CN112552560A - 一种石墨烯添加物的天然橡胶抗静电鞋垫 - Google Patents

一种石墨烯添加物的天然橡胶抗静电鞋垫 Download PDF

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CN112552560A
CN112552560A CN202011461093.XA CN202011461093A CN112552560A CN 112552560 A CN112552560 A CN 112552560A CN 202011461093 A CN202011461093 A CN 202011461093A CN 112552560 A CN112552560 A CN 112552560A
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graphene
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insole
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丁天宁
丁德材
丁幼丝
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Fujian Wuchiheng Technology Development Co ltd
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Abstract

本发明提供一种石墨烯添加物的天然橡胶抗静电鞋垫，包括以下原料：天然橡胶，POE弹性体，三元乙丙胶，石墨烯，抗静电粉，氧化锌，硬脂酸锌，硬脂酸，无味交联剂，发泡剂。所述鞋垫材料制备流程如下：将用硬脂酸处理的石墨烯加热后，依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，得到混合原胶；再向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，即得石墨烯抗静电鞋垫材料；然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，该鞋垫具有抗静电、抗菌、弹性高、耐磨性好，无毒，不易变形，易清洁等优点。

Description

一种石墨烯添加物的天然橡胶抗静电鞋垫
技术领域
本发明属于橡胶基复合材料技术领域，具体涉及一种石墨烯添加物的天然橡胶抗静电鞋垫。
背景技术
鞋垫大量应用于制鞋业、保健、特殊功用；一般分为制鞋业应用型鞋厂应用型鞋垫和市场商品型两种模式。制鞋业应用的鞋垫主要是配合鞋子大底、中底、做出相应的型体；按照楦底板或者面板制作尺码板，并制作出相应的形状。市场商品型鞋垫主要是把鞋垫直接作为一种商品出售，由开发师设计，在市场上流通的产品。
鞋垫按作用分类，可分为保健鞋垫，就是对人身体有健康益处的鞋垫，如：抗菌鞋垫，除臭鞋垫，中药鞋垫等；功能鞋垫，就是具备特殊功用的鞋来垫，如：抗静电鞋垫，增高鞋垫，防水鞋垫，空气循环鞋垫等；常规鞋垫：就是不具备以上2点的鞋垫，这个很常见。按材质分类，包括EVA鞋垫、海绵鞋垫、硅胶鞋垫、TPR鞋垫、乳胶鞋垫、布料鞋垫、皮革鞋垫、CPU鞋垫、软木鞋垫。
目前市面常见的橡胶鞋垫，主要是软橡胶和硬橡胶，软橡胶在潮湿或出汗的情况穿着很不错，但磨损得很快，容易变形；选择硬橡胶比较耐用，但抓地力较差，舒适度差。石墨烯是一种由碳原子以sp2杂化轨道组成六角型呈蜂巢晶格的二维碳纳米材料，其作为橡胶的补强材料，少量填充即可大幅度提高橡胶的机械性能，并且能展现其良好的电、热特性，可以作为一种非常理想的橡胶添加材料。
为了解决以上问题，开发一种石墨烯添加物的天然橡胶抗静电鞋垫，不仅增加弹性，还能增加韧性和抗撕力。
发明内容
基于以上现有技术，本发明的目的在于提供一种石墨烯添加物的天然橡胶抗静电鞋垫，该鞋垫具有抗静电、抗菌、防臭、弹性高、耐磨性好，韧性和抗撕力强、无毒，不易变形，易清洁等优点，可有效改善足部健康情况，而且舒适度和外观都得到了提升。
为了实现以上目的，本发明采用的技术方案为：
一种石墨烯添加物的天然橡胶抗静电鞋垫，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶60～80份，POE弹性体15～25份，三元乙丙胶5～15份，石墨烯2～8份，抗静电粉4～8份，氧化锌4～8份，硬脂酸锌1～3份，硬脂酸1～3份，无味交联剂0.5～2.0份，发泡剂2～6份。
为了更好的实现本发明，进一步的，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶70份，POE弹性体20份，三元乙丙胶10份，石墨烯5份，抗静电粉5份，氧化锌6份，硬脂酸锌2份，硬脂酸2份，无味交联剂1.0份，发泡剂4份。
