CN113527790A - 一种防静电辐照交联聚乙烯发泡材料及其制备方法 - Google Patents
一种防静电辐照交联聚乙烯发泡材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种防静电辐照交联聚乙烯发泡材料,包括按重量份计的如下组分:低密度聚乙烯25~35份、烯烃嵌段共聚物10~15份、发泡剂5~8份、发泡助剂5~8份、交联剂1~5份、敏化助剂0.5~3份、聚乙烯蜡2~5份、导电炭黑3~10份、抗氧剂0.1~0.5份和填料4~8份;其中,所述低密度聚乙烯在190℃×2.16kg条件下的熔融指数MI=1‑3g/10min;所述烯烃嵌段共聚物为乙烯‑辛烯共聚物,其中辛烯含量为20‑30%,密度为0.865‑0.895g/cm3。本发明还公开了所述防静电辐照交联聚乙烯发泡材料的制备方法。本发明的防静电辐照交联聚乙烯发泡材料,可一步成型制得待交联母片,大大简化了工艺流程,得到的产品导电性能稳定、质轻、无毒、无异味、力学性能优良。
Description
技术领域
本发明涉及发泡聚乙烯制品技术领域,具体涉及一种防静电辐照交联聚乙烯发泡材料及其制备方法。
背景技术
防静电发泡材料可运用在消费电子领域,如手机、电脑、手机配件等各种电子器件,以及小型家电、大型家电等各种电子产品的包装等领域,起到缓冲减震同时防止静电的作用。当前的防静电发泡材料综合性能差,防静电时效短,生产效率低。
目前市场上应用的防静电发泡材料主要有防静电珍珠泡棉、模压块状聚乙烯或EVA导电发泡材料。其中,防静电珍珠泡棉因其是未交联的聚乙烯,发泡为物理发泡,导致泡棉的泡孔很大,压缩强度低,回弹性和手感均较差。另外,由于是物理发泡,导致产品的发泡倍率单一,厚度单一,误差较大,耐温性较差,因此其应用领域受限,应用场合档次较低。最后,未交联聚乙烯表面电阻率和体积电阻率不稳定,无法根据客户要求进行调节,电阻率较大,通过在珍珠棉内加入抗静电剂,做成的防静电珍珠泡棉防静电时效短,一般为3-6个月,防静电性能受环境干湿度影响较大。
对于模压发泡的聚乙烯或EVA块状导电泡棉,虽然泡孔细腻,但是力学性能较差,压缩强度、压缩永久变形、撕裂强度较辐射交联产品差,产品无法连续生产,不同厚度的产品仅仅依靠刨切获得,产品无结皮表皮,产品软硬密度不好控制,后加工中不能进行热粘合,耗能高,生产效率低。
公告号为CN101358004B的中国专利公开了一种IXPE电子辐射交联聚乙烯导电泡棉及其制备方法,解决了现有技术中导电泡棉存在的综合性能差这一技术问题,但是该方案中,IXPE泡棉的制备工艺较为繁复,需要先将原料混炼挤出为母粒,然后将母粒挤出成型为母片,接着对挤出的母片进行辐照加工,最后进行加热发泡处理,得到辐射交联聚乙烯导电泡棉。公告号为CN107629289B的中国专利公开了一种防静电超薄型发泡片材,采用聚烯烃树脂和抗静电剂以发泡工艺直接制备获得。但是该方案的发泡片材的制备工艺同样比较复杂,需要先通过混炼、造粒得到多种母粒,然后将母粒与树脂基材混合挤出,得到发泡基片,最后将发泡基片进行辐照交联、加热发泡,得到发泡片材。
发明内容
本发明要解决的技术问题是提供一种防静电辐照交联聚乙烯发泡材料及其制备方法,该方法可一步成型制得待交联母片,大大简化了工艺流程,得到的产品导电性能稳定、质轻、无毒、无异味、力学性能优良。
为了解决上述技术问题,本发明提供了如下的技术方案:
本发明提供了一种防静电辐照交联聚乙烯发泡材料,包括按重量份计的如下组分:
低密度聚乙烯 25~35份
烯烃嵌段共聚物 10~15份
发泡剂 5~8份
发泡助剂 5~8份
交联剂 1~5份
敏化助剂 0.5~3份
聚乙烯蜡 2~5份
导电炭黑 3~10份
抗氧剂 0.1~0.5份
填料 4~8份;
其中,所述低密度聚乙烯在190℃×2.16kg条件下的熔融指数MI=1-3g/10min;所述烯烃嵌段共聚物为乙烯-辛烯共聚物,其中辛烯含量为20-30%,密度为0.865-0.895g/cm3。优选地,所述烯烃嵌段共聚物的密度为0.870-0.885g/cm3。
