CN107418069B - 一种橡胶专用石墨烯微片母料及制备方法 - Google Patents

一种橡胶专用石墨烯微片母料及制备方法 Download PDF

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CN107418069B
CN107418069B CN201710362357.8A CN201710362357A CN107418069B CN 107418069 B CN107418069 B CN 107418069B CN 201710362357 A CN201710362357 A CN 201710362357A CN 107418069 B CN107418069 B CN 107418069B
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陈庆
王镭迪
曾军堂
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Fei Jianfeng
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Chengdu New Keli Chemical Science Co Ltd
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Abstract

本发明提供的一种橡胶专用石墨烯微片母料及制备方法，采用硅源材料与石墨烯混合，将石墨烯分散于硅源材料中，在制备气相白炭黑时，通过水解反应实现石墨烯分散于白炭黑中，然后经过送旋风分离得到石墨烯白炭黑混合材料，进一步与硫磺、树脂载体混炼造粒，得到橡胶专用石墨烯微片母料，该石墨烯微片母料易于分散于橡胶，且白炭黑、硫磺均为橡胶常用助剂。该母料典型的用于橡胶轮胎增强、提高耐磨、防老化、阻燃，用于汽车的各类密封圈特种橡胶，具有优异的耐老化、耐磨性。公开的方案制备工艺简单，易于实现规模化工业生产。

Description

一种橡胶专用石墨烯微片母料及制备方法
技术领域
本发明涉及石墨烯材料领域，具体涉及一种橡胶专用石墨烯微片母料及制备方法。
背景技术
石墨烯是由碳原子构成的具有单原子层厚度的二维晶体，碳原子之间以sp2 杂化方式互相键合形成蜂窝状晶格网络，其基本结构单元是苯六元环，可看作是一层被剥离的石墨片。石墨烯是世界上最薄的二维材料，其厚度仅为0.35 nm。石墨烯内部的碳原子由很高键能的大共轭π键相互连接，其碳碳键长度约为0.142 nm。石墨烯各个碳原子间的连接非常柔韧，当施加外部机械力时，碳原子面就弯曲变形。这样，碳原子就不需要重新排列来适应外力，这也就保证了石墨烯结构的稳定，使得石墨烯可以像拉橡胶一样进行拉伸。而且这种稳定的晶格结构还使石墨烯具有优秀的导热性。
近年来，石墨烯用于橡胶的增强、散热被得到了广泛的关注，将石墨烯加入橡胶、塑料等可以大幅提高导热性能以及机械性能。目前已有将石墨烯作为导热材料用于橡胶、塑料、涂料等领域。中国发明专利CN105037821A公开了一种基于石墨烯改性技术的天然橡胶改性方法，该方法应用水相分散技术将石墨烯及其衍生物均匀分散在天然橡胶中，使导热率增加18-39%；中国发明专利CN104072868A公开了一种类石墨烯改性导热塑料及其制备方法，采用高度密的类石墨烯粉末与塑料基材混合，并具有良好的导热性能；中国发明专利CN103627223A公开了一种新型石墨烯导热涂料，采用石墨烯和纳米金刚石改性制备而成，石墨烯和纳米金刚石的加入总量占新型石墨烯导热涂料总量的百分比为0.1-5%，具有较好的导热性，较好的成膜强度，与