为了更好的实现本发明，进一步的，所述POE弹性体为乙烯-辛烯共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物中的一种。
为了更好的实现本发明，进一步的，所述抗静电粉为乙氧基化脂肪族烷基胺、烷基磺酸钠、烷基咪唑啉盐、聚环氧乙烷、聚醚酯酰胺中的一种。
为了更好的实现本发明，进一步的，所述无味交联剂为双叔丁基过氧化二异丙基苯；发泡剂为偶氮二甲酰胺、二苯磺酰肼醚、对甲苯磺酰肼中的一种。
一种石墨烯添加物的天然橡胶抗静电鞋垫，包括以下步骤：
步骤1、将用硬脂酸处理的石墨烯加热后，依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，得到混合原胶；
步骤2、向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，即得石墨烯抗静电鞋垫材料；
步骤3、然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，得到石墨烯添加物天然抗静电鞋垫。
为了更好的实现本发明，进一步的，步骤1中石墨烯处理的具体步骤为，将硬脂酸和去离子水按照1～3:100的重量比进行配比，混合均匀后加热至100～160℃，缓慢逐步加入石墨烯，加入时不断搅拌，加入后继续搅拌1～3h，石墨烯加入量为2～8mg/ml，得到硬脂酸处理的石墨烯。
为了更好的实现本发明，进一步的，步骤1中混炼温度为120～160℃，混炼时间为3～6h。
为了更好的实现本发明，进一步的，步骤2中硫化交联时，先在平板硫化机上在120～160℃，8～10Mpa压力下，热压20～30min，然后在烘箱中进行二次硫化，硫化条件为175～185℃，2～4h，195～205℃，2～3h，215～225℃，1～2h，得到所述石墨烯抗静电鞋垫材料。
有益效果
本发明的有益效果如下：
(1)本发明的材料中含有石墨烯，其作为橡胶的补强材料，少量填充即可大幅度提高橡胶的机械性能，并且能展现其良好的电、热特性，是一种非常理想的橡胶纳米材料，在鞋垫中加入石墨烯不仅增加弹性，还能增加韧性和抗撕力；POE弹性体具有杰出的低温抗冲击性，低比重、洁净，能够和各种基础聚合物相容，柔顺性和抗刺穿性优异，伸长率和高弹性性能优越，还有良好的透光率以及极佳的电绝缘性能。
(2)本发明的材料具有抗静电效果，本发明使用的抗静电粉为内混型抗静电剂，是指在制品的加工过程中添加到橡胶内部的一类抗静电剂。乙氧基化脂肪族烷基胺、烷基磺酸钠、烷基咪唑啉盐为表面活性剂类，聚环氧乙烷、聚醚酯酰胺属于高分子永久型抗静电剂，本发明使用防静电剂可赋予材料表面一定的润滑性、降低摩擦系数、抑制和减少静电荷产生，并且具有持久抗静电的特点。
(3)本发明的鞋垫制备过程先将石墨烯均匀分散于橡胶中，其先用硬脂酸进行石墨烯处理，然后利用了POE弹性体的具有的低温抗冲击性，低比重、洁净，能够和各种基础聚合物相容，柔顺性和抗刺穿性优异，伸长率和高弹性性能优越，还有良好的透光率以及极佳的电绝缘性能，在进行硫化交联，从而得到的鞋垫材料具有抗静电、抗菌、防臭、弹性高、耐磨性好，韧性和抗撕力强、无毒，不易变形，易清洁等优点，
具体实施方式
下面结合具体实施例对本发明作进一步详细说明。
实施例1
本实施例提供一种石墨烯添加物的天然橡胶抗静电鞋垫，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶60份，POE弹性体15份，三元乙丙胶5份，石墨烯2份，抗静电粉4份，氧化锌4份，硬脂酸锌1份，硬脂酸1份，无味交联剂0.5份，发泡剂2份。
一种石墨烯添加物的天然橡胶抗静电鞋垫制备方法，包括以下步骤：
步骤1、将硬脂酸和去离子水按照1:100的重量比进行配比，混合均匀后加热至120℃，缓慢逐步加入石墨烯，加入时不断搅拌，加入后继续搅拌3h，石墨烯加入量为2mg/ml，得到硬脂酸处理的石墨烯，然后依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，混炼温度为160℃，混炼时间为3h，得到混合原胶；
步骤2、向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，先在平板硫化机上在120℃，8Mpa压力下，热压30min，然后在烘箱中进行二次硫化，硫化条件为175℃，4h，195℃，3h，215℃，2h，得到所述石墨烯抗静电鞋垫材料；
步骤3、然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，得到石墨烯添加物天然抗静电鞋垫。
实施例2
本实施例提供一种石墨烯添加物的天然橡胶抗静电鞋垫，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶65份，POE弹性体18份，三元乙丙胶8份，石墨烯3份，抗静电粉5份，氧化锌5份，硬脂酸锌2份，硬脂酸2份，无味交联剂0.8份，发泡剂3份。
一种石墨烯添加物的天然橡胶抗静电鞋垫制备方法，包括以下步骤：
