CN111635631A - 一种高介电常数聚酰亚胺复合材料及其制备方法 - Google Patents
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Abstract
本发明涉及复合材料领域,具体涉一种高介电常数聚酰亚胺复合材料及其制备方法,S1.将GO溶于DMF中,Co2+和对苯二甲酸,得到Co‑MOF/GO;S2.得到Co‑MOF/GO微球;S3.得到Co‑MOF/RGO微球;S4.将纳米BaTiO3溶于N,N‑二甲基乙酰胺中;S5.在步骤S3中加入Co‑MOF/RGO微球;S6.在步骤S5中加入聚酰胺酸;S7.将步骤S6反应之后的悬浮液涂覆于玻璃板上,然后在100~120℃下加热1~2h;再在200~210℃下加热1~2h,再在300~310℃下加热1~2h即得。本发明得到聚酰亚胺复合材料明显提高了介电常数,并且具有良好的机械性能。
Description
技术领域
本发明涉及复合材料领域,具体涉及一种高介电常数聚酰亚胺复合材料及其制备方法。
背景技术
石墨烯是一种单原子厚度的二维碳纳米材料,具有优异的光、电、热和力学性能,它可以明显改善聚合物基复合材料的机械性能、热性能以及介电性能。石墨烯/聚合物复合材料作为一类新型的柔韧、高强、轻质的高性能介电材料,在薄膜电容器、超大规模集成电路以及电极材料等诸多领域显示出良好的应用前景。
石墨烯虽然具有良好的导电性能和较大的比表面积,但是随着石墨烯的添加对材料的介电常数的增加会达到一个峰值,然后再加入石墨烯由于材料不能再形成均相的原因,材料的机械性能降低,材料的介电常数的增加不明显。
发明内容
本发明的目的在于克服现有技术中的石墨烯的添加达到一定值后,材料的机械性能下降,且介电常数增加不明显的问题,提供了一种高介电常数聚酰亚胺复合材料的制备方法。
本发明的另一个目的在于,提供上述制备方法所获得的高介电常数聚酰亚胺复合材料。
为了解决上述问题,本发明通过以下技术方案予以实现:
一种高介电常数聚酰亚胺复合材料的制备方法,包括以下步骤:
S1.将GO溶于DMF中,得到浓度为(1~5)mg/mL的GO溶液,再获得的GO溶液中加入摩尔比为1:(0.5~2)的Co2+和对苯二甲酸,然后再在90~120℃条件下,反应15~25h,过滤后保留沉淀干燥得到Co-MOF/GO,其中Co2+与GO的摩尔比为(2~5):1;
S2.将步骤S1获得的Co-MOF/GO溶于水中配置0.01~0.05g/mL的溶液,再按照每毫升溶液中加入0.02~0.06g的海藻酸钠,在90~95℃条件下搅拌1~3h;再向溶液中加入溶液体积3~5倍4wt%的氯化钙溶液;得到Co-MOF/GO微球;
S3.将步骤S2得到的Co-MOF/GO微球还原得到Co-MOF/RGO微球;
S4.将纳米BaTiO3溶于N,N-二甲基乙酰胺中,超声1~3h形成3~10mg/mL的分散液;
S5.在步骤S3中加入Co-MOF/RGO微球,超声1~2h形成5~20mg/mL的溶液,待Co-MOF/RGO微球分散均匀以后继续超声1~2h;
S6.在步骤S5中加入聚酰胺酸,超声反应20~30h得到悬浮液;其中聚酰胺酸的加入的质量为Co-MOF/RGO微球质量的2~8倍;
S7.将步骤S6反应之后的悬浮液涂覆于玻璃板上,然后在100~120℃下加热1~2h;再在200~210℃下加热1~2h,再在300~310℃下加热1~2h即得。