基体较高的结合强度。
然而，石墨烯作为一种纳米级材料，由于具有非常高的比表面积，导致其团聚非常严重，尤其是橡胶树与弹性体，热流动性较差，如将石墨烯直接用于橡胶基体中，难以分散，容易再团聚，而且这种团聚由于发生在原子间，是一种不可逆团聚，使得其无法充分发挥石墨烯的片层优异的增强特性。母料法是一种解决石墨烯分散的又效方法，现有的母料制备技术主要通过增加分散剂和低分子蜡或者液体化增加流动性以促使其在橡胶中分散，而低分子蜡等极易导致橡胶性能的劣化。
发明内容
针对现有技术中主要通过对母料添加低分子蜡等原料导致橡胶性能的劣化的技术缺陷，本发明提出一种橡胶专用石墨烯微片母料，通过采用硅源材料与石墨烯混合，与硫磺、树脂载体混炼造粒，得到橡胶专用石墨烯微片母料，从而提高石墨烯在橡胶中分散性和橡胶使用寿命。
为解决上述问题，本发明采用以下技术方案：
一种橡胶专用石墨烯微片母料的制备方法，所述制备方法如下：
（1）在密闭腔室中，将5-15重量份石墨烯微片加热至200-300℃，充分震荡搅拌，在空间内形成石墨烯浮动尘埃；
（2）将20-35重量份硅源材料从喷雾干燥口喷出，进入石墨烯尘埃密闭腔室，石墨烯物料与硅源材料在空间碰撞，充分均匀混合；
（3）向密闭腔室中喷入200-300 ℃水蒸气，所述硅源材料发生水解反应，与石墨烯一起沉降，再经过旋风分离得到石墨烯/白炭黑复合材料；
（4）将石墨烯/白炭黑复合材料、2-5重量份硫磺、40-50重量份高分子载体、0.5-0.5重量份表面活性剂混炼造粒得到橡胶专用石墨烯微片母料。
其中，所述高分子载体为尼龙、聚乙烯、聚苯乙烯、聚丙烯、聚碳酸酯、聚氯乙烯、聚酰胺、天然橡胶和丁晴橡胶中的至少一种；
所述硅源为硅氧烷、六乙基硅氧烷、四氯化硅、四氟化硅中的至少一种；
所述石墨烯微片为单层石墨烯、多层石墨烯、氧化石墨烯、还原氧化石墨烯、氟化石墨烯、石墨烯纳米带和石墨烯纳米片中的至少一种；
所述硫磺为纯度为99%的硫磺粉，粒径为100-200目；
所述表面活性剂为聚酰胺蜡、聚丙烯蜡、EVA蜡、硬脂酸钙和硬脂酸镁、乙撑基双硬脂酰胺、油酸酰胺、芥酸酰胺、邻苯二甲酸酯、柠檬酸酯、十二烷基硫酸钠、十二烷基磺酸钠的一种或几种。
优选的，所述震荡频率为10-35Hz，震荡时间为1-3h。
优选的，所述尘埃密度为10-103个/L。
优选的，所述水蒸气喷入后，静置1-3 小时，等待材料沉降。
优选的，旋风分离装置中的风速为5-10m/s。
优选的，所述混炼造粒采用锥形螺杆挤出机。
一种橡胶专用石墨烯微片母料，其特征是由上述方法制备得到。
现有方案中的有一些方法可以抑制石墨烯团聚的发生，但这需要精确地控制反应条件，或需要添加价格较为昂贵的小分子稳定剂、使用特殊有机溶剂等，而且特殊的存储条件使得石墨烯的应用受限。鉴于此，本发明提出一种橡胶专用石墨烯微片母料及制备方法，采用硅源材料与石墨烯混合，将石墨烯分散于硅源材料中，在制备气相白炭黑时，通过水解反应实现石墨烯分散于白炭黑中，然后经过送旋风分离得到石墨烯白炭黑混合材料，进一步与硫磺、树脂载体混炼造粒，得到橡胶专用石墨烯微片母料，该石墨烯微片母料易于分散于橡胶，且白炭黑、硫磺均为橡胶常用助剂。该母料典型的用于橡胶轮胎增强、提高耐磨、防老化、阻燃，用于汽车的各类密封圈特种橡胶，具有优异的耐老化、耐磨性。
