CN112940497A - 一种电磁屏蔽pa6/ps复合泡沫材料的制备方法 - Google Patents
一种电磁屏蔽pa6/ps复合泡沫材料的制备方法 Download PDFInfo
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Abstract
本发明提供了一种电磁屏蔽PA6/PS复合泡沫材料的制备方法:将功能化碳纳米管分散在熔融己内酰胺单体中,得到己内酰胺/功能化碳纳米管悬浮液;在120~140℃下,将石墨烯和聚苯乙烯加入所得己内酰胺/功能化碳纳米管悬浮液中,保温搅拌2~4h,之后于130~160℃下真空除水,加入引发剂氢氧化钠、活化剂甲苯二异氰酸酯,得到聚合反应体系,在150~200℃下聚合20~60min,得到复合材料;将所得复合材料进行超临界CO2发泡处理,得到所述电磁屏蔽PA6/PS复合泡沫材料;该方法制备的电磁屏蔽PA6/PS复合泡沫材料能够满足低反射、高吸收及高电磁屏蔽效能的要求。
Description
技术领域
本发明属于电磁屏蔽技术领域,具体涉及一种电磁屏蔽PA6/PS复合泡沫材料的制备方法。
背景技术
随着现代高新技术的发展及第五代移动通信网络(5G)时代的到来,我们的生活、工作会变得更快速、便捷,但电磁波带来的越加严重的电磁干扰(EMI)问题也将是我们尤其需要解决的。高导电的金属作为电磁屏蔽材料具有很大的优势,但是它价格昂贵、质量大、不耐腐蚀且对电磁波的反射率极大等固有缺点限制了它的实际应用。金属材料之外的碳材料导电性也很优异,且种类繁多,如石墨、碳纳米管、石墨烯等纳米碳材料,以及天然植物碳化得到的碳材料等均能应用于电磁屏蔽领域,但其强度很难达到实际应用要求,因此极大的限制了其在电磁屏蔽领域的应用。因此,设计一种新的方案制备出具有低反射、高吸收且质量轻的电磁屏蔽材料具有重要意义。
目前已有相关技术公开了制备PA6(聚酰胺-6)、PS(聚苯乙烯)电磁屏蔽材料的方法。专利申请号201611242257.3和201721000670.9分别报道了利用碳纤维、超细镍粉和PA6熔融共混制得PA6的电磁屏蔽材料以及制备了一种多层的PS片材作为电磁屏蔽材料,其中专利一将导电和吸波填料同时添加到一个体系中满足目前市场倾向于吸收主导电磁屏蔽材料的需求,但是碳纤维、超细镍粉添加量较大,且碳纤维和超细镍粉都需要预先处理才能使用,专利二利用多层结构对电磁波进行吸收反射再吸收的作用,多层结构包括PS片材层、由碳纤维构成的屏蔽层和绝缘层,但是层间结合力较差形成的空隙会影响其对电磁波的反射和吸收作用,最终影响其电磁屏蔽效能,而且两项专利的制备工艺均较为繁琐,而本发明原料购得不需要预处理,且一步法制得具有较高电磁屏蔽效能的材料。
PA6、PS强度高,相较于金属材料具有价廉、质轻、耐腐蚀和易成型加工等优点,而碳纳米管、石墨烯具有优异的导电性能和极大的比表面积,同时,本设计方案制备得到的具有“相反转”形貌的PA6/PS复合材料中分散相是PA6微球,而连续相PS则是利用超临界CO2发泡技术形成PS泡沫,微球和泡孔的存在均有利于材料对电磁波的吸收,从而增强材料的电磁屏蔽效能。因此本发明提出的方案得到的复合材料密度低且具有极高的电磁屏蔽效能,在电磁屏蔽领域具有广泛的应用价值。
发明内容
本发明目的在于提供一种电磁屏蔽PA6/PS复合泡沫材料的制备方法,该方法制备的电磁屏蔽PA6/PS复合泡沫材料能够满足低反射、高吸收及高电磁屏蔽效能的要求。
本发明技术方案中,提供了一种通过反应诱导相分离法制备PA6微球的方法;提供了一种高电磁屏蔽效能的PA6/功能化碳纳米管/PS/石墨烯复合泡沫材料的制备方法,可以通过改变配方来调控微球和泡孔的尺寸,并通过功能化碳纳米管、石墨烯的添加以及结合超临界CO2发泡技术来实现。
本发明的技术方案如下:
一种电磁屏蔽PA6/PS复合泡沫材料的制备方法,包括如下步骤:
(1)将功能化碳纳米管(FCNT)分散在熔融己内酰胺单体(CL)中,得到己内酰胺/功能化碳纳米管(CL/FCNT)悬浮液;
所述功能化碳纳米管包括但不限于羟基化碳纳米管(CNTs-OH)、羧基化碳纳米管(CNTs-COOH)等;
所得己内酰胺/功能化碳纳米管悬浮液中,功能化碳纳米管浓度为0.001~5wt%;