本发明通过将纳米BaTiO3和Co-MOF/RGO微球依次分散在溶剂中,纳米BaTiO3是良好的高介电常数铁电氧化物,可以有效提高合成的聚酰亚胺的介电常数。采用将纳米BaTiO3分散在聚酰亚胺的前驱体中,有利于提高BaTiO3的分散度,有利于纳米无机材料与有机材料形成均一稳定的体系。Co-MOF/RGO微球,采用金属有机框架Co-MOF与氧化石墨烯(GO)复合在形成纳米微球,然后再在还原剂的作用下将GO还原成石墨烯(RGO)。石墨烯本身是具有良好的电子迁移率的材料,在提高聚酰亚胺材料的介电常数中得到广泛的应用。但是在研究过程中发现,随着石墨烯的加入聚酰亚胺的介电常数增加不明显,而且材料的机械性能反而下降,因此本发明通过石墨烯(RGO)修饰金属框架(Co-MOF)的方式提高了材料的介电常数和机械性能。主要是由于Co-MOF中的有机相对苯二甲酸可以在聚酰亚胺聚合过程中与前驱体中的氨基结合,从而使得Co-MOF/RGO与聚酰氨基形成更稳定的均相。而且金属有机框架复合石墨烯微球具有更大的比表面积,从而有效提高了材料的介电常数。金属MOF通过有机配位物与聚酰亚胺之间形成共价键,便于聚酰亚胺分子之间的电子迁移,而填充在立体网络结构的聚酰亚胺的空隙中的无机纳米BaTiO3使电子的传递方式,不再仅限于沿着分子链或分子链之间传递,而是可以沿着整个材料任意方向的传递,进一步提供了复合材料的电子迁移能力,因此Co-MOF/RGO与纳米BaTiO3协同作用提高聚酰亚胺复合材料的介电常数。
上述纳米BaTiO3的制备通过如下方法获得:称取3~5g的TiO2与50~60mL的去离子水混合均匀,在磁力搅拌下一次加入10~20g的Ba(OH)2·8H2O和2~5g的表面活性剂PEG200,搅拌均匀,最后0.1~0.2mol/L 15~20mL的氢氧化钠溶液。搅拌均匀后将反应混合物倒入带聚四氟乙烯内衬的水热反应釜内,填充度40~50%,在220~250℃烘箱中进行水热反应30~40min。反应结束后自然冷却至室温。然后在1000~2000r/min下离心分离,再用去离子水、0.1mol/L稀醋酸和乙醇洗涤数次,出去颗粒表面残留的有机杂质。最后,置于60℃干燥箱中干燥12h,即得到。
合成聚酰胺酸包括,称取N,N-二甲基乙酰胺76.5g和6.4615g的4,4'-二氨基二苯醚,混合置于烧杯中,搅拌0.5~1.2h,在称取与4,4'-二氨基二苯醚摩尔比为1:1的均苯四甲酸二酐,分4~5i加入烧杯中,充分搅拌,使其反应完全,即得。
优选地,所述步骤S1中Co2+和对苯二甲酸的摩尔比为1:1。
优选地,所述步骤S1中Co2+与GO的摩尔比为3:1。
优选地,所述步骤S3中Co-MOF/GO微球采用抗坏血酸钠还原得到Co-MOF/RGO微球。
优选地,所述步骤S4中纳米BaTiO3的大小为10~15nm。
优选地,所述步骤S6中超声时间为22~28h。
优选地,所述步骤S6中超声时间为24h。
优选地,将悬浮液涂覆于玻璃板上,然后在100℃下反应1h,再在200℃下反应1h,再在300℃下反应1h。
上述高介电常数聚酰亚胺复合材料的制备方法所制备得到的高介电常数聚酰亚胺复合材料。
与现有技术相比,本发明具有以下技术效果:
本发明公开的一种高介电常数聚酰亚胺复合材料的制备方法,通过将纳米BaTiO3和Co-MOF/RGO微球依次分散在溶剂中,由于Co-MOF/RGO微球具有较大的比表面积并能够与聚酰亚胺形成稳定的均相,可以有效提高材料的机械性能。并且Co-MOF/RGO微球和纳米BaTiO3可以协同得到的复合材料的介电常数高。
具体实施方式