本发明一种橡胶专用石墨烯微片母料及制备方法，与现有技术相比，其突出的特点和优异的效果在于：
1、本发明提供的一种橡胶专用石墨烯微片母料及制备方法，在制备气相白炭黑时，将石墨烯分散于前驱物，通过反应将石墨烯分散于白炭黑中，然后进一步与硫磺、树脂载体混炼造粒，得到橡胶专用石墨烯微片母料，通过与分散形成母料，克服了现有技术中主要通过对母料添加低分子蜡等原料导致橡胶性能的劣化的技术缺陷，提高了石墨烯在橡胶中分散性和橡胶使用寿命。
2、本发明公开的方案制备工艺简单，原料来源广泛，成本低，制备出的前驱体性质稳定，易储存输运，易于实现规模化工业生产。
3、本发明提供的一种橡胶专用石墨烯微片母料典型用于橡胶轮胎增强、提高耐磨、防老化、阻燃，用于汽车的各类密封圈特种橡胶，具有优异的耐老化、耐磨性。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明，但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
实施例1
（1）在密闭腔室中，将5重量份多层石墨烯粉加热至300℃，设置震荡频率为35Hz，震荡时间为1h充分震荡搅拌，在空间内形成尘埃密度为10-103个/L的石墨烯浮动尘埃；
（2）从干燥无水的存储空间取纯度为99%，35重量份硅氧烷从喷雾干燥口喷出，进入石墨烯尘埃密闭腔室，石墨烯物料与硅氧烷在空间碰撞，充分均匀混合；
（3）向密闭腔室中喷入200℃水蒸气，水蒸气喷入后，静置3小时，硅氧烷发生水解反应，与石墨烯一起沉降，等待材料沉降后，再设置旋风分离装置中的风速为10m/s，经过旋风分离得到石墨烯/白炭黑复合材料；
（4）采用混炼机设备，设定混炼温度为200℃，将石墨烯/白炭黑复合材料、纯度为99%，5重量份粒径为200目的硫磺粉，与55重量份聚苯乙烯，0.5重量份EVA蜡在锥形螺杆机混炼造粒，获得橡胶专用石墨烯微片母料。
将实施例1得到的橡胶专用石墨烯微片母料以5%质量比与95%的丁基橡胶（IIR）直接共混制备橡胶制品,与5%市售石墨烯母料（直接将石墨烯分散于载体树脂造粒得到）增强性能相比，实施例1橡胶专用石墨烯微片母料表现出极佳的增强性、耐磨性，增加丁基橡胶杨氏模量、拉伸强度、断裂伸长率。具体测试能如表1所示。
实施例2
（1）在密闭腔室中，将10重量份氧化石墨烯、还原氧化石墨烯混合粉末加热至250℃，设置震荡频率为10Hz，震荡时间为1.5h充分震荡搅拌，在空间内形成尘埃密度为10-103个/L的石墨烯浮动尘埃；
（2）从干燥无水的存储空间取纯度为99%，32重量份六乙基硅氧烷从喷雾干燥口喷出，进入石墨烯尘埃密闭腔室，石墨烯物料与六乙基硅氧烷在空间碰撞，充分均匀混合；
（3）向密闭腔室中喷入250 ℃水蒸气，水蒸气喷入后，静置2.5 小时，六乙基硅氧烷发生水解反应，与石墨烯一起沉降，等待材料沉降后，再设置旋风分离装置中的风速为10m/s，经过旋风分离得到石墨烯/白炭黑复合材料；
