CN107254096A - 一种石墨烯改性高分子柔软抗变形复合发泡材料及其制备方法 - Google Patents

一种石墨烯改性高分子柔软抗变形复合发泡材料及其制备方法 Download PDF

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CN107254096A
CN107254096A CN201710196585.2A CN201710196585A CN107254096A CN 107254096 A CN107254096 A CN 107254096A CN 201710196585 A CN201710196585 A CN 201710196585A CN 107254096 A CN107254096 A CN 107254096A
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ethylene
agent
foam material
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graphene
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丁爱娥
吴金华
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Graphene Mstar Technology Ltd
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract

本发明提供一种石墨烯改性高分子柔软抗变形复合发泡材料及其制备方法,如下成分及其质量百分比:乙烯‑醋酸乙烯酯共聚物(EVA):15%~30%、乙烯‑辛烯共聚物(POE):5%~20%、聚烯烃类嵌段共聚物(OBCs):10%~25%、三元乙丙橡胶(EPDM):5%~15%、苯乙烯‑乙烯‑丁烯‑苯乙烯共聚物(SEBS):15%~40%、填充剂:5%~20%、石墨烯:0.1%~3%、偶联剂:0.5%~1.5%、润滑剂:0.5%~1.5%、金属氧化物:0.8%~1.5%、架桥剂:0.6%~1%、发泡剂:1.5%~3.5%,各原料经密炼机进行二阶段密炼密炼、滚轮机混炼、造粒机造粒、发泡成型。本发明通过引入石墨烯,从而有效对复合材料的力学性能进行补强,使复合发泡材料达到轻质柔软、抗变形、耐撕裂等特性。