下面结合具体实施例对本发明作进一步地详细阐述,所述实施例只用于解释本发明,并非用于限定本发明的范围。下述实施例中所使用的试验方法如无特殊说明,均为常规方法;所使用的材料、试剂等,如无特殊说明,为可从商业途径得到的试剂和材料。
实施例1
一种高介电常数聚酰亚胺复合材料的制备方法,包括以下步骤:
制备纳米BaTiO3;
称取3~5g的TiO2与50~60mL的去离子水混合均匀,在磁力搅拌下一次加入10~20g的Ba(OH)2·8H2O和2~5g的表面活性剂PEG200,搅拌均匀,最后0.1~0.2mol/L 15~20mL的氢氧化钠溶液。搅拌均匀后将反应混合物倒入带聚四氟乙烯内衬的水热反应釜内,填充度40~50%,在220~250℃烘箱中进行水热反应30~40min。反应结束后自然冷却至室温。然后在1000~2000r/min下离心分离,再用去离子水、0.1mol/L稀醋酸和乙醇洗涤数次,出去颗粒表面残留的有机杂质。最后,置于60℃干燥箱中干燥12h,即得到。所述纳米BaTiO3的大小为10nm。
合成聚酰胺酸;
称取N,N-二甲基乙酰胺76.5g和6.4615g的4,4'-二氨基二苯醚,混合置于烧杯中,搅拌0.5~1.2h,在称取与4,4'-二氨基二苯醚摩尔比为1:1的均苯四甲酸二酐,分4~5i加入烧杯中,充分搅拌,使其反应完全,即得。
一种高介电常数聚酰亚胺复合材料的制备方法,包括以下步骤:
S1.将GO溶于DMF中,得到浓度为1mg/mL的GO溶液,再获得的GO溶液中加入摩尔比为1:0.5的Co2+和对苯二甲酸,然后再在120℃条件下,反应25h,过滤后保留沉淀干燥得到Co-MOF/GO,其中Co2+与GO的摩尔比为5:1;
S2.将步骤S1获得的Co-MOF/GO溶于水中配置0.01g/mL的溶液,再按照每毫升溶液中加入0.06g的海藻酸钠,在90℃条件下搅拌1h;再向溶液中加入溶液体积5倍4wt%的氯化钙溶液;得到Co-MOF/GO微球;
S3.将步骤S2得到的Co-MOF/GO微球还原得到Co-MOF/RGO微球;
S4.将纳米BaTiO3溶于N,N-二甲基乙酰胺中,超声1h形成10mg/mL的分散液;
S5.在步骤S3中加入Co-MOF/RGO微球,超声1h形成5mg/mL的溶液,待Co-MOF/RGO微球分散均匀以后继续超声1h;
S6.在步骤S5中加入聚酰胺酸,超声反应20h得到悬浮液;其中聚酰胺酸的加入的质量为Co-MOF/RGO微球质量的8倍;
S7.将步骤S6反应之后的悬浮液涂覆于玻璃板上,然后在100℃下加热2h;再在200℃下加热2h,再在300℃下加热1h即得。
上述高介电常数聚酰亚胺复合材料的制备方法所制备得到的高介电常数聚酰亚胺复合材料。
实施例2
一种高介电常数聚酰亚胺复合材料的制备方法,其特征在于,包括以下步骤:
S1.将GO溶于DMF中,得到浓度为5mg/mL的GO溶液,再获得的GO溶液中加入摩尔比为1:2的Co2+和对苯二甲酸,然后再在90℃天减小,反应15h,过滤后保留沉淀干燥得到Co-MOF/GO,其中Co2+与GO的摩尔比为2:1;
S2.将步骤S1获得的Co-MOF/GO溶于水中配置0.05g/mL的溶液,再按照每毫升溶液中加入0.02g的海藻酸钠,在95℃条件下搅拌3h;再向溶液中加入溶液体积3倍4wt%的氯化钙溶液;得到Co-MOF/GO微球;
S3.将步骤S2得到的Co-MOF/GO微球还原得到Co-MOF/RGO微球;
S4.将纳米BaTiO3溶于N,N-二甲基乙酰胺中,超声3h形成3mg/mL的分散液;