（4）采用混炼机设备，设定混炼温度为180℃，将石墨烯/白炭黑复合材料、3重量份纯度为99%，粒径为200目的硫磺粉，与55重量份聚乙烯、聚苯乙烯混合物，0.3重量份硬脂酸钙和硬脂酸镁混炼造粒，获得橡胶专用石墨烯微片母料。
将实施例2得到的橡胶专用石墨烯微片母料以5%质量比与95%的丁基橡胶（IIR）直接共混制备橡胶制品,与5%市售石墨烯母料（直接将石墨烯分散于载体树脂造粒得到）增强性能相比，实施例2橡胶专用石墨烯微片母料表现出极佳的增强性、耐磨性，增加丁基橡胶杨氏模量、拉伸强度、断裂伸长率。具体测试能如表1所示。
实施例3
（1）在密闭腔室中，将15重量份氟化石墨烯粉加热至300℃，设置震荡频率为15Hz，震荡时间为3h充分震荡搅拌，在空间内形成尘埃密度为10-103个/L的石墨烯浮动尘埃；
（2）从干燥无水的存储空间取纯度为99%，30重量份四氯化硅从喷雾干燥口喷出，进入石墨烯尘埃密闭腔室，石墨烯物料与四氯化硅在空间碰撞，充分均匀混合；
（3）向密闭腔室中喷入300 ℃水蒸气，水蒸气喷入后，静置2小时，四氯化硅发生水解反应，与石墨烯一起沉降，等待材料沉降后，再设置旋风分离装置中的风速为8m/s，经过旋风分离得到石墨烯/白炭黑复合材料；
（4）采用混炼机设备，设定混炼温度为180℃，将石墨烯/白炭黑复合材料、2重量份纯度为99%，粒径为120目的硫磺粉，与53重量份聚酰胺，0.4份柠檬酸酯混炼造粒，获得橡胶专用石墨烯微片母料。
将实施例3得到的橡胶专用石墨烯微片母料以5%质量比与95%的丁基橡胶（IIR）直接共混制备橡胶制品,与5%市售石墨烯母料（直接将石墨烯分散于载体树脂造粒得到）增强性能相比，实施例3橡胶专用石墨烯微片母料表现出极佳的增强性、耐磨性，增加丁基橡胶杨氏模量、拉伸强度、断裂伸长率。具体测试能如表1所示。
实施例4
（1）在密闭腔室中，将15重量份石墨烯纳米带和石墨烯纳米片粉末加热至200℃，设置震荡频率为25Hz，震荡时间为1.9h充分震荡搅拌，在空间内形成尘埃密度为10-103个/L的石墨烯浮动尘埃；
（2）从干燥无水的存储空间取纯度为99%，将30重量份六乙基硅氧烷从喷雾干燥口喷出，进入石墨烯尘埃密闭腔室，石墨烯物料与六乙基硅氧烷在空间碰撞，充分均匀混合；
（3）向密闭腔室中喷入280 ℃水蒸气，水蒸气喷入后，静置2.5 小时，六乙基硅氧烷发生水解反应，与石墨烯一起沉降，等待材料沉降后，再设置旋风分离装置中的风速为9m/s，经过旋风分离得到石墨烯/白炭黑复合材料；
（4）采用混炼机设备，设定混炼温度为250℃，将石墨烯/白炭黑复合材料、5重量份纯度为99%，粒径为130目的硫磺粉，与50重量份聚氨酯与聚碳酸酯混合材料，0.3重量份聚酰胺蜡混炼造粒，获得橡胶专用石墨烯微片母料。
将实施例4得到的橡胶专用石墨烯微片母料以5%质量比与95%的丁基橡胶（IIR）直接共混制备橡胶制品,与5%市售石墨烯母料（直接将石墨烯分散于载体树脂造粒得到）增强性能相比，实施例4橡胶专用石墨烯微片母料表现出极佳的增强性、耐磨性，增加丁基橡胶杨氏模量、拉伸强度、断裂伸长率。具体测试能如表1所示。
实施例5
（1）在密闭腔室中，将5重量份单层石墨烯粉加热至300℃，设置震荡频率为35Hz，震荡时间为3h充分震荡搅拌，在空间内形成尘埃密度为10-103个/L的石墨烯浮动尘埃；
（2）从干燥无水的存储空间取纯度为99%，35重量份六乙基硅氧烷加入喷雾干燥进料口，从喷雾干燥口喷出，进入石墨烯尘埃密闭腔室，石墨烯物料与六乙基硅氧烷在空间碰撞，充分均匀混合；