进一步地,所述发泡剂为偶氮二甲酰胺、偶氮二甲酸二异丙酯或偶氮二异丁腈。优选地,所述发泡剂为偶氮二甲酰胺,其目数为300-1000,pH值为5-8。更优选地,所述偶氮二甲酰胺的目数500-700,pH值为6-7。
进一步地,所述发泡助剂为氧化锌和硬脂酸中的一种或两种的复配物。优选地,所述发泡剂与发泡助剂的质量比为1:0.5-1。优选地,所述复配物中,氧化锌与硬脂酸的质量比为1:1-10。
进一步地,所述敏化助剂为二盐基亚磷酸铅、三盐基硫酸铅、硬脂酸钙或硬脂酸锌,优选为硬脂酸锌。敏化助剂的加入,有利于降低发泡的温度,从而减小高温对发泡材料性能的影响。
进一步地,所述交联剂为三烯丙基异氰脲酸酯(TAIC)、三聚氰酸三烯丙酯(TAC)和三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)中的一种或多种。本发明中,通过加入交联剂,降低了辐照剂量和辐照成本,减少了辐照对材料性能的损伤。
进一步地,所述填料为碳酸钙或滑石粉。通过添加碳酸钙或者滑石粉,对制品的尺寸稳定性和加工性能够起到帮助作用。
进一步地,所述导电炭黑为粉状,粒径为15-45nm,pH值为6-9。处于这一粒径范围的导电炭黑具有更好的导电效果,有利于提高制品的抗静电能力。
进一步地,所述抗氧剂由主抗氧剂和辅助抗氧剂组成,所述主抗氧剂为酚类主抗氧剂1010或1076,所述辅助抗氧剂为硫代酯类辅助型抗氧剂硫代二丙酸双月桂酯(DLTP)、硫代二丙酸二(十四)酯(DMTP)或硫代二丙酸双十八酯(DSTP)。
本发明还提供了所述的防静电辐照交联聚乙烯发泡材料的制备方法,包括以下步骤:
S1:将配方量的低密度聚乙烯、烯烃嵌段共聚物、发泡剂、发泡助剂、交联剂、聚乙烯蜡和抗氧剂于密炼机中混合均匀,然后加入导电炭黑和填料,加热密炼至120~130℃;
S2:将步骤S1中密炼的材料与敏化助剂加入挤出机中,挤出得到母片;
S3:将步骤S2中得到的母片按6-14Mrad的辐照剂量进行辐照,得到交联片材;
S4:将步骤S3中得到的交联片材在230~260℃下进行发泡,得到所述防静电辐照交联聚乙烯发泡材料。
与现有技术相比,本发明的有益效果在于:
1. 本发明的防静电辐照交联聚乙烯发泡材料,可通过将各原料一步成型制得待交联母片,母片经辐射交联和高温发泡后得到防静电辐照交联聚乙烯发泡材料成型制品。与现有技术中的辐照交联聚乙烯发泡材料相比,本发明的制备方法无需制备母粒,一步成型得到母片,减化了造粒再挤出工艺,提高了生产效率,节省了加工成本(可实现每吨产品降低550-850元综合成本)。
2. 本发明的防静电辐照交联聚乙烯发泡材料,通过在配方中引入了交联剂和敏化助剂,有利于降低辐照的剂量和发泡的温度,从而减小了因辐照和发泡温度对材料性能的损失。
3. 本发明的防静电辐照交联聚乙烯发泡材料,导电性能稳定、质轻、无毒、无异味、力学性能优良,适用于对材料静电要求较高的服装、家居、消费电子和汽车领域。
附图说明
图1为本发明的防静电辐照交联聚乙烯发泡材料的制备工艺路线图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法,所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1~3:制备防静电辐照交联聚乙烯发泡材料
本实施例提供了一种防静电辐照交联聚乙烯发泡材料及其制备方法,包括以下步骤:
步骤一:混料
按照表1的配方,将低密度聚乙烯、烯烃嵌段共聚物、发泡剂、发泡助剂、交联剂、聚乙烯蜡和抗氧剂先在密炼机中搅拌1分钟,混合均匀,然后加入导电炭黑和填料,加热密炼至120℃。
步骤二:一步成型得到母片
将步骤一中密炼的材料直接放进单螺杆挤出机的主喂料料斗,单螺杆挤出机中间段有喂料段,将敏化助剂从该喂料段按比例加入,单螺杆挤出机端部安装符合要求的模头,挤出母片。
步骤三:辐照交联
将步骤二中得到的母片按12Mrad的辐照剂量进行辐照,得到交联后的片材。
步骤四:高温发泡
将步骤三中得到的交联后的片材在发泡炉中进行高温发泡,发泡倍率为15倍,得到厚度为2mm的防静电发泡材料成型制品。
表1 实施例1-3及对比例1-2的防静电辐照交联聚乙烯发泡材料的配方
