CN110229369A - 一种疏水疏油抗静电pvc复合薄膜及其制备方法 - Google Patents

一种疏水疏油抗静电pvc复合薄膜及其制备方法 Download PDF

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CN110229369A
CN110229369A CN201910499656.5A CN201910499656A CN110229369A CN 110229369 A CN110229369 A CN 110229369A CN 201910499656 A CN201910499656 A CN 201910499656A CN 110229369 A CN110229369 A CN 110229369A
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李刚
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JIANGSU YINGTAI PLASTICS Co.,Ltd.
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Abstract

本发明公开一种抗污抗静电PVC复合薄膜及其制备方法：以抗静电PVC复合薄膜为基底，将抗污自洁剂丝网印刷在其表面；所述抗静电PVC复合薄膜，包括以下重量百分比组分：聚氯乙烯45‑65％、聚四氟乙烯10‑14％、丙烯酸单体12‑18％、羟基化石墨烯6‑10％、氨基化石墨烯4‑6％、催化剂0.1‑0.5％、超支化聚苯乙烯1.8‑4％、聚吡咯1‑2％、分散剂0.1‑0.5％；所述抗污自洁剂包括以下重量百分比组分：纳米TiO2溶胶30‑55％、纳米银粉5‑10％、荷叶疏水剂10‑15％、全氟辛基三乙氧基硅烷10‑15％、全氟烷基乙基丙烯酸酯20‑30％。本发明利用具有特殊官能团结构的石墨烯与丙烯酸树脂化学交联作用将石墨烯引入聚丙烯酸酯分子链中，利用介质间相似相容原理使改性石墨烯导电微粒与PVC树脂稳定相容，进而使PVC复合薄膜具有永久性抗静电能力。