步骤1、将硬脂酸和去离子水按照2:100的重量比进行配比，混合均匀后加热至130℃，缓慢逐步加入石墨烯，加入时不断搅拌，加入后继续搅拌3h，石墨烯加入量为3mg/ml，得到硬脂酸处理的石墨烯，然后依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，混炼温度为150℃，混炼时间为4h，得到混合原胶；
步骤2、向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，先在平板硫化机上在130℃，10Mpa压力下，热压30min，然后在烘箱中进行二次硫化，硫化条件为180℃，3h，200℃，3h，220℃，2h，得到所述石墨烯抗静电鞋垫材料；
步骤3、然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，得到石墨烯添加物天然抗静电鞋垫。
实施例3
本实施例提供一种石墨烯添加物的天然橡胶抗静电鞋垫，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶70份，POE弹性体20份，三元乙丙胶10份，石墨烯5份，抗静电粉5份，氧化锌6份，硬脂酸锌2份，硬脂酸2份，无味交联剂1.0份，发泡剂4份。
一种石墨烯添加物的天然橡胶抗静电鞋垫制备方法，包括以下步骤：
步骤1、将硬脂酸和去离子水按照2:100的重量比进行配比，混合均匀后加热至150℃，缓慢逐步加入石墨烯，加入时不断搅拌，加入后继续搅拌2h，石墨烯加入量为5mg/ml，得到硬脂酸处理的石墨烯，然后依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，混炼温度为150℃，混炼时间为4h，得到混合原胶；
步骤2、向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，先在平板硫化机上在140℃，10Mpa压力下，热压25min，然后在烘箱中进行二次硫化，硫化条件为180℃，3h，200℃，2.5h，220℃，1.5h，得到所述石墨烯抗静电鞋垫材料；
步骤3、然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，得到石墨烯添加物天然抗静电鞋垫。
实施例4
本实施例提供一种石墨烯添加物的天然橡胶抗静电鞋垫，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶75份，POE弹性体22份，三元乙丙胶12份，石墨烯6份，抗静电粉6份，氧化锌6份，硬脂酸锌2份，硬脂酸3份，无味交联剂1.8份，发泡剂5份。
一种石墨烯添加物的天然橡胶抗静电鞋垫制备方法，包括以下步骤：
步骤1、将硬脂酸和去离子水按照3:100的重量比进行配比，混合均匀后加热至120℃，缓慢逐步加入石墨烯，加入时不断搅拌，加入后继续搅拌3h，石墨烯加入量为6mg/ml，得到硬脂酸处理的石墨烯，然后依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，混炼温度为140℃，混炼时间为5h，得到混合原胶；
步骤2、向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，先在平板硫化机上在150℃，9Mpa压力下，热压20min，然后在烘箱中进行二次硫化，硫化条件为183℃，3h，200℃，2h，220℃，1.5h，得到所述石墨烯抗静电鞋垫材料；
步骤3、然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，得到石墨烯添加物天然抗静电鞋垫。
实施例5
本实施例提供一种石墨烯添加物的天然橡胶抗静电鞋垫，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶80份，POE弹性体25份，三元乙丙胶15份，石墨烯8份，抗静电粉8份，氧化锌8份，硬脂酸锌3份，硬脂酸3份，无味交联剂2.0份，发泡剂6份。
一种石墨烯添加物的天然橡胶抗静电鞋垫制备方法，包括以下步骤：
步骤1、将硬脂酸和去离子水按照3:100的重量比进行配比，混合均匀后加热至130℃，缓慢逐步加入石墨烯，加入时不断搅拌，加入后继续搅拌2h，石墨烯加入量为8mg/ml，得到硬脂酸处理的石墨烯，然后依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，混炼温度为130℃，混炼时间为4h，得到混合原胶；
步骤2、向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，先在平板硫化机上在160℃，8Mpa压力下，热压20min，然后在烘箱中进行二次硫化，硫化条件为185℃，2h，205℃，2h，225℃，1h，得到所述石墨烯抗静电鞋垫材料；
步骤3、然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，得到石墨烯添加物天然抗静电鞋垫。
