CN111961305A - 一种微孔发泡hips电磁屏蔽材料及其制备方法与应用 - Google Patents
一种微孔发泡hips电磁屏蔽材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种微孔发泡HIPS电磁屏蔽材料及其制备方法与应用,属于功能高分子材料的制备技术领域。所述电磁屏蔽材料是先将HIPS、发泡剂和交联剂进行熔融共混制备共混料I,再将HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂进行熔融共混制备共混料II,最后将共混料I和共混料II进行混料后,经微孔发泡制备而成。本发明制备的微孔发泡HIPS电磁屏蔽材料具有高的电磁屏蔽效能和优异的电磁屏蔽效能稳定性,可以广泛地用于家用电器、医用电器、户外电器、工矿用电器等电器外壳的内衬,具有较高的经济价值和社会效益。对出口各国的一个强制认证要求起到关键作用。
Description
技术领域
本发明属于功能高分子材料的制备技术领域,具体涉及一种微孔发泡HIPS电磁屏蔽材料及其制备方法与应用。
背景技术
近年来,随着数字通讯和信息化产业的高速发展,电磁波作为信息传播的重要载体,已经渗入到无线电通讯设备、电子仪器、计算机和家用电器等国民经济的各个方面。现代人们的生活水平日益提高,越来越多的电器产品进入家庭,这些电器或多或少都会产生电磁辐射,长期的电磁辐射会损害人体健康,导致出现神经衰弱、失眠、健忘、白细胞减少、心率不齐、血压改变、孕妇流产和胎儿畸形等问题。过量的电磁辐射还会干扰周围其他电子设备,影响其正常工作而发生电磁兼容性问题。因此,电磁辐射已被世界卫生组织列为继水源、大气、噪声之后的第四大环境污染源,成为危害人类健康的隐形“杀手”,防护家用电器的电磁辐射已成当务之急。将常规电磁屏蔽材料添加到现有电器外壳中,是防止电器产生电磁辐射对人体造成伤害的有效手段。目前,常规电磁屏蔽材料主要有金、银、铜、镍、铁磁类、碳、石墨等。其中,金系材料虽导电性好,电磁屏蔽效果佳,但成本高,不利于工业化生产;铜系材料电阻率低,导电性好,但是存在易氧化、密度较大易下沉、在聚合物基体中分散不好的缺点;铁氧体、铁镍合金和硅铁合金等铁磁类材料虽然具有磁导率高,电磁屏蔽效果好的优点,但是具有比重大、不耐腐蚀、柔韧性差和加工困难等缺点;碳系材料中炭黑虽然容易加工,对塑料有补强作用,但导电性较差,一般用作抗静电材料,而石墨烯具有优异的导电性、导热性、力学性能、质轻以及耐腐蚀性,被认为是一种理想的电磁屏蔽填料;银系材料导电性高,成本较金系材料低,屏蔽效能一般可达65 dB,具有优异的屏蔽性能。但是,将电磁屏蔽材料直接添加到聚合物基体中,因为电磁屏蔽材料与聚合物之间的相容性差,电磁屏蔽材料在聚合物基体中易团聚、分散性和分散稳定性较差,影响电磁屏蔽效果的发挥。此外,微孔发泡技术可以大幅度地降低复合材料的密度,通过导电粒子在微孔发泡过程中聚并、取向、重排和连接等形成更加有效的导电网络,本身的泡孔结构在减轻重量的同时还会多次反射电磁波,进一步提高发泡材料的电磁屏蔽效能,在制备电磁屏蔽材料中具有独特优势。
发明内容
本发明针对目前HIPS电器外壳存在电磁屏蔽效果差的问题,提供一种微孔发泡HIPS电磁屏蔽材料及其制备方法。本发明制备的微孔发泡HIPS电磁屏蔽材料具有高的电磁屏蔽效能和优异的电磁屏蔽效能稳定性,主要用作家用电器、医用电器、户外电器、工矿用电器等电器外壳的内衬,具有较高的经济价值和社会效益。
为实现上述目的,本发明采用如下技术方案:
一种微孔发泡HIPS电磁屏蔽材料是先将HIPS、发泡剂和交联剂进行熔融共混制备共混料I,再将HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂进行熔融共混制备共混料II,最后将共混料I和共混料II进行混料后,经微孔发泡制备而成。
所述微孔发泡HIPS电磁屏蔽材料的制备方法,具体包括以下步骤:
(1)将100份HIPS、2~8份发泡剂和0.5~2份交联剂,利用高速混合机混合5~10 min,得到HIPS、发泡剂和交联剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为160~190 ℃,螺杆转速为90~120 rpm,熔融共混物经挤出、造粒和干燥,制得共混料I。
(2)将100份HIPS、5~10份相容剂、20~40份电磁屏蔽助剂、0.5~1份抗氧剂、4~8份活化剂、3~10份成核剂和4~10份润滑剂,利用高速混合机混合5~10 min,得到HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为160~190 ℃,螺杆转速为90~120 rpm,熔融共混物经挤出、造粒和干燥,制得共混料II。