Description

一种疏水疏油抗静电PVC复合薄膜及其制备方法
技术领域
本发明属于PVC薄膜制备技术领域，具体涉及一种疏水疏油抗静电PVC复合薄膜及其制备方法。
背景技术
PVC薄膜,全名为Polyvinylchlorid薄膜,是由聚氯乙烯树脂与增塑剂、稳定剂、润滑剂等功能性改性剂经过压延工艺或吹塑工艺成膜，厚度为0.08～0.2mm。PVC薄膜透明度、光泽度优良，其强度优于PE膜，气体阻隔性(如阻CO2气体)和耐油性较大，是当今世界应用广泛的一种合成材料，其全球使用量在各种合成材料中高居第二。
PVC薄膜电绝缘性高，表面电阻率为1012-1016Ω·cm，体积电阻率为1014-1016Ω·cm，因此，PVC薄膜在加工、生产过程中易造成静电荷积累的问题，不仅影响正常使用，还因静电作用吸附环境中粉尘、灰粒或油脂，影响其表面光洁度。现有技术，主要通过采用物理掺杂的方式将炭黑、碳纤维、碳纳米管、石墨、金属微粒等导电填料填充在聚氯乙烯树脂中制造抗静电PVC薄膜，无机填料和有机高分子材料之间相容性较差，易出现界面分层现象或无机粒子沉积析出现象，影响PVC薄膜抗静电性，随着时间的增长，复合体系的稳定性越差，抗静电性不断衰减。如申请号为CN201610990417.6的专利，公开一种聚氯乙烯抗静电薄膜的制备方法，通过直接将抗静电助剂物理添加到聚氯乙烯树脂中的方式改善抗静电性能；如申请号为CN201710866133.0的专利，公开一种抗静电硬质聚氯乙烯材料的制备方法，以膨胀石墨和一维碳纤维作为导电填料，与PVC物理共混制备抗静电材料。
基于以上所述，本发明利用具有特殊官能团结构的石墨烯与丙烯酸树脂间化学交联共聚反应，将石墨烯引入聚丙烯酸酯分子链中，利用介质间相似相容原理使石墨烯接枝聚丙烯酸酯与PVC树脂稳定融合，极大地提高了石墨烯导电微粒与PVC树脂结合力，使PVC复合薄膜具有永久性抗静电能力；同时，本发明还利用抗污自洁剂极大提高薄膜表面光洁度。
发明内容
针对现有技术的不足之处，本发明的目的在于提供一种疏水疏油抗污抗静电PVC复合薄膜及其制备方法。
本发明的技术方案概述如下：
一种抗污抗静电PVC复合薄膜：以抗静电PVC复合薄膜为基底，将抗污自洁剂丝网印刷在其表面；
所述抗静电PVC复合薄膜，包括以下重量百分比组分：聚氯乙烯45-65％、聚四氟乙烯10-14％、丙烯酸单体12-18％、羟基化石墨烯6-10％、氨基化石墨烯4-6％、催化剂0.1-0.5％、超支化聚苯乙烯1.8-4％、聚吡咯1-2％、分散剂0.1-0.5％；所述抗污自洁剂包括以下重量百分比组分：纳米TiO2溶胶30-55％、纳米银粉5-10％、荷叶疏水剂10-15％、全氟辛基三乙氧基硅烷10-15％、全氟烷基乙基丙烯酸酯20-30％。
优选的是，所述超支化聚苯乙烯是具有拓扑结构和共轭结构的超支化共轭聚合物。
优选的是，所述催化剂为氯化亚砜。
优选的是，所述分散剂包括脂肪酸聚氧乙烯醚酯、季戊四醇硬脂酸酯、聚乙烯醇中的一种或多种。
优选的是，所述纳米TiO2溶胶中纳米TiO2含量为10-15％。
一种抗污抗静电PVC复合薄膜的制备方法，包括以下步骤：
S1：制备石墨烯接枝聚丙烯酸酯：将丙烯酸单体溶液加入羟基化石墨烯、氨基化石墨烯，分散均匀后，加热至80-95℃，加入催化剂，反应3-8h,冷却至室温后，备用；
S2：制备抗静电PVC复合薄膜：将S1制出的石墨烯接枝聚丙烯酸酯与聚氯乙烯、聚四氟乙烯、超支化聚苯乙烯、聚吡咯、分散剂混合均匀，135-160℃熔炼3h，再压延成0.08-0.18mm的薄膜，压延温度为115-135℃；
S3：按100-150ml/m2的用量将抗污自洁剂丝网印刷在S2制出的抗静电PVC复合薄膜表面，75℃干燥固化即得成品。
附图说明
图1为抗静电PVC复合薄膜制备方法工艺流程图。
本发明的有益效果：
(1)本发明通过将具有羟基和氨基官能团结构的石墨烯与丙烯酸单体中羧基间化学交联成反应中间体，再共聚成目标产物的方法，将石墨烯引入聚丙烯酸酯分子链中，利用介质间相似相容原理使石墨烯接枝聚丙烯酸酯与PVC树脂稳定融合，极大地提高了石墨烯导电微粒与PVC树脂结合力，使PVC复合薄膜具有永久性抗静电能力；同时，本发明还利用抗污自洁剂显著提高薄膜表面光洁度、自洁性能和抗菌性能，通过全氟辛基三乙氧基硅烷、全氟烷基乙基丙烯酸酯和纳米TiO2、纳米银粉形成超疏水、疏油的微纳米复合结构，与荷叶疏水剂协同改善复合薄膜的疏水疏油性能，并利用纳米TiO2和纳米银粉的光催化性质分解污渍和油脂，抗菌杀菌。
(2)超支化聚苯乙烯是具有拓扑结构和共轭结构的超支化共轭聚合物，能使电子、π电子、σ电子在三维空间内的共轭基团中离域化，表现出高导电性，本发明首次将超支化聚苯乙烯掺入PVC树脂中，与PVC树脂形成的导电海岛结构耗散静电荷，极大地提高了PVC材料的抗静电性，降低复合薄膜电阻率。
具体实施方式