S5.在步骤S3中加入Co-MOF/RGO微球,超声2h形成20mg/mL的溶液,待Co-MOF/RGO微球分散均匀以后继续超声2h;
S6.在步骤S5中加入聚酰胺酸,超声反应0h得到悬浮液;其中聚酰胺酸的加入的质量为Co-MOF/RGO微球质量的2倍;
S7.将步骤S6反应之后的悬浮液涂覆于玻璃板上,然后在120℃下加热1h;再在210℃下加热1h,再在310℃下加热2h即得。
其他步骤同实施例1。
实施例3
一种高介电常数聚酰亚胺复合材料的制备方法,其特征在于,包括以下步骤:
S1.将GO溶于DMF中,得到浓度为3mg/mL的GO溶液,再获得的GO溶液中加入摩尔比为1:1的Co2+和对苯二甲酸,然后再在100℃天减小,反应20h,过滤后保留沉淀干燥得到Co-MOF/GO,其中Co2+与GO的摩尔比为3:1;
S2.将步骤S1获得的Co-MOF/GO溶于水中配置0.03g/mL的溶液,再按照每毫升溶液中加入0.04g的海藻酸钠,在92℃条件下搅拌2h;再向溶液中加入溶液体积4倍4wt%的氯化钙溶液;得到Co-MOF/GO微球;
S3.将步骤S2得到的Co-MOF/GO微球还原得到Co-MOF/RGO微球;
S4.将纳米BaTiO3溶于N,N-二甲基乙酰胺中,超声2h形成5mg/mL的分散液;
S5.在步骤S3中加入Co-MOF/RGO微球,超声1.5h形成10mg/mL的溶液,待Co-MOF/RGO微球分散均匀以后继续超声1.5h;
S6.在步骤S5中加入聚酰胺酸,超声反应0h得到悬浮液;其中聚酰胺酸的加入的质量为Co-MOF/RGO微球质量的5倍;
S7.将步骤S6反应之后的悬浮液涂覆于玻璃板上,然后在110℃下加热1.5h;再在205℃下加热1.5h,再在305℃下加热1.5h即得。
其他步骤同实施例1。
上述高介电常数聚酰亚胺复合材料的制备方法所制备得到的高介电常数聚酰亚胺复合材料。
对比例1
与实施例3相比,本对比例中未加入纳米BaTiO3,其他与实施例3相同。
对比例2
与实施例3相比,本对比例中为加入Co-MOF/RGO微球,其他与实施例3相同。
对比例3
与实施例3相比,本对比例中用石墨烯替代Co-MOF/RGO微球,其他与实施例3相同。
上述高介电常数聚酰亚胺复合材料的制备方法所制备得到的高介电常数聚酰亚胺复合材料。
实验例1
将Co-MOF/RGO微球和石墨烯分别配置为质量浓度为:0.05%、0.1%、0.5%、1%、2%和3%的水溶液,采用湿式比表面积测定法,分别测定Co-MOF/RGO微球和石墨烯的比表面积,结果如表下所示。
从上表可以看出Co-MOF/RGO微球的比面积明显大于石墨烯的比表面积。
实验例2
测试各实施例以及对比例所得到的复合材料的介电常数以及机械性能。并与纯的聚酰亚胺做对比。测试结果如下表所示。
从上表可以看出,实施例组的介电常数均大于对比例组的介电常数。对比例1未加入Co-MOF/RGO微球,对比例2为加入纳米BaTiO3,介电常数相比于实施例有明显的降低,说明Co-MOF/RGO微球和纳米BaTiO3对提高聚酰亚胺的介电常数具有协同作用。对比例3的介电常数由于对比例1和对比例2,但是与实施例相比介电常数要求。主要是由于石墨烯在添加一定量以后对介电常数没有明显的影响。另外,实施例材料的机械强度明显高于对比例组和纯聚酰亚胺,说明石墨烯和纳米BaTiO3与聚酰亚胺形成有机的整体,有利于提高复合材料的机械性能。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案,而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细地说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (9)