(3)将100份共混料I和60~100份共混料II,利用高速混合机混合10~20 min,得到两种共混料的初混料;将上述初混料利用注射机进行微孔发泡成型,制得所述微孔发泡HIPS电磁屏蔽材料。
所述发泡剂为偶氮二甲酰胺。
所述交联剂为过氧化二异丙苯。
所述相容剂为HIPS接枝马来酸酐,其中马来酸酐的重量百分比为1.9 %。
所述电磁屏蔽助剂为负载银纳米粒子的氨基接枝还原氧化石墨烯,银纳米粒子的重量百分比为53~64 %,制备方法参照文献(Guler M, Turkoglu V, Basi Z;Determination of malation, methidathion, and chlorpyrifos ethyl pesticidesusing acetylcholinesterase biosensor based on Nafion/Ag@rGO-NH2nanocomposites, Electrochimica Acta, 2017, 240: 129-135)。
所述抗氧剂为抗氧剂1010和抗氧剂168按照1:1的重量比组成。
所述活化剂为氧化锌或硬脂酸锌中的任意一种。
所述成核剂为碳酸钙或滑石粉中的任意一种。
所述润滑剂为硬脂酸钙与硬脂酸按照1:1的重量比组成。
所述微孔发泡成型的料筒温度为160~190 ℃,注射压力为60~90 MPa,保压压力为15~20 MPa,保压时间为2~10 s,模具温度为60~80 ℃。
所述微孔发泡HIPS电磁屏蔽材料主要用于制备电器外壳的内衬。
本发明与现有技术相比具有以下优点:
(1)石墨烯具有比表面积大、比重小、电导率和热导率高等特点,在电磁波的吸收方面具有极大的优势。银纳米粒子能够提高材料的界面极化、多重反射和自然共振等作用,增强材料对电磁波的吸收损耗,具有优异的电磁屏蔽作用。单独将石墨烯或者银纳米粒子加入到聚合物中制备电磁屏蔽材料时,石墨烯或者银纳米粒子容易团聚,严重影响它们的电磁屏蔽效果。本发明采用负载银纳米粒子的石墨烯,可以有效防止石墨烯和银纳米粒子的团聚,提高它们在HIPS基体中的分散性。
(2)为了进一步提高负载银纳米粒子的石墨烯在HIPS基体中的分散性,本发明将负载银纳米粒子的氨基接枝还原氧化石墨烯和相容剂HIPS接枝马来酸酐进行熔融共混,通过氨基和马来酸酐基团之间的化学反应,将负载银纳米粒子的石墨烯接枝在HIPS上,这样可以进一步提高负载银纳米粒子的石墨烯在HIPS基体中的分散性,特别是分散稳定性。
(3)微孔发泡材料可以大幅度地降低复合材料的密度,通过导电纳米粒子在微孔发泡过程中的聚并、取向、重排、连接形成更加有效的导电网络,本身的泡孔结构在减轻重量的同时还会多次反射电磁波,进一步提高微孔复合材料的导电性能和电磁屏蔽效能。本发明将负载银纳米粒子的石墨烯均匀稳定地分散在HIPS基体中,可以制备电磁屏蔽性能优异的HIPS微孔发泡材料。
(4)本发明制备的微孔发泡HIPS电磁屏蔽材料具有高的电磁屏蔽效能和优异的电磁屏蔽效能稳定性,对频率为100 KHz、1 MHz、10 MHz、100 MHz、1 GHz和10 GHz电磁波的电磁屏蔽效能分别为35.4 dB、46.2 dB、59.1 dB、72.2 dB、60.6 dB和51.5 dB,热老化时间为0 h、500 h、1000 h、1500 h和2000 h后,电磁屏蔽效能分别为72.2 dB、71.9 dB、71.1 dB、69.4 dB和66.0 dB,主要用作家用电器、医用电器、户外电器、工矿用电器等电器外壳的内衬,具有较高的经济价值和社会效益。
具体实施方式
下面通过几组实施例和对比例对本发明所述的技术方案的优势及其效果作进一步的阐述。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1
(1)将100份HIPS、2份发泡剂和0.5份交联剂,利用高速混合机混合5 min,得到HIPS、发泡剂和交联剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为160 ℃,螺杆转速为90 rpm,熔融共混物经挤出、造粒和干燥,制得共混料I。
(2)将100份HIPS、10份相容剂、40份电磁屏蔽助剂、1份抗氧剂、8份活化剂、10份成核剂和10份润滑剂,利用高速混合机混合10 min,得到HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为190 ℃,螺杆转速为120 rpm,熔融共混物经挤出、造粒和干燥,制得共混料II。