对上述实施例1至5制得的石墨烯添加物的天然橡胶抗静电鞋垫进行力学性能够测试，测试方法如下：
(1)按照GB/T1410-2006固体绝缘材料体积电阻率和表面电阻率测试试验方法进行体积电阻率和表面电导率检测。
(2)撕裂强度：根据GB 6039-85，撕裂强度的定义为：在于试样主轴平行的方向上，拉伸试样直至开裂时的最大力，按照GB529和GB530的方法准备试样，测试步骤(1)硫化后的试片(厚2.0±0.3mm)应在标准室温下停放(不少于6小时，不超过15天)；(2)采取试样时，裁刀撕裂角等分线的方向与压延方向一致；(3)将试样垂直夹于上下夹持器重一定深度，并且使其在平等的位置上充分均匀夹紧；(4)调好拉伸速度(夹持器中以500±100mm/min的速度在运行)开动试验机，即可对试样施加一个逐渐增加的牵引力，直至试样被撕断后停机。
(3)拉伸强度：按照ASTM D-412标准的方法进行。
测试结果如下：
表1测试结果
测试结果 实施例1 实施例2 实施例3 实施例4 实施例5
体积电阻率Ω·m 10<sup>14</sup> 10<sup>14</sup> 10<sup>14</sup> 10<sup>14</sup> 10<sup>14</sup>
表面电阻率Ω 10<sup>15</sup> 10<sup>15</sup> 10<sup>15</sup> 10<sup>15</sup> 10<sup>15</sup>
撕裂强度kN/m 88 100 108 103 98
拉伸强度Mpa 43 44 48 47 45
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶60~80份，POE弹性体15~25份，三元乙丙胶5~15份，石墨烯2~8份，抗静电粉4~8份，氧化锌4~8份，硬脂酸锌1~3份，硬脂酸1~3份，无味交联剂0.5~2.0份，发泡剂2~6份。
2.根据权利要求1所述的一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，所述鞋垫材料的基本组成包括以下重量份原料：天然橡胶70份，POE弹性体20份，三元乙丙胶10份，石墨烯5份，抗静电粉5份，氧化锌6份，硬脂酸锌2份，硬脂酸2份，无味交联剂1.0份，发泡剂4份。
3.根据权利要求1或2所述的一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，所述POE弹性体为乙烯-辛烯共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物中的一种。
4.根据权利要求1或2所述的一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，所述抗静电粉为乙氧基化脂肪族烷基胺、烷基磺酸钠、烷基咪唑啉盐、聚环氧乙烷、聚醚酯酰胺中的一种。
5.根据权利要求1或2所述的一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，所述无味交联剂为双叔丁基过氧化二异丙基苯；发泡剂为偶氮二甲酰胺、二苯磺酰肼醚、对甲苯磺酰肼中的一种。
6.一种权利要求1或2所述的石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，包括以下步骤：
步骤1、将用硬脂酸处理的石墨烯加热后，依次加入天然橡胶，POE弹性体，三元乙丙胶，在混炼机中进行混炼，得到混合原胶；
步骤2、向混合原胶中加入抗静电粉，氧化锌，硬脂酸锌，无味交联剂，发泡剂进行再次混炼硫化交联，即得石墨烯抗静电鞋垫材料；
步骤3、然后将鞋垫材料根据需要裁减成相应的尺寸和厚度，得到石墨烯添加物天然抗静电鞋垫。
7.根据权利要求6所述的一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，步骤1中石墨烯处理的具体步骤为，将硬脂酸和去离子水按照1~3:100的重量比进行配比，混合均匀后加热至100~160℃，缓慢逐步加入石墨烯，加入时不断搅拌，加入后继续搅拌1~3h，石墨烯加入量为2~8mg/ml，得到硬脂酸处理的石墨烯。
8.根据权利要求6所述的一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，步骤1中混炼温度为120~160℃，混炼时间为3~6h。
9.根据权利要求6所述的一种石墨烯添加物的天然橡胶抗静电鞋垫，其特征在于，步骤2中硫化交联时，先在平板硫化机上在120~160℃，8~10Mpa压力下，热压20~30min，然后在烘箱中进行二次硫化，硫化条件为175~185℃，2~4h，195~205℃，2~3h，215~225℃，1~2h，得到所述石墨烯抗静电鞋垫材料。
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