CN112126197A - 一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法 - Google Patents
一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,包括:将环氧树脂100份、固化剂60‑100份、助剂0.05‑1份在80‑95℃下反应至体系扭矩值为0.02‑0.08dN.m,冷却得到固态混合物;取100份与导电粒子0‑30份、发泡剂0.3‑3份球磨分散2‑30min得到环氧混合物粉末;先将一种环氧混合物粉末压实,再倒入相同质量另一种配方的环氧混合物粉末,压实为两层结构,如此重复得到多层待发泡样,在90‑160℃发泡成型2‑4h;然后升温至180‑200℃保温2h,自然冷却至室温脱模即得到。本发明可简单方便的调控相邻层中的泡孔结构、层厚、导电粒子含量及层界面,材料电磁波吸收性能及力学性能较好。
Description
技术领域
本发明涉及聚合物加工技术领域,具体涉及一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法。
背景技术
环氧发泡材料具有较好的热稳定性、力学性能、隔热性能以及轻质等优点,已经广泛应用在汽车、电子灌封、飞机制件、船体外壳等领域。通过向环氧发泡体系中加入碳系导电物质,可以制备出既具有导电功能又具有良好力学性能的环氧树脂基导电复合材料,赋予环氧发泡制品抗静电、电磁屏蔽等功能。国内外广泛报道了通过超临界气体间歇发泡法制备环氧树脂导电复合微孔发泡材料,然而,这种工艺发泡时间长,工艺复杂,且难以制备大件复杂制品。采用化学发泡法可以方便、高效、简单的制备出大尺寸环氧发泡制品,但由于环氧树脂初期粘度较低,制备的发泡材料的泡孔尺寸较大,且泡孔分布也不均匀,严重降低了环氧发泡材料的力学性能。
交替多层结构结合了不同发泡材料的优点,其形成的受限空间可以有效抑制泡孔过分生长,从而降低泡孔尺寸,此外,通过单层设计每一层的结构,可以赋予材料更多复杂的功能。研究表明,多层发泡结构可以有效改善材料的吸波、隔音及力学性能。中国专利CN106393541A于2017年2月15日公开了发明名称为“交替多层聚合物微孔发泡材料的制备方法”,其选择了维卡软化点或熔点不同的实体层和发泡层基体,将其成型为交替多层结构的初始样品后,再通过超临界发泡制备了具有实体层和发泡层交替排列的发泡材料,可以降低发泡材料的平均泡孔尺寸。中国专利CN110216958A于2019年9月10日公开了发明名称为“一种低热导率耐拉耐压的多层发泡材料及其制备方法”,其通过多层共挤及间歇发泡法制备了一种发泡层和实体层交替叠合的聚烯烃材料,该发泡材料具有较高的隔热和力学性能。中国专利CN109532047A于2019年3月29日公开了发明名称为“一种交替多层微孔硅橡胶泡沫材料的制备方法”,其利用不同种类白炭黑在硅橡胶基体中的成核效能的差异,通过多层共挤及间歇发泡法制备了一种相邻层中泡孔分布不一的多层微孔硅橡胶泡沫材料。但上述专利申请采用的是多层共挤和间歇发泡法制备多层发泡材料,得到的材料大多存在实体不发泡层,增大了材料的密度;如果相邻层为不同聚合物材料,由于较差的界面结合容易使得材料剥离,严重降低材料的使用价值;此外,这种技术路线难以调控每层的泡孔结构和厚度,也难以应用于制备多层环氧发泡材料。
发明内容
本发明的目的在于克服上述缺点而提供的一种可简单方便的调控相邻层中的泡孔结构、层厚、导电粒子含量及层界面,材料电磁波吸收性能及力学性能较好的交替多层环氧树脂基导电复合微孔发泡材料的制备方法。
为实现本发明的发明目的,采用以下技术方案:
本发明的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,包括如下步骤:
(1)预固化:将环氧树脂100份、固化剂60-100份、助剂0.05-1份在80-95℃下反应至体系扭矩值为0.02-0.08dN.m,冷却得到固态混合物;
(2)共混制粉:将预固化后的固态混合物100份、导电粒子0-30份、发泡剂0.3-3份球磨分散2-30min得到环氧混合物粉末;
(3)多层压片:选择上述范围的两种不同配方的环氧混合物粉末,先将一种在10MPa的压力下压实,再倒入相同质量另一种配方的环氧混合物粉末,10MPa的压力下压实为两层结构,如此重复得到多层待发泡样,控制单层厚度为0.2-2mm;
(4)发泡固化:将上述多层待发泡样放入模具中,在90- 160℃发泡成型2-4h;然后升温至180-200℃保温2h,自然冷却至室温脱模即得到交替多层环氧树脂基导电复合微孔发泡材料。
上述的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,其中:所述步骤(1)中环氧树脂为双酚A类环氧树脂,固化剂为液态酸酐,助剂为DMP-30。