Description

一种石墨烯改性高分子柔软抗变形复合发泡材料及其制备 方法
技术领域
本发明涉及高分子材料制造技术领域,具体涉及一种石墨烯改性高分子柔软抗变形复合发泡材料及其制备方法。
背景技术
随着人们生活水平的提高,锻炼健身成为人们日常生活中的常事,那么选择一双好的鞋至关重要,如何提高鞋子的触感,提高鞋子的舒适度,使鞋子轻质、耐磨、抗菌、舒适、止滑、高弹、透气、环保、安全,成为了人们饱受关注的需求。因此寻找新的方案提高鞋子的性能,打造各种功能性、人性化、高品位的新型合成材料,成为当今鞋业材料发展的方向。
发明内容
本发明的目的是提供一种石墨烯改性高分子柔软抗变形复合发泡材料及其制备方法,通过在复合发泡材料中引入石墨烯,从而有效提高复合发泡材料的力学性能,使复合发泡材料具有柔软舒适、高弹性、抗变形、耐撕裂等特性。
为了实现上述目的,本发明采用的技术方案如下:
一种石墨烯改性高分子柔软抗变形复合发泡材料,包括如下成分及其质量百分比:
乙烯-醋酸乙烯酯共聚物(EVA):15%~30%;
乙烯-辛烯共聚物(POE) :5%~20%;
聚烯烃类嵌段共聚物(OBCs):10%~25%;
三元乙丙橡胶(EPDM):5%~15%;
苯乙烯-乙烯-丁烯-苯乙烯共聚物(SEBS):15%~40%;
填充剂:5%~20%;
石墨烯:0.1%~3%;
偶联剂:0.5%~1.5%;
润滑剂:0.5%~1.5%;
金属氧化物:0.8%~1.5%;
架桥剂:0.6%~1%;
发泡剂:1.5%~3.5%。
根据以上方案,所述填充剂为滑石粉、偶联剂为铝酸酯偶联剂、润滑剂为硬脂酸、金属氧化物为氧化锌、架桥剂为无味交联剂、发泡剂为偶氮二甲酰胺。
一种石墨烯改性高分子柔软抗变形复合发泡材料的制备方法,包括如下步骤:
1)取乙烯-醋酸乙烯酯共聚物、乙烯-辛烯共聚物、聚烯烃类嵌段共聚物、三元乙丙橡胶、苯乙烯-乙烯-丁烯-苯乙烯共聚物、填充剂、石墨烯、偶联剂、润滑剂和金属氧化物混合后倒入密炼机中进行第一阶段密炼,翻料3-4次,密炼温度控制在105-108℃,时间为9-10min,再加入架桥剂和发泡剂的混合物,再次启动密炼机进行第二阶段密炼,翻料3-4次,密炼温度控制在115-120℃,时间为9-10min,即得到混合料;
2)将密炼好的混合料在滚轮机上进行混炼,先进行打厚,厚度为1.0-1.5cm;再进行打薄,厚度为2-3mm;最后进行打厚,厚度为1.0-1.5cm;
3)将混炼混合均匀的料传送到造粒机中进行造粒,得到粒料 ;
4)将粒料经注塑机注入模具中发泡,再经恒温箱定型,得到成品;或将粒料直接倒入模具进行一次发泡,再进行二次发泡并冷却得到成品。
根据以上方案,所述发泡的温度为177-183℃,时间为370-430 S。
根据以上方案,所述冷却的时间为370-430 S。
本发明制备方法步骤1)主要是混炼原材料,得到各组分均匀混合一起的原材料;步骤2)主要是使原材料混合更均匀,同时降低原材料温度;步骤3)是为了将原材料进行造粒;步骤4)是加工粒料,得到所要的复合发泡材料。
本发明的有益效果是:
本发明以聚合物EVA、POE、OBCs、EPDM、SEBS为主胶,能增加材料弹性和柔软性;石墨烯能提高材料拉伸强度、撕裂、延伸率等力学性能,增加材料密闭性,提升材料抗变形性能;填料能稳定产品尺寸以及降低材料成本;偶联剂能改善复合材料的分散性;润滑剂能避免复合发泡材料在加工过程中粘在机械上;金属氧化物能降低发泡剂的发泡温度;架桥剂能起交联作用;发泡剂主能使材料进行发泡,表现出优异的抗冲击性能,而且撕裂强度高;总之,本发明产品能有效补强复合发泡材料的力学性能,使复合发泡材料具有柔软舒适、高弹性、抗变形、耐撕裂等特性,适合于作为运动鞋、篮球鞋、足球鞋、跑鞋等的鞋底;且制备方法简单、操作简便。
具体实施方式
下面结合实施例对本发明的技术方案进行说明。
实施例1:
本发明提供一种石墨烯改性高分子柔软抗变形复合发泡材料,包括如下成分及其质量:EVA:20g、POE:10g、OBCs:15g、EPDM:15g、SEBS:20g、填充剂(滑石粉):14g、石墨烯:0.5g、铝酸酯偶联剂:0.5g、润滑剂(硬脂酸):0.8g、金属氧化物(ZnO):1.2g、架桥剂(无味交联剂):0.9g、发泡剂(偶氮二甲酰胺) :2.1g,其制备方法,包括如下步骤:
1)取EVA、POE、OBCs、EPDM、SEBS、填充剂、石墨烯、偶联剂、润滑剂和金属氧化物混合后倒入密炼机中进行第一阶段密炼,翻料4次,密炼温度控制在106℃,时间为9min,再加入架桥剂和发泡剂的混合物,再次启动密炼机进行第二阶段密炼,翻料3次,密炼温度控制在118℃,时间为10min,即得到混合料;
2)将密炼好的混合料在滚轮机上进行混炼,先进行打厚,厚度为1.3cm;再进行打薄,厚度为2.5mm;最后进行打厚,厚度为1.3cm;
3)将混炼混合均匀的料传送到造粒机中进行造粒,得到粒料 ;
4)将粒料经注塑机注入模具中在180℃下,发泡400 S,再经恒温箱定型,得到成品。
实施例2:
本发明提供一种石墨烯改性高分子柔软抗变形复合发泡材料,包括如下成分及其质量:EVA:20g、POE:15g、OBCs:15g、EPDM:13.5、SEBS:15g、填充剂(滑石粉):15g、石墨烯:0.3g、铝酸酯偶联剂:0.7g、润滑剂(硬脂酸):1.5g、金属氧化物(ZnO):0.8g、架桥剂(无味交联剂) :1g、发泡剂(偶氮二甲酰胺) :2.2g,其制备方法,包括如下步骤:
1)取EVA、POE、OBCs、EPDM、SEBS、填充剂、石墨烯、偶联剂、润滑剂和金属氧化物混合后倒入密炼机中进行第一阶段密炼,翻料4次,密炼温度控制在105℃,时间为10min,再加入架桥剂和发泡剂的混合物,再次启动密炼机进行第二阶段密炼,翻料4次,密炼温度控制在120℃,时间为9min,即得到混合料;
2)将密炼好的混合料在滚轮机上进行混炼,先进行打厚,厚度为1.5cm;再进行打薄,厚度为3mm;最后进行打厚,厚度为1.5cm;
3)将混炼混合均匀的料传送到造粒机中进行造粒,得到粒料 ;
4)将粒料经注塑机注入模具中在177℃下,发泡430 S,再经恒温箱定型,得到成品。
实施例3:
本发明提供一种石墨烯改性高分子柔软抗变形复合发泡材料,包括如下成分及其质量:EVA:30g、POE:5g、OBCs:10g、EPDM:9.4g、SEBS:24.5g、填充剂(滑石粉):15g、石墨烯:1g、铝酸酯偶联剂:0.8g、润滑剂(硬脂酸):0.5g、金属氧化物(ZnO):1.2g、架桥剂(无味交联剂):0.6g、发泡剂(偶氮二甲酰胺) :2g,其制备方法,包括如下步骤:
1)取EVA、POE、OBCs、EPDM、SEBS、填充剂、石墨烯、偶联剂、润滑剂和金属氧化物混合后倒入密炼机中进行第一阶段密炼,翻料3次,密炼温度控制在108℃,时间为9min,再加入架桥剂和发泡剂的混合物,再次启动密炼机进行第二阶段密炼,翻料4次,密炼温度控制在115℃,时间为10min,即得到混合料;
2)将密炼好的混合料在滚轮机上进行混炼,先进行打厚,厚度为1.0cm;再进行打薄,厚度为2mm;最后进行打厚,厚度为1.0cm;
3)将混炼混合均匀的料传送到造粒机中进行造粒,得到粒料 ;
4)将粒料直接倒入模具在180℃下,进行一次发泡370 S,再在183℃下,进行二次发泡400 S,冷却400 S,得到成品。
根据DIN53504、DIN53512等测量实施例1产品的主要性能指标,其结果如表1所示:
表1 实施例1产品的主要性能指标
检测项目 实验数据 实验方法
硬度 31AskerC HG/T2489
密度 0.186 g/cm3 HG/T2872
弹性 57% GB/T1681
拉伸强度 1.5MPa GB/T528
断裂伸长率 280% GB/T528
裤型撕裂 1.6N/mm GB/T529
压缩变形 35% GB/T2876
从测量结果可知,本发明的产品质轻柔软,且具有良好的力学性能。
以上实施例仅用以说明而非限制本发明的技术方案,尽管上述实施例对本发明进行了详细说明,本领域的相关技术人员应当理解:可以对本发明进行修改或者同等替换,但不脱离本发明精神和范围的任何修改和局部替换均应涵盖在本发明的权利要求范围内。