组份 | 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 |
低密度聚乙烯 | 25 | 30 | 35 | 30 | 30 |
烯烃嵌段共聚物 | 15 | 14 | 14 | 14 | 14 |
发泡剂 | 4 | 5 | 5 | 5 | 5 |
发泡助剂 | 2 | 2.5 | 5 | 0 | 2.5 |
交联剂 | 3 | 3 | 4 | 3 | 0 |
敏化助剂 | 1 | 1 | 2 | 0 | 0 |
聚乙烯蜡 | 2.5 | 2.5 | 3 | 2.5 | 2.5 |
导电炭黑 | 5 | 5.5 | 5.5 | 5.5 | 5.5 |
抗氧剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
滑石粉 | 5 | 5 | 5 | 5 | 5 |
以上各实施例和对比例中:
实施例1中:低密度聚乙烯的熔融指数MI=1.5g/10min;发泡助剂为氧化锌;导电炭黑的粒径为15-25nm,pH=6-7.5;抗氧剂为主抗氧剂1076+辅助抗氧剂DSTP;交联剂为TAIC与TAC的混合物。
实施例2中:低密度聚乙烯的熔融指数MI=2g/10min;发泡助剂为氧化锌和硬脂酸混合物,质量比为1:5;导电炭黑的粒径为15-25nm,pH=6-7.5;抗氧剂为主抗氧剂1076+辅助抗氧剂DSTP;交联剂为TAIC与TMPTMA的混合物。
实施例3中:低密度聚乙烯的熔融指数MI=2g/10min;发泡助剂为氧化锌和硬脂酸混合物,质量比为1:5;导电炭黑的粒径为25-40nm,pH=7.5-8.5;抗氧剂为主抗氧剂1010+辅助抗氧剂DSTP;交联剂为TAC与TMPTMA的混合物。
对比例1中:低密度聚乙烯的熔融指数MI=1.5g/10min;导电炭黑的粒径为15-25nm,pH=6-7.5;抗氧剂为主抗氧剂1076+辅助抗氧剂DSTP;交联剂为TAIC与TAC的混合物。
对比例2中:低密度聚乙烯的熔融指数MI=1.5g/10min;发泡助剂为氧化锌;导电炭黑的粒径为15-25nm,pH=6-7.5;抗氧剂为主抗氧剂1076+辅助抗氧剂DSTP。
性能测试:
对实施例及对比例制备的聚乙烯发泡材料进行性能测试,所得结果如表2所示。
表2 实施例1~3,对比例1~2制备的聚乙烯发泡制品的性能测试结果
测试项目 | 单位 | 实施例1 | 实施例2 | 对比例3 | 对比例1 | 对比例2 |
拉伸强度 | MPa | 0.4 | 0.45 | 0.45 | 0.36 | 0.15 |
断裂伸长率 | % | 55 | 55 | 57 | 34 | 26 |
表面电阻 | Ω*m | 10<sup>7</sup>-10<sup>8</sup> | 10<sup>5</sup>-10<sup>7</sup> | 10<sup>6</sup>-10<sup>7</sup> | 10<sup>8</sup>-10<sup>9</sup> | 10<sup>8</sup>-10<sup>9</sup> |
从表2中可以看出,实施例制备的聚乙烯发泡制品,在拉伸强度、断裂伸长率和表面电阻等指标上均优于对比例的聚乙烯发泡制品。对比例1-2的制品,由于未加交联剂和敏化剂,相同工艺条件难以制备出合格样品,产品辐照后交联度不够,发泡温度也需要提高,发泡效果也不好,导电炭黑的分散性也不均匀,导致产品力学性能下降,表面电阻增大,产品外观也不美观,尺寸也不稳定,难以进行相应测试。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。
Claims (10)
1.一种防静电辐照交联聚乙烯发泡材料,其特征在于,包括按重量份计的如下组分:
低密度聚乙烯 25~35份
烯烃嵌段共聚物 10~15份
发泡剂 5~8份
发泡助剂 5~8份
交联剂 1~5份
敏化助剂 0.5~3份
聚乙烯蜡 2~5份
导电炭黑 3~10份
抗氧剂 0.1~0.5份
填料 4~8份;