下面结合实施例对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
实施例1
一种抗污抗静电PVC复合薄膜：以抗静电PVC复合薄膜为基底，将抗污自洁剂丝网印刷在其表面；
所述抗静电PVC复合薄膜，包括以下重量百分比组分：聚氯乙烯65％、聚四氟乙烯10％、丙烯酸单体12％、羟基化石墨烯6％、氨基化石墨烯4％、氯化亚砜0.1％、超支化聚苯乙烯1.8％、聚吡咯1％、脂肪酸聚氧乙烯醚酯0.1％；所述抗污自洁剂包括以下重量百分比组分：纳米TiO2溶胶55％、纳米银粉5％、荷叶疏水剂10％、全氟辛基三乙氧基硅烷10％、全氟烷基乙基丙烯酸酯20％；所述纳米TiO2溶胶中纳米TiO2含量为10％。
该抗污抗静电PVC复合薄膜的制备方法，包括以下步骤：
S1：制备石墨烯接枝聚丙烯酸酯：将丙烯酸单体溶液加入羟基化石墨烯、氨基化石墨烯，分散均匀后，加热至80℃，加入催化剂，反应5h,冷却至室温后，备用；
S2：制备抗静电PVC复合薄膜：将S1制出的石墨烯接枝聚丙烯酸酯与聚氯乙烯、聚四氟乙烯、超支化聚苯乙烯、聚吡咯、分散剂混合均匀，135℃熔炼3h，再压延成0.10mm的薄膜，压延温度为115℃；
S3：按100ml/m2的用量将抗污自洁剂丝网印刷在S2制出的抗静电PVC复合薄膜表面，75℃干燥固化即得成品。
实施例2
一种抗污抗静电PVC复合薄膜：以抗静电PVC复合薄膜为基底，将抗污自洁剂丝网印刷在其表面；
所述抗静电PVC复合薄膜，包括以下重量百分比组分：聚氯乙烯45-65％、聚四氟乙烯12％、丙烯酸单体15％、羟基化石墨烯8％、氨基化石墨烯5％、氯化亚砜0.2％、超支化聚苯乙烯3％、聚吡咯1.5％、脂肪酸聚氧乙烯醚酯0.3％；所述抗污自洁剂包括以下重量百分比组分：纳米TiO2溶胶42％、纳米银粉8％、荷叶疏水剂12.5％、全氟辛基三乙氧基硅烷12.5％、全氟烷基乙基丙烯酸酯25％；所述纳米TiO2溶胶中纳米TiO2含量为12.5％。
该抗污抗静电PVC复合薄膜的制备方法，包括以下步骤：
S1：制备石墨烯接枝聚丙烯酸酯：将丙烯酸单体溶液加入羟基化石墨烯、氨基化石墨烯，分散均匀后，加热至90℃，加入催化剂，反应5h,冷却至室温后，备用；
S2：制备抗静电PVC复合薄膜：将S1制出的石墨烯接枝聚丙烯酸酯与聚氯乙烯、聚四氟乙烯、超支化聚苯乙烯、聚吡咯、分散剂混合均匀，150℃熔炼3h，再压延成0.15mm的薄膜，压延温度为125℃；
S3：按125ml/m2的用量将抗污自洁剂丝网印刷在S2制出的抗静电PVC复合薄膜表面，75℃干燥固化即得成品。
实施例3
一种抗污抗静电PVC复合薄膜：以抗静电PVC复合薄膜为基底，将抗污自洁剂丝网印刷在其表面；
所述抗静电PVC复合薄膜，包括以下重量百分比组分：聚氯乙烯45％、聚四氟乙烯14％、丙烯酸单体18％、羟基化石墨烯10％、氨基化石墨烯6％、氯化亚砜0.5％、超支化聚苯乙烯4％、聚吡咯2％、聚乙烯醇0.5％；所述抗污自洁剂包括以下重量百分比组分：纳米TiO2溶胶30％、纳米银粉10％、荷叶疏水剂15％、全氟辛基三乙氧基硅烷15％、全氟烷基乙基丙烯酸酯30％；所述纳米TiO2溶胶中纳米TiO2含量为15％。
该抗污抗静电PVC复合薄膜的制备方法，包括以下步骤：
S1：制备石墨烯接枝聚丙烯酸酯：将丙烯酸单体溶液加入羟基化石墨烯、氨基化石墨烯，分散均匀后，加热至95℃，加入催化剂，反应8h,冷却至室温后，备用；
S2：制备抗静电PVC复合薄膜：将S1制出的石墨烯接枝聚丙烯酸酯与聚氯乙烯、聚四氟乙烯、超支化聚苯乙烯、聚吡咯、分散剂混合均匀，160℃熔炼3h，再压延成0.18mm的薄膜，压延温度为135℃；
S3：按150ml/m2的用量将抗污自洁剂丝网印刷在S2制出的抗静电PVC复合薄膜表面，75℃干燥固化即得成品。
对实施例1-3制出的PVC复合薄膜进行性能检测，试验结构如下表所示：
实施例1 实施例2 实施例3
表面电阻率/Ω·cm 5.2×10<sup>6</sup> 2.8×10<sup>6</sup> 7.5×10<sup>5</sup>
体积电阻率/Ω·cm 4.6×10<sup>6</sup> 2.0×10<sup>6</sup> 6.8×10<sup>5</sup>
与水的接触角/° 156 164 170
水滴滚动角/° 5 5 4
拉伸强度/MPa 28 30 31
伸长率/％ 35 33 30
线膨胀系数/×10<sup>-5</sup>K<sup>-1</sup> 10 11 9
由上表数据可知，本发明显著降低了PVC复合薄膜表面电阻率和体积电阻率，进而大幅度改善其抗静电性能，且其膜表面与水的接触角≥156°，水滴在膜表面的滚动角≤5°，具有明显荷叶疏水效应，提高PVC复合薄膜疏水疏油性能，进而改善其光洁度与自洁性能。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。