上述的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,其中:所述步骤(2)中导电粒子为碳系导电粒子:纳米导电炭黑、多壁碳纳米管、石墨烯或纳米碳纤维中的一种。
上述的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,其中:所述步骤(2)中发泡剂为为碳酸氢钠、4,4-氧代双苯磺酰肼、偶氮二异丁腈或N,N’-二亚硝基五次甲基四胺中的一种。
本发明与现有技术相比,具有明显的有益效果,从以上技术方案可知:本发明采用的交替多层排列方式中相邻两种材料中配方不同,并采用多层冷压及化学发泡技术,可以简单方便的调控相邻层中的泡孔结构、层厚、导电粒子含量及层界面,制备出相邻层泡孔结构明显不同的交替多层微孔环氧发泡材料,多层发泡材料固化后,界面清晰,且由于发生交联反应形成较高的层间界面结合强度,无论是受力弯曲时还是平行于界面压缩时,多层环氧发泡材料都不会发生剥离,具有较好力学性能。同时由于发泡材料为交替多层泡孔结构,且可以使得相邻层中的导电粒子含量和种类不同,层界面能够引起电磁波的多次反射,增强电磁波的损耗,当电导率低的一面对着入射电磁波,电磁波在表面的反射减少,而内部的吸收作用增强使得材料电磁波吸收性能好。
附图说明
图1 是CNT含量为0.5%和2%的两种材料叠层形成的4层环氧发泡材料的电镜照片;
图2为实施例1中电磁屏蔽吸收效率随层数的变化图;
图3是发泡剂含量为0.5%和1.5%的两种材料叠层形成的4层环氧发泡材料的电镜照片;
图4是实施例3中多层发泡材料的压缩强度的变化图。
具体实施方式
下结合附图及较佳实施例,对依据本发明提出的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,具体实施方式、结构、特征及其功效,详细说明如下:
实施例1:
一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,包括如下步骤:
取双酚A型环氧树脂100份,液态酸酐固化剂85份,DMP-30助剂0.3份在高速分散机中搅拌均匀,然后加入反应器中在85℃反应至体系扭矩值为0.04dN.m,冷却得到固态混合物。然后取100份固态环氧树脂混合物,多壁碳纳米管0.5份,发泡剂N,N’-二亚硝基五次甲基四胺0.5份在球磨机中,球磨分散4min,得到混合物粉末A;取100份固体环氧树脂混合物,多壁碳纳米管2份,发泡剂N,N’-二亚硝基五次甲基四胺0.5份在球磨机中,球磨分散4min,得到混合物粉末B;先取粉末A倒入直径为25mm的圆柱形模具中在10MPa压力下压实成单层厚度为0.2 mm片层,再倒入相同质量的粉末B,10MPa的压力下压成AB两层结构,每层单层厚度为0.2mm,如此重复得到ABAB四层结构或ABABAB六层结构等待发泡样;将多层待发泡样放入模具中,在90℃下发泡成型2h后,烘箱升高温度至200℃保温2h,自然冷却至室温脱模得到交替多层环氧树脂基微孔发泡材料。
实验结果:低倍照片图1(1)中基本看不出4L发泡材料的层界面及泡孔差异,高倍照片图1(2)可以看出相邻两层的泡孔存在一定差异,B层中多壁碳纳米管含量高如图1(3),泡孔尺寸略小,泡孔密度高;A层中多壁碳纳米管含量低如图1(4),泡孔尺寸略大,泡孔密度低。从图2中可以看出,随着层数的增加,多层环氧发泡材料的电磁屏蔽吸收效率SEr不断增大。
实施例2:
一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,包括如下步骤:
取双酚A型环氧树脂100份,液态酸酐固化剂80份,DMP-30助剂0.15份,在高速分散机中搅拌均匀,然后加入反应器中在85℃反应至体系扭矩值为0.04dN.m,冷却得到固态混合物。然后取100份固态环氧树脂混合物,多壁碳纳米管2份,发泡剂N,N’-二亚硝基五次甲基四胺0.5份在球磨机中球磨分散4min,得到混合物粉末A;取100份固体环氧树脂混合物,多壁碳纳米管2份,发泡剂N,N’-二亚硝基五次甲基四胺1.5份在球磨机中球磨分散4min,得到混合物粉末B;先取A倒入直径为25mm的圆柱形模具中在10MPa压力下压实成单层厚度为0.5 mm片层,再倒入相同质量的粉末B,10MPa的压力下压成AB两层结构,每层单层厚度为0.5mm,如此重复可以得到ABAB四层结构、ABABAB六层结构等待发泡样;然后将多层待发泡样放入模具中,在110℃下发泡成型2h后,烘箱升高温度至200℃保温2h,自然冷却至室温脱模得到交替多层环氧树脂基微孔发泡材料。
实验结果:低倍照片图2(1)中可以明显看出4L发泡材料的层界面及泡孔差异,高倍照片图1(2)可以看出相邻两层的界面清晰,且粘结紧密,B层中发泡剂含量高,泡孔尺寸大,泡孔密度高;A层中发泡剂含量低,泡孔尺寸小,泡孔密度低。
实施例3:
一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,包括如下步骤:
取双酚A型环氧树脂100份,液态酸酐固化剂90份,DMP-30助剂0.15份,加入反应器中在85℃反应至至体系扭矩值为0.08dN.m,冷却得到固态混合物。然后取100份固态环氧树脂混合物,发泡剂偶氮二异丁腈0.5份在球磨机中球磨分散4min,得到不同混合物粉末A;取100份固体环氧树脂混合物,多壁碳纳米管2份,发泡剂偶氮二异丁腈0.5份,在球磨机中球磨分散4min,得到混合物粉末B;先取A在10MPa压力下压实成单层厚度1mm片层,再倒入相同质量的粉末B,10MPa的压力下压成AB两层结构,每层单层厚度为1mm,如此重复可以得到ABAB四层结构、ABABAB六层结构等待发泡样;然后将多层待发泡样放入模具中,在110℃下发泡成型2h后,提升烘箱温度至200℃保温2h,自然冷却至室温脱模得到交替多层环氧树脂基微孔发泡材料。
经测试,如图4所示,固定交替发泡层数为4层,A组分中加入0-30份的碳纤维,随着A层中碳纤维含量增加,多层发泡材料的压缩强度不断增大;固定A层中碳纤维含量为20份,随着交替多层层数的增加,多层发泡材料的压缩强度略有增大。因而可以通过增强交替层中的一种发泡层即可达到整体增强的效果。
实施例4:
取双酚A型环氧树脂100份,液态酸酐固化剂100份,DMP-30助剂1份,加入反应器中在80℃反应至室温下至体系扭矩值为0.02dN.m,冷却得到固态混合物。然后取100份固态环氧树脂混合物,石墨烯8份,发泡剂碳酸氢钠0.3份在球磨机中球磨分散2min,得到混合物粉末A;取100份固态环氧树脂混合物,纳米导电炭黑10份,发泡剂碳酸氢钠0.3份在球磨机中球磨分散2min,得到混合物粉末B;先取一定质量的A在10MPa压力下压实成单层厚度为2mm片层,再倒入相同质量的粉末B 在10MPa的压力下压成AB两层结构,每层单层厚度为2mm,如此重复可以得到ABAB四层结构、ABABAB六层结构等待发泡样;然后将多层待发泡样放入模具中,在150℃下发泡成型2h后,提升烘箱温度至200℃保温2h,自然冷却至室温脱模得到交替多层环氧树脂基微孔发泡材料。
实施例5:
取双酚A型环氧树脂100份,液态酸酐固化剂60份,DMP-30助剂0.05份,加入反应器中在95℃反应至体系扭矩值为0.08dN.m,冷却得到固态混合物。然后取100份固态环氧树脂混合物,纳米碳纤维30份,4,4-氧代双苯磺酰肼3份在球磨机中球磨分散30min,得到混合物粉末A;取100份固态环氧树脂混合物,多壁碳纳米管2份,4,4-氧代双苯磺酰肼3份在球磨机中球磨分散30min,得到混合物粉末B;先取A在10MPa压力下压实成单层厚度为1.5mm片层,再倒入一定质量的粉末B,10MPa的压力下压成AB两层结构,每层单层厚度为1.5mm,如此重复可以得到ABAB四层结构、ABABAB六层结构等待发泡样;然后将多层板放入模具中,在160℃下发泡成型4h后,提升烘箱温度至180℃保温2h,自然冷却至室温脱模得到交替多层环氧树脂基微孔发泡材料。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,任何未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (4)
1.一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,包括如下步骤:
(1)预固化:将环氧树脂100份、固化剂60-100份、助剂0.05-1份在80-95℃下反应至体系扭矩值为0.02-0.08dN.m,冷却得到固态混合物;
(2)共混制粉:将预固化后的固态混合物100份、导电粒子0-30份、发泡剂0.3-3份球磨分散2-30min得到环氧混合物粉末;
(3)多层压片:选择上述范围的两种不同配方的环氧混合物粉末,先将一种在10MPa的压力下压实,再倒入相同质量另一种配方的环氧混合物粉末,10MPa的压力下压实为两层结构,如此重复得到多层待发泡样,控制单层厚度为0.2-2mm;
(4)发泡固化:将上述多层待发泡样放入模具中,在90- 160℃发泡成型2-4h;然后升温至180-200℃保温2h,自然冷却至室温脱模即得到交替多层环氧树脂基导电复合微孔发泡材料。
2.如权利要求1所述的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,其中:所述步骤(1)中环氧树脂为双酚A类环氧树脂,固化剂为液态酸酐,助剂为DMP-30。
3.如权利要求1或2所述的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,其中:所述步骤(2)中导电粒子为碳系导电粒子:纳米导电炭黑、多壁碳纳米管、石墨烯或纳米碳纤维中的一种。
4.如权利要求3所述的一种交替多层环氧树脂基导电复合微孔发泡材料的制备方法,其中:所述步骤(2)中发泡剂为为碳酸氢钠、4,4-氧代双苯磺酰肼、偶氮二异丁腈或N,N’-二亚硝基五次甲基四胺中的一种。
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