其中,所述低密度聚乙烯在190℃×2.16kg条件下的熔融指数MI=1-3g/10min;所述烯烃嵌段共聚物为乙烯-辛烯共聚物,其中辛烯含量为20-30%,密度为0.865-0.895g/cm3。
2.根据权利要求1所述的一种防静电辐照交联聚乙烯发泡材料,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或偶氮二异丁腈;所述偶氮二甲酰胺的目数为300-1000,pH值为5-8。
3.根据权利要求2所述的一种防静电辐照交联聚乙烯发泡材料,其特征在于,所述偶氮二甲酰胺的目数500-700,pH值为6-7。
4.根据权利要求1所述的一种防静电辐照交联聚乙烯发泡材料,其特征在于,所述发泡助剂为氧化锌和硬脂酸中的一种或两种的复配物;所述发泡剂与发泡助剂的质量比为1:0.5-1。
5.根据权利要求4所述的一种防静电辐照交联聚乙烯发泡材料,其特征在于,所述复配物中,氧化锌与硬脂酸的质量比为1:1-10。
6.根据权利要求1所述的一种防静电辐照交联聚乙烯发泡材料,其特征在于,所述敏化助剂为二盐基亚磷酸铅、三盐基硫酸铅、硬脂酸钙或硬脂酸锌。
7.根据权利要求1所述的一种防静电辐照交联聚乙烯发泡材料,其特征在于,所述交联剂为TAIC、TAC和TMPTMA中的一种或多种;所述填料为碳酸钙或滑石粉。
8.根据权利要求1所述的一种防静电辐照交联聚乙烯发泡材料,其特征在于,所述导电炭黑为粉状,粒径为15-45nm,pH值为6-9。
9.根据权利要求1所述的一种防静电辐照交联聚乙烯发泡材料,其特征在于,所述抗氧剂由主抗氧剂和辅助抗氧剂组成,所述主抗氧剂为酚类主抗氧剂1010或1076,所述辅助抗氧剂为硫代酯类辅助型抗氧剂DLTP、DMTP或DSTP。
10.根据权利要求1-9任一项所述的防静电辐照交联聚乙烯发泡材料的制备方法,其特征在于,包括以下步骤:
S1:将配方量的低密度聚乙烯、烯烃嵌段共聚物、发泡剂、发泡助剂、交联剂、聚乙烯蜡和抗氧剂于密炼机中混合均匀,然后加入导电炭黑和填料,加热密炼至120~130℃;
S2:将步骤S1中密炼的材料与敏化助剂加入挤出机中,挤出得到母片;
S3:将步骤S2中得到的母片按6-14Mrad的辐照剂量进行辐照,得到交联片材;
S4:将步骤S3中得到的交联片材在230~260℃下进行发泡,得到所述防静电辐照交联聚乙烯发泡材料。
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杨鸿昌: "IXPE泡棉表面张力影响因素的研究", 《塑料工业》 * |
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CN114714556A (zh) * | 2022-04-01 | 2022-07-08 | 启东纽昇塑胶科技有限公司 | 一种生产开孔聚乙烯发泡材料的制备方法 |
CN115353680A (zh) * | 2022-08-12 | 2022-11-18 | 中广核高新核材科技(苏州)有限公司 | 一种抗菌辐照交联聚乙烯发泡材料及其制备方法 |
CN115353680B (zh) * | 2022-08-12 | 2023-12-01 | 中广核高新核材科技(苏州)有限公司 | 一种抗菌辐照交联聚乙烯发泡材料及其制备方法 |
CN115850832A (zh) * | 2022-09-06 | 2023-03-28 | 东莞市盈圆合创新材料有限公司 | 环保抗菌型电子辐射交联聚烯烃泡棉及其制备方法 |
CN115572429A (zh) * | 2022-10-13 | 2023-01-06 | 深圳市盛林纸品包装有限公司 | 一种永久防静电复合材料 |
WO2024206777A1 (en) * | 2023-03-31 | 2024-10-03 | Toray Plastics (America), Inc. | Crosslinked polyethylene foam and methods of making |
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