1.一种高介电常数聚酰亚胺复合材料的制备方法,其特征在于,包括以下步骤:
S1.将GO溶于DMF中,得到浓度为(1~5)mg/mL的GO溶液,再获得的GO溶液中加入摩尔比为1:(0.5~2)的Co2+和对苯二甲酸,然后再在90~120℃条件下,反应15~25h,过滤后保留沉淀干燥得到Co-MOF/GO,其中Co2+与GO的摩尔比为(2~5):1;
S2.将步骤S1获得的Co-MOF/GO溶于水中配置0.01~0.05g/mL的溶液,再按照每毫升溶液中加入0.02~0.06g的海藻酸钠,在90~95℃条件下搅拌1~3h;再向溶液中加入溶液体积3~5倍4wt%的氯化钙溶液;得到Co-MOF/GO微球;
S3.将步骤S2得到的Co-MOF/GO微球还原得到Co-MOF/RGO微球;
S4.将纳米BaTiO3溶于N,N-二甲基乙酰胺中,超声1~3h形成3~10mg/mL的分散液;
S5.在步骤S3中加入Co-MOF/RGO微球,超声1~2h形成5~20mg/mL的溶液,待Co-MOF/RGO微球分散均匀以后继续超声1~2h;
S6.在步骤S5中加入聚酰胺酸,超声反应20~30h得到悬浮液;其中聚酰胺酸的加入的质量为Co-MOF/RGO微球质量的2~8倍;
S7.将步骤S6反应之后的悬浮液涂覆于玻璃板上,然后在100~120℃下加热1~2h;再在200~210℃下加热1~2h,再在300~310℃下加热1~2h即得。
2.根据权利要求1所述高介电常数聚酰亚胺复合材料的制备方法,其特征在于,所述步骤S1中Co2+和对苯二甲酸的摩尔比为1:1。
3.根据权利要求1所述高介电常数聚酰亚胺复合材料的制备方法,其特征在于,所述步骤S1中Co2+与GO的摩尔比为3:1。
4.根据权利要求1所述高介电常数聚酰亚胺复合材料的制备方法,其特征在于,所述步骤S3中Co-MOF/GO微球采用抗坏血酸钠还原得到Co-MOF/RGO微球。
5.根据权利要求1所述高介电常数聚酰亚胺复合材料的制备方法,其特征在于,所述步骤S4中纳米BaTiO3的大小为10~15nm。
6.根据权利要求1所述高介电常数聚酰亚胺复合材料的制备方法,其特征在于,所述步骤S6中超声时间为22~28h。
7.根据权利要求6所述高介电常数聚酰亚胺复合材料的制备方法,其特征在于,所述步骤S6中超声时间为24h。
8.根据权利要求1所述高介电常数聚酰亚胺复合材料的制备方法,其特征在于,所述步骤S7中,将悬浮液涂覆于玻璃板上,然后在100℃下反应1h,再在200℃下反应1h,再在300℃下反应1h。
9.权利要求1至8任一项所述高介电常数聚酰亚胺复合材料的制备方法所制备得到的高介电常数聚酰亚胺复合材料。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116390607A (zh) * | 2023-03-17 | 2023-07-04 | 天津大学 | 一种提高晶体管光电性能的方法 |
CN116390607B (zh) * | 2023-03-17 | 2023-10-20 | 天津大学 | 一种提高晶体管光电性能的方法 |
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