(2)在120~140℃下,将石墨烯和聚苯乙烯(PS)加入步骤(1)所得己内酰胺/功能化碳纳米管悬浮液中,保温搅拌2~4h,之后于130~160℃下真空除水,加入引发剂氢氧化钠(NaOH)、活化剂甲苯二异氰酸酯(TDI),得到聚合反应体系,在150~200℃下聚合20~60min,得到复合材料(记作:FCNT@PA6/PS/石墨烯复合材料);
所述聚合反应体系中,聚苯乙烯含量为10~30wt%,石墨烯含量为聚苯乙烯的0.001~5wt%,氢氧化钠含量为0.1~1wt%,甲苯二异氰酸酯含量为0.1~1wt%,余下为己内酰胺/功能化碳纳米管悬浮液;
(3)将步骤(2)所得复合材料进行超临界CO2发泡处理,得到所述电磁屏蔽PA6/PS复合泡沫材料(记作:FCNT@PA6/PS/石墨烯复合泡沫材料);
所述超临界CO2发泡处理的参数为:发泡温度100~150℃、发泡压力9~15MPa,保压时间30~300min。
本发明制得的电磁屏蔽PA6/PS复合泡沫材料以功能化碳纳米管/PA6(FCNT@PA6)微球为分散相,石墨烯/PS为连续相,其中微球的尺寸可控制在1000~50000nm,泡孔尺寸可控制在1000~10000nm。
本发明的有益效果在于:
本发明通过一种操作简单、耗时短的方法制备得到了双填料双结构的电磁屏蔽复合材料,其中,利用FCNT、石墨烯的选择性分散以及CL单体在PS存在下通过阴离子开环聚合得到具有相反转结构的FCNT@PA6微球,且FCNT、石墨烯的选择性分散使得材料内部的导电网络相较于随机分散更致密;而石墨烯/PS作为连续相,再通过绿色环保的超临界CO2发泡技术使PS相发泡形成一种功能化碳纳米管@PA6/PS/石墨烯复合泡沫材料,微球和泡孔的存在均能引起电磁波在材料内部的多重反射、折射和散射,从而提高材料的阻抗匹配和对电磁波的吸收,最终得到高吸收高屏蔽效能的电磁屏蔽材料。
本发明将微球和泡孔结构结合,并利用FCNT、石墨烯选择性分布在CL和PS中,一步实现填料的可控定位,以增强材料的电磁屏蔽效能;另外,泡孔结构的引入能引起电磁波在界面间的多重反射、折射以及散射,增强了材料对电磁波的吸收能力,本发明操作简便,导电填料需求量低,复合泡沫具有密度小、低反射以及屏蔽效能高等特点,为制备高性能绿色电磁屏蔽材料设计提供了新的方法。
附图说明
图1为本发明实施例1中制备的PA6/PS复合材料的SEM图。
图2为本发明实施例2中制备的PA6/PS复合泡沫材料的SEM图。
具体实施方式
下面通过具体实施例进一步描述本发明,但本发明的保护范围并不仅限于此。
以下实施例中用到的CNTs-OH购于阿拉丁,是内径5-10nm,外径10-30nm,长度10-30μm,CAS号为308068-56-6的工业级羟基化多壁碳纳米管;CNTs-COOH购于成都有机化学研究所,直径10-20nm,长度20-30μm,产品型号为TNMC3;PS购于奇美化工产品有限公司,熔体流动速率为200℃、5kg下8.0cm3/10min,密度为1.04g/cm3,牌号为PG-22。
实施例1
一种电磁屏蔽PA6/PS复合材料制备方法
将0.50g CNTs-OH加入85g熔融CL中,在85℃下水浴超声45min得到FNCT均匀分散的CL/FCNT悬浮液。在125℃下加入15gPS、0.50g石墨烯,机械搅拌3h得到CL/PS/CNTs-OH/石墨烯悬浮液。将该悬浮液置于150℃加热套中真空除水30min,加入0.4gNaOH,继续除水30min,加入0.6gTDI,迅速剧烈摇晃后倒入180℃模具中聚合30min,最终得到CNTs-OH@PA6/PS/石墨烯复合材料。
实施例2
一种电磁屏蔽PA6/PS复合泡沫材料制备方法
将0.50g CNTs-OH加入85g熔融CL中,在85℃下水浴超声45min得到FNCT均匀分散的CL/FCNT悬浮液。在125℃下加入15gPS、0.50g石墨烯,机械搅拌3h得到CL/PS/CNTs-OH/石墨烯悬浮液。将该悬浮液置于150℃加热套中真空除水30min,加入0.4gNaOH,继续除水30min,加入0.6gTDI,迅速剧烈摇晃后倒入180℃模具中聚合30min。将得到的CNTs-OH@PA6/PS/石墨烯复合材料在100℃、10.8MPa以及保压2h的条件下进行超临界CO2发泡处理,最终得到CNTs-OH@PA6/PS/石墨烯复合泡沫材料。
实施例3
一种电磁屏蔽PA6/PS复合泡沫材料制备方法