(3)将100份共混料I和60份共混料II,利用高速混合机混合10 min,得到两种共混料的初混料;将上述初混料利用注射机进行微孔发泡成型,制得所述微孔发泡HIPS电磁屏蔽材料。
所述发泡剂为偶氮二甲酰胺。
所述交联剂为过氧化二异丙苯。
所述相容剂为HIPS接枝马来酸酐,其中马来酸酐的重量百分比为1.9 %。
所述电磁屏蔽助剂为负载银纳米粒子的氨基接枝还原氧化石墨烯,银纳米粒子的重量百分比为64 %。
所述抗氧剂为抗氧剂1010和抗氧剂168按照1:1的重量比组成。
所述活化剂为氧化锌。
所述成核剂为碳酸钙。
所述润滑剂为硬脂酸钙与硬脂酸按照1:1的重量比组成。
所述微孔发泡成型的料筒温度为190 ℃,注射压力为60 MPa,保压压力为15 MPa,保压时间为10 s,模具温度为60 ℃。
实施例2
(1)将100份HIPS、5份发泡剂和1份交联剂,利用高速混合机混合8 min,得到HIPS、发泡剂和交联剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为180 ℃,螺杆转速为110 rpm,熔融共混物经挤出、造粒和干燥,制得共混料I。
(2)将100份HIPS、8份相容剂、30份电磁屏蔽助剂、0.8份抗氧剂、6份活化剂、7份成核剂和7份润滑剂,利用高速混合机混合8 min,得到HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为180 ℃,螺杆转速为110 rpm,熔融共混物经挤出、造粒和干燥,制得共混料II。
(3)将100份共混料I和80份共混料II,利用高速混合机混合15 min,得到两种共混料的初混料;将上述初混料利用注射机进行微孔发泡成型,制得所述微孔发泡HIPS电磁屏蔽材料。
所述发泡剂为偶氮二甲酰胺。
所述交联剂为过氧化二异丙苯。
所述相容剂为HIPS接枝马来酸酐,其中马来酸酐的重量百分比为1.9 %。
所述电磁屏蔽助剂为负载银纳米粒子的氨基接枝还原氧化石墨烯,银纳米粒子的重量百分比为57 %。
所述抗氧剂为抗氧剂1010和抗氧剂168按照1:1的重量比组成。
所述活化剂为氧化锌。
所述成核剂为滑石粉。
所述润滑剂为硬脂酸钙与硬脂酸按照1:1的重量比组成。
所述微孔发泡成型的料筒温度为180 ℃,注射压力为80 MPa,保压压力为18 MPa,保压时间为6 s,模具温度为70 ℃。
实施例3
(1)将100份HIPS、8份发泡剂和2份交联剂,利用高速混合机混合10 min,得到HIPS、发泡剂和交联剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为190 ℃,螺杆转速为120 rpm,熔融共混物经挤出、造粒和干燥,制得共混料I。
(2)将100份HIPS、5份相容剂、20份电磁屏蔽助剂、0.5份抗氧剂、4份活化剂、3份成核剂和4份润滑剂,利用高速混合机混合5 min,得到HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为160 ℃,螺杆转速为90 rpm,熔融共混物经挤出、造粒和干燥,制得共混料II。
(3)将100份共混料I和100份共混料II,利用高速混合机混合20 min,得到两种共混料的初混料;将上述初混料利用注射机进行微孔发泡成型,制得所述微孔发泡HIPS电磁屏蔽材料。
所述发泡剂为偶氮二甲酰胺。
所述交联剂为过氧化二异丙苯。
所述相容剂为HIPS接枝马来酸酐,其中马来酸酐的重量百分比为1.9 %。
所述电磁屏蔽助剂为负载银纳米粒子的氨基接枝还原氧化石墨烯,银纳米粒子的重量百分比为53 %。
所述抗氧剂为抗氧剂1010和抗氧剂168按照1:1的重量比组成。
所述活化剂为硬脂酸锌。
所述成核剂为滑石粉。
所述润滑剂为硬脂酸钙与硬脂酸按照1:1的重量比组成。
所述微孔发泡成型的料筒温度为160 ℃,注射压力为90 MPa,保压压力为20 MPa,保压时间为2 s,模具温度为80 ℃。
对比例1
将实施例2中的电磁屏蔽助剂换成等重量的负载银纳米粒子的还原氧化石墨烯,银纳米粒子的重量百分比仍为57 %,其余实施路线不变,制得微孔发泡HIPS电磁屏蔽材料。
对比例2
将实施例2中的电磁屏蔽助剂换成等重量的银纳米粒子和还原氧化石墨烯混合物,银纳米粒子和还原氧化石墨烯的重量比为57:43,其余实施路线不变,制得微孔发泡HIPS电磁屏蔽材料。
对比例3
将实施例2中的电磁屏蔽助剂换成等重量的银纳米粒子,其余实施路线不变,制得微孔发泡HIPS电磁屏蔽材料。
对比例4
将实施例2中的电磁屏蔽助剂换成等重量的还原氧化石墨烯,其余实施路线不变,制得微孔发泡HIPS电磁屏蔽材料。