（3）向密闭腔室中喷入250 ℃水蒸气，水蒸气喷入后，静置1 小时，六乙基硅氧烷发生水解反应，与石墨烯一起沉降，等待材料沉降后，再设置旋风分离装置中的风速为5-10m/s，经过旋风分离得到石墨烯/白炭黑复合材料；
（4）采用混炼机设备，设定混炼温度为300℃，将石墨烯/白炭黑复合材料、5重量份纯度为99%，粒径为100目的硫磺粉，与50重量份聚氨酯材料，0.3重量份乙撑基双硬脂酰胺炼造粒，获得橡胶专用石墨烯微片母料。
将实施例5得到的橡胶专用石墨烯微片母料以5%质量比与95%的丁基橡胶（IIR）直接共混制备橡胶制品,与5%市售石墨烯母料（直接将石墨烯分散于载体树脂造粒得到）增强性能相比，实施例5橡胶专用石墨烯微片母料表现出极佳的增强性、耐磨性，增加丁基橡胶杨氏模量、拉伸强度、断裂伸长率。具体测试能如表1所示。
表1：
Figure DEST_PATH_IMAGE001

Claims (8)

1.一种橡胶专用石墨烯微片母料的制备方法，所述制备方法如下：
（1）在密闭腔室中，将5-15重量份石墨烯微片加热至200-300℃，充分震荡搅拌，在空间内形成石墨烯浮动尘埃；
（2）将20-35重量份硅源材料从喷雾干燥口喷出，进入石墨烯尘埃密闭腔室，石墨烯物料与硅源材料在空间碰撞，充分均匀混合；所述硅源为硅氧烷、四氯化硅、四氟化硅中的至少一种；所述尘埃密度为10-103个/L；
（3）向密闭腔室中喷入200-300℃水蒸气，所述硅源材料发生水解反应，与石墨烯一起沉降，再经过旋风分离得到石墨烯/白炭黑复合材料；所述水蒸气喷入后，静置1-3小时，等待材料沉降；所述的旋风分离装置中的风速为5-10m/s；
（4）将石墨烯/白炭黑复合材料、2-5重量份硫磺、40-50重量份高分子载体、0.5-0.5重量份表面活性剂混炼造粒得到橡胶专用石墨烯微片母料。
2.根据权利要求1所述一种橡胶专用石墨烯微片母料的制备方法，其特征在于：所述高分子载体为聚乙烯、聚苯乙烯、聚丙烯、聚碳酸酯、聚氯乙烯、聚酰胺、天然橡胶和丁腈橡胶中的至少一种。
3.根据权利要求1所述一种橡胶专用石墨烯微片母料的制备方法，其特征在于：所述石墨烯微片为单层石墨烯、多层石墨烯、氧化石墨烯、还原氧化石墨烯、氟化石墨烯、石墨烯纳米带和石墨烯纳米片中的至少一种。
4.根据权利要求1所述一种橡胶专用石墨烯微片母料的制备方法，其特征在于：所述硫磺为纯度为99%的硫磺粉，粒径为100-200目。
5.根据权利要求1所述一种橡胶专用石墨烯微片母料的制备方法，其特征在于：所述表面活性剂为聚酰胺蜡、聚丙烯蜡、EVA蜡、硬脂酸钙和硬脂酸镁、乙撑基双硬脂酰胺、油酸酰胺、芥酸酰胺、邻苯二甲酸酯、柠檬酸酯、十二烷基硫酸钠、十二烷基磺酸钠的一种或几种。
6.根据权利要求1所述一种橡胶专用石墨烯微片母料的制备方法，其特征在于：所述震荡采用振荡频率为10-35Hz，震荡时间为1-3h。
7.根据权利要求1所述一种橡胶专用石墨烯微片母料的制备方法，其特征在于：所述混炼造粒采用锥形螺杆挤出机。
8.一种橡胶专用石墨烯微片母料，其特征在于：所述石墨烯微片母料是由权利要求1-7任一项所述方法制备得到的橡胶专用石墨烯微片母料。
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