将1.00g CNTs-OH加入85g熔融CL中,在85℃下水浴超声45min得到FNCT均匀分散的CL/FCNT悬浮液。在125℃下加入15gPS、1.00g石墨烯,机械搅拌3h得到CL/PS/CNTs-OH/石墨烯悬浮液。将该悬浮液置于150℃加热套中真空除水30min,加入0.4gNaOH,继续除水30min,加入0.6gTDI,迅速剧烈摇晃后倒入180℃模具中聚合30min,最终得到CNTs-OH@PA6/PS/石墨烯复合材料。
实施例4
一种电磁屏蔽PA6/PS复合泡沫材料制备方法
将1.00g CNTs-OH加入85g熔融CL中,在85℃下水浴超声45min得到FNCT均匀分散的CL/FCNT悬浮液。在125℃下加入15gPS、1.00g石墨烯,机械搅拌3h得到CL/PS/CNTs-OH/石墨烯悬浮液。将该悬浮液置于150℃加热套中真空除水30min,加入0.4gNaOH,继续除水30min,加入0.6gTDI,迅速剧烈摇晃后倒入180℃模具中聚合30min。将得到的CNTs-OH@PA6/PS/石墨烯复合材料在100℃、10.8MPa以及保压2h的条件下进行超临界CO2发泡处理,最终得到CNTs-OH@PA6/PS/石墨烯复合泡沫材料。
实施例5
一种电磁屏蔽PA6/PS复合泡沫材料制备方法
将1.00g CNTs-COOH加入85g熔融CL中,在85℃下水浴超声45min得到FNCT均匀分散的CL/FCNT悬浮液。在125℃下加入15gPS、1.00g石墨烯,机械搅拌3h得到CL/PS/CNTs-COOH/石墨烯悬浮液。将该悬浮液置于150℃加热套中真空除水30min,加入0.4gNaOH,继续除水30min,加入0.6gTDI,迅速剧烈摇晃后倒入180℃模具中聚合30min。将得到的CNTs-COOH@PA6/PS/石墨烯复合材料在100℃、10.8MPa以及保压2h的条件下进行超临界CO2发泡处理,最终得到CNTs-COOH@PA6/PS/石墨烯复合泡沫材料。
测试例1
电磁屏蔽效能测试
按照波导法,使用矢量网络分析仪(安捷伦E5071C)测试实施例1-5在8.2-12.4GHz频率范围内的电磁屏蔽效能(EMI SE)。用于测试电磁屏蔽效能的样品尺寸为长22.9mm、宽10.2mm、厚度2mm的矩形试样。
表1电磁屏蔽测试结果(电磁屏蔽材料的商用标准为20dB)
一般电磁屏蔽效能以20dB(商用标准)为划分依据。从表1可以看出,本发明电磁屏蔽材料的磁屏蔽效果能够达到并优于商用。同时,采用本发明制备得到的PA6/PS复合泡沫材料的电磁屏蔽效能,远高于未发泡的PA6/PS复合材料。其原因在于:发泡样品给材料内部提高了更多的界面,能引起电磁波的多重反射和折射,从而提高复合泡沫材料的电磁屏蔽效能。
Claims (5)
1.一种电磁屏蔽PA6/PS复合泡沫材料的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)将功能化碳纳米管分散在熔融己内酰胺单体中,得到己内酰胺/功能化碳纳米管悬浮液;
(2)在120~140℃下,将石墨烯和聚苯乙烯加入步骤(1)所得己内酰胺/功能化碳纳米管悬浮液中,保温搅拌2~4h,之后于130~160℃下真空除水,加入引发剂氢氧化钠、活化剂甲苯二异氰酸酯,得到聚合反应体系,在150~200℃下聚合20~60min,得到复合材料;
(3)将步骤(2)所得复合材料进行超临界CO2发泡处理,得到所述电磁屏蔽PA6/PS复合泡沫材料。
2.如权利要求1所述电磁屏蔽PA6/PS复合泡沫材料的制备方法,其特征在于,步骤(1)中所述功能化碳纳米管为羟基化碳纳米管或羧基化碳纳米管。
3.如权利要求1所述电磁屏蔽PA6/PS复合泡沫材料的制备方法,其特征在于,步骤(1)所得己内酰胺/功能化碳纳米管悬浮液中,功能化碳纳米管浓度为0.001~5wt%。
4.如权利要求1所述电磁屏蔽PA6/PS复合泡沫材料的制备方法,其特征在于,步骤(2)所述聚合反应体系中,聚苯乙烯含量为10~30wt%,石墨烯含量为聚苯乙烯的0.001~5wt%,氢氧化钠含量为0.1~1wt%,甲苯二异氰酸酯含量为0.1~1wt%,余下为己内酰胺/功能化碳纳米管悬浮液。
5.如权利要求1所述电磁屏蔽PA6/PS复合泡沫材料的制备方法,其特征在于,步骤(3)所述超临界CO2发泡处理的参数为:发泡温度100~150℃、发泡压力9~15MPa,保压时间30~300min。
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