Claims (6)

1.一种抗污抗静电PVC复合薄膜，其特征在于：以抗静电PVC复合薄膜为基底，将抗污自洁剂丝网印刷在其表面；
所述抗静电PVC复合薄膜，包括以下重量百分比组分：聚氯乙烯45-65％、聚四氟乙烯10-14％、丙烯酸单体12-18％、羟基化石墨烯6-10％、氨基化石墨烯4-6％、催化剂0.1-0.5％、超支化聚苯乙烯1.8-4％、聚吡咯1-2％、分散剂0.1-0.5％；所述抗污自洁剂包括以下重量百分比组分：纳米TiO2溶胶30-55％、纳米银粉5-10％、荷叶疏水剂10-15％、全氟辛基三乙氧基硅烷10-15％、全氟烷基乙基丙烯酸酯20-30％。
2.根据权利要求1所述一种抗污抗静电PVC复合薄膜，其特征在于，所述超支化聚苯乙烯是具有拓扑结构和共轭结构的超支化共轭聚合物。
3.根据权利要求1所述一种抗污抗静电PVC复合薄膜，其特征在于，所述催化剂为氯化亚砜。
4.根据权利要求1所述一种抗污抗静电PVC复合薄膜，其特征在于，所述分散剂包括脂肪酸聚氧乙烯醚酯、季戊四醇硬脂酸酯、聚乙烯醇中的一种或多种。
5.根据权利要求1所述一种抗污抗静电PVC复合薄膜，其特征在于，所述纳米TiO2溶胶中纳米TiO2含量为10-15％。
6.一种抗污抗静电PVC复合薄膜的制备方法，其特征在于，包括以下步骤：
S1：制备石墨烯接枝聚丙烯酸酯：将丙烯酸单体溶液加入羟基化石墨烯、氨基化石墨烯，分散均匀后，加热至80-95℃，加入催化剂，反应3-8h,冷却至室温后，备用；
S2：制备抗静电PVC复合薄膜：将S1制出的石墨烯接枝聚丙烯酸酯与聚氯乙烯、聚四氟乙烯、超支化聚苯乙烯、聚吡咯、分散剂混合均匀，135-160℃熔炼3h，再压延成0.08-0.18mm的薄膜，压延温度为115-135℃；
S3：按100-150ml/m2的用量将抗污自洁剂丝网印刷在S2制出的抗静电PVC复合薄膜表面，75℃干燥固化即得成品。
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