Claims (5)

1.一种石墨烯改性高分子柔软抗变形复合发泡材料,其特征在于,包括如下成分及其质量百分比:
乙烯-醋酸乙烯酯共聚物:15%~30%;
乙烯-辛烯共聚物:5%~20%;
聚烯烃类嵌段共聚物:10%~25%;
三元乙丙橡胶:5%~15%;
苯乙烯-乙烯-丁烯-苯乙烯共聚物:15%~40%;
填充剂:5%~20%;
石墨烯:0.1%~3%;
偶联剂:0.5%~1.5%;
润滑剂:0.5%~1.5%;
金属氧化物:0.8%~1.5%;
架桥剂:0.6%~1%;
发泡剂:1.5%~3.5%。
2.根据权利要求1所述的石墨烯改性高分子柔软抗变形复合发泡材料,其特征在于,所述填充剂为滑石粉、偶联剂为铝酸酯偶联剂、润滑剂为硬脂酸、金属氧化物为氧化锌、架桥剂为无味交联剂、发泡剂为偶氮二甲酰胺。
3.一种石墨烯改性高分子柔软抗变形复合发泡材料的制备方法,其特征在于,包括如下步骤:
1)取乙烯-醋酸乙烯酯共聚物、乙烯-辛烯共聚物、聚烯烃类嵌段共聚物、三元乙丙橡胶、苯乙烯-乙烯-丁烯-苯乙烯共聚物、填充剂、石墨烯、偶联剂、润滑剂和金属氧化物混合后倒入密炼机中进行第一阶段密炼,翻料3-4次,密炼温度控制在105-108℃,时间为9-10min,再加入架桥剂和发泡剂的混合物,再次启动密炼机进行第二阶段密炼,翻料3-4次,密炼温度控制在115-120℃,时间为9-10min,即得到混合料;
2)将密炼好的混合料在滚轮机上进行混炼,先进行打厚,厚度为1.0-1.5cm;再进行打薄,厚度为2-3mm;最后进行打厚,厚度为1.0-1.5cm;
3)将混炼混合均匀的料传送到造粒机中进行造粒,得到粒料 ;
4)将粒料经注塑机注入模具中发泡,再经恒温箱定型,得到成品;或将粒料直接倒入模具进行一次发泡,再进行二次发泡并冷却得到成品。
4.根据权利要求3所述的石墨烯改性高分子柔软抗变形复合发泡材料的制备方法,其特征在于,所述发泡的温度为177-183℃,时间为370-430 S。
5.根据权利要求3所述的石墨烯改性高分子柔软抗变形复合发泡材料的制备方法,其特征在于,所述冷却的时间为370-430 S。
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