8Mrad的辐照剂量进行辐照交联，得到交联后的片材；
(3)将交联后的片材在200℃下发泡5min，得到厚度为2mm左右的发泡聚乙烯制品，将其剪裁为长、宽各为1m的片材。
实施例3
一种辐照交联发泡聚乙烯制品的制备方法，具体步骤为：
(1)将原料(如表1所示)中的发泡剂以一半量的线性低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到发泡母粒，将交联剂、抗氧剂和发泡助剂混合，以一半量的低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到添加剂母粒；然后将两种母粒与乙烯-醋酸乙烯酯和余下的线性低密度聚乙烯、低密度聚乙烯在高混机中混合10分钟，混合均匀后通过双螺杆挤出机挤出片材，双螺杆挤出机的长径比为30:1，加工温度为150-180℃，螺杆转速为50r/min，挤出的片材的厚度为0.4mm，长度为100m，宽度为600mm。
(2)将得到的片材用8Mrad的辐照剂量进行辐照交联，得到交联后的片材；
(3)将交联后的片材在230℃下发泡5min，得到厚度为2mm左右的发泡聚乙烯制品，将其剪裁为长、宽各为1m的片材。
对比例1
一种发泡聚乙烯制品的制备方法，具体步骤为：
(1)将原料(如表1所示)中的发泡剂以一半量的线性低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到发泡母粒，将抗氧剂和发泡助剂混合，以一半量的低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到添加剂母粒；然后将两种母粒与乙烯-醋酸乙烯酯和余下的线性低密度聚乙烯、低密度聚乙烯在高混机中混合10分钟，混合均匀后通过双螺杆挤出机挤出片材，双螺杆挤出机的长径比为30:1，加工温度为150-180℃，螺杆转速为50r/min，挤出的片材的厚度为0.4mm，长度为100m，宽度为600mm。
(2)将得到的片材用8Mrad的辐照剂量进行辐照交联，得到交联后的片材；
(3)将交联后的片材在250℃下发泡5min，得到厚度为2mm左右的发泡聚乙烯制品，将其剪裁为长、宽各为1m的片材。
对比例2
一种发泡聚乙烯制品的制备方法，具体步骤为：
(1)将原料(如表1所示)中的发泡剂以一半量的低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到发泡母粒，将抗氧剂和发泡助剂混合，以一半量的线性低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到添加剂母粒；然后将两种母粒与乙烯-醋酸乙烯酯和余下的线性低密度聚乙烯、低密度聚乙烯在高混机中混合10分钟，混合均匀后通过双螺杆挤出机挤出片材，双螺杆挤出机的长径比为30:1，加工温度为150-180℃，螺杆转速为50r/min，挤出的片材的厚度为0.5mm，长度为100m，宽度为600mm。
(2)将上述片材在160℃下发泡5min，得到厚度为2mm左右的发泡聚乙烯制品，将其剪裁为长、宽各为1m的片材。
表1各实施例和对比例的原料组成
组份 实施例1 实施例2 实施例3 对比例1 对比例2
线性低密度聚乙烯 50份 60份 65份 50份 50份
低密度聚乙烯 25份 25份 30份 25份 25份
乙烯-醋酸乙烯酯 5份 10份 10份 5份 5份
偶氮二甲酰胺 10份 20份 10份 10份 10份
三烯丙基异氰酸酯 3份 3份 3份 0份 0份
抗氧剂 0.5份 0.5份 0.5份 0.5份 0.5份
硬脂酸锌 2份 5份 10份 2份 2份
氧化锌 1份 5份 1份 1份 1份
将以上各实施例和对比例制得的发泡聚乙烯制品进行性能测试，计算出各实施例和对比例制备的发泡聚乙烯制品的厚度尺寸公差，并观察各实施例和对比例制得的发泡聚乙烯制品的泡孔形态，其结果如表2所示。由表2中的数据可知，本发明的实施例1-3添加交联剂后，达到同样的形态，辐照剂量只需要8Mrad，而对比例1未加交联剂，所需辐照剂量高达15Mrad，而且添加了交联剂的尺寸公差更小、尺寸均一性更好，对比不辐照的对比例2，产品尺寸稳定性、泡孔致密性和均一性都更好。
表2各实施例和对比例制得的发泡聚乙烯制品的性能测试表
发泡温度 辐照剂量 厚度尺寸公差 泡孔形态
实施例1 220℃ 8Mrad 0.02mm 致密、均匀
实施例2 200℃ 8Mrad 0.02mm 致密、均匀
实施例3 230℃ 8Mrad 0.02mm 致密、均匀
对比例1 250℃ 15Mrad 0.05mm 致密、均匀性稍差
对比例2 160℃ 0Mrad 0.2mm 泡孔大、均匀性差
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。

Claims (8)

1.一种辐照交联发泡聚乙烯制品，其特征在于，原料包括以质量份计的线性低密度聚乙烯40-70份、低密度聚乙烯20-40份、乙烯-醋酸乙烯酯5-20份、发泡剂5-30份、交联剂1-10份、抗氧剂0.1-1份和发泡助剂3-25份。
2.如权利要求1所述的辐照交联发泡聚乙烯制品，其特征在于，所述发泡剂为偶氮二甲酰胺、偶氮二甲酸二异丙酯和偶氮二异丁氰中的一种；所述交联剂为三烯丙基异氰酸酯、三烯丙基氰酸酯和三羟甲基丙烷三甲基丙烯酸酯中的一种或其分子量低于1500的均聚物；所述抗氧剂为N,N’-双[β-(3，5-二叔丁基-4-羟基苯基)丙酰]肼；所述发泡助剂为金属脂肪酸盐和/或金属氧化物。
3.一种权利要求1或2所述的辐照交联发泡聚乙烯制品的制备方法，其特征在于，包括以下步骤：
步骤1：将原料制成发泡母片片材；
步骤2：将上述母片片材进行辐照，得到交联后的片材；
步骤3：将上述交联后的片材进行加热发泡，得到最终的发泡聚乙烯制品。
4.如权利要求3所述的辐照交联发泡聚乙烯制品的制备方法，其特征在于，所述步骤1中制成发泡母片片材的方法为：将原料中的发泡剂以线性低密度聚乙烯或低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到发泡母粒，将交联剂、抗氧剂和发泡助剂混合，以线性低密度聚乙烯或低密度聚乙烯为载体，混合后通过双螺杆挤出机进行造粒、包装，得到添加剂母粒；然后将两种母粒与线性低密度聚乙烯、低密度聚乙烯和乙烯-醋酸乙烯酯在高混机中混合均匀后，通过单螺杆或双螺杆挤出机挤出母片片材。
5.如权利要求3所述的辐照交联发泡聚乙烯制品的制备方法，其特征在于，所述步骤2中辐照的剂量为5-15Mrad。
6.如权利要求3所述的辐照交联发泡聚乙烯制品的制备方法，其特征在于，所述步骤3中加热发泡的温度为160-250℃，时间为5min。
7.如权利要求4所述的辐照交联发泡聚乙烯制品的制备方法，其特征在于，所述挤出母片片材的方法为采用双螺杆挤出机挤出母片片材。
8.如权利要求7所述的辐照交联发泡聚乙烯制品的制备方法，其特征在于，所述双螺杆挤出机的工艺参数为：长径比30:1，加工温度150-180℃，螺杆转速50r/min。
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