三组实施例和四组对比例制得产物的电磁屏蔽性能按GB12190-2006进行测试,测试结果如表1所示。将三组实施例和四组对比例制得产物置于热老化烘箱中,烘箱温度为85oC,湿度为85% RH,测试产物在不同热老化时间时,100 MHz电磁波作用下的电磁屏蔽性能,测试结果如表2所示。
表1 电磁屏蔽性能测试结果
表2 电磁屏蔽稳定性测试结果
从三组实施例和四组对比例的测试结果可以看出,三组实施例具有高的电磁屏蔽效能和优异的电磁屏蔽效能稳定性。这说明将银纳米粒子负载在石墨烯表面,并且通过在熔融共混过程中,还原氧化石墨烯的氨基和相容剂的马来酸酐基团之间的化学反应,将负载银纳米粒子的还原氧化石墨烯接枝在HIPS上,可以进一步提高负载银纳米粒子的还原氧化石墨烯在HIPS基体中的分散性和分散稳定性,制得具有高的电磁屏蔽效能和优异的电磁屏蔽效能稳定性的微孔发泡HIPS电磁屏蔽材料。
上述说明示出并描述了本发明的优选实施例,如前所述,应当理解本发明并非局限于本文所披露的形式,不应看作是对其他实施例的排除,而可用于各种其他组合、修改和环境,并能够在本文所述发明构想范围内,通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围,则都应在本发明所附权利要求的保护范围内。
Claims (10)
1.一种微孔发泡HIPS电磁屏蔽材料,其特征在于:所述电磁屏蔽材料是先将HIPS、发泡剂和交联剂进行熔融共混制备共混料I,再将HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂进行熔融共混制备共混料II,最后将共混料I和共混料II进行混料后,经微孔发泡制备而成。
2.一种权利要求1所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:它包括以下步骤:
(1)将100份HIPS、2~8份发泡剂和0.5~2份交联剂,利用高速混合机混合5~10 min,得到HIPS、发泡剂和交联剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为160~190 ℃,螺杆转速为90~120 rpm,熔融共混物经挤出、造粒和干燥,制得共混料I;
(2)将100份HIPS、5~10份相容剂、20~40份电磁屏蔽助剂、0.5~1份抗氧剂、4~8份活化剂、3~10份成核剂和4~10份润滑剂,利用高速混合机混合5~10 min,得到HIPS、相容剂、电磁屏蔽助剂、抗氧剂、活化剂、成核剂和润滑剂的初混料;将上述初混料用双螺杆挤出机进行熔融共混,熔融温度为160~190 ℃,螺杆转速为90~120 rpm,熔融共混物经挤出、造粒和干燥,制得共混料II;
(3)将100份共混料I和60~100份共混料II,利用高速混合机混合10~20 min,得到两种共混料的初混料;将上述初混料利用注射机进行微孔发泡成型,制得所述微孔发泡HIPS电磁屏蔽材料。
3.根据权利要求2所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:所述发泡剂为偶氮二甲酰胺。
4.根据权利要求2所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:所述交联剂为过氧化二异丙苯。
5. 根据权利要求2所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:所述相容剂为HIPS接枝马来酸酐,其中马来酸酐的重量百分比为1.9 %。
6. 根据权利要求2所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:所述电磁屏蔽助剂为负载银纳米粒子的氨基接枝还原氧化石墨烯,银纳米粒子的重量百分比为53~64 %。
7.根据权利要求2所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:所述抗氧剂为抗氧剂1010和抗氧剂168按照1:1的重量比组成。
8.根据权利要求2所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:所述润滑剂为硬脂酸钙与硬脂酸按照1:1的重量比组成。
9. 根据权利要求2所述的微孔发泡HIPS电磁屏蔽材料的制备方法,其特征在于:所述微孔发泡成型的料筒温度为160~190 ℃,注射压力为60~90 MPa,保压压力为15~20 MPa,保压时间为2~10 s,模具温度为60~80 ℃。
10.一种权利要求1所述微孔发泡HIPS电磁屏蔽材料的应用,其特征在于,所述电磁屏蔽材料用于制备电器外壳内衬。
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