CN115109285B - 一种耐磨聚酰亚胺绝缘薄膜及其制备方法 - Google Patents
一种耐磨聚酰亚胺绝缘薄膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐磨聚酰亚胺绝缘薄膜,是将二硫化钼纳米片、纳米氧化铝加入纳米纤维素悬液中得到的纳米分散液加入聚酰胺酸溶液中,搅拌分散均匀,然后流延成膜,经过热亚胺化得到。本发明的聚酰亚胺薄膜不仅具有优良的绝缘性能,而且机械性能良好,耐磨性能优异,能够有效提高其作为电力电子行业绝缘封装材料的使用性能以及使用寿命。
Description
技术领域
本发明涉及绝缘材料技术领域,尤其涉及一种耐磨聚酰亚胺绝缘薄膜及其制备方法。
背景技术
聚酰亚胺薄膜具有优良的耐高低温性能、电气绝缘性和良好的化学稳定性,应用广泛涉及航天航空、交通运输、电力电子等行业,其中一个重要的用途是作为各种电力设备、电线电缆、电磁线等的绝缘封装材料。近年来,随着电力电子行业的迅速发展,对绝缘封装材料的性能要求越来越高。为了提高聚酰亚胺薄膜的使用寿命,避免频繁维修、更换,以及拓展聚酰亚胺薄膜封装材料的应用范围,不仅要求聚酰亚胺薄膜具有优良的绝缘性能,还对其机械性能、耐磨性能提出了更高的要求。
发明内容
基于背景技术存在的技术问题,本发明提出了一种耐磨聚酰亚胺绝缘薄膜及其制备方法。
本发明提出的一种耐磨聚酰亚胺绝缘薄膜的制备方法,包括以下步骤:
S1、依次将二硫化钼纳米片、纳米氧化铝加入纳米纤维素悬液中超声分散均匀,得到纳米分散液;
S2、将二胺单体加入溶剂中混合均匀,然后加入二酐单体,于惰性气体保护下搅拌反应,得到聚酰胺酸溶液;
S3、将所述纳米分散液加入聚酰胺酸溶液中,搅拌分散均匀,然后流延成膜,经过热亚胺化得到耐磨聚酰亚胺绝缘薄膜。
优选地,S1中,所述二硫化钼纳米片、纳米氧化铝与纳米纤维素悬液的质量比为(1-2):(0.2-0.4):100,所述纳米纤维素悬液的固含量为0.3-0.5%。
优选地,所述二硫化钼纳米片的制备方法为:将钼酸铵和硫脲加入去离子水中,得到混合溶液,然后用硫酸溶液将pH调至1-1.5,在180-220℃下水热反应15-20h,离心后将得到的固体物质洗涤后分散在溶剂中,在冰浴下超声剥离,干燥后得到二硫化钼纳米片,所述混合溶液中,钼酸铵的浓度为0.01-0.02mmol/L,硫脲的浓度为0.2-0.4mmol/L,二硫化钼纳米片的制备过程中超声剥离的功率为300-400W,时间为2-4h。
优选地,所述纳米纤维素悬液的制备方法为:将TEMPO、NaBr和木浆纤维粉末加入NaClO水溶液中,用氢氧化钠溶液将pH调至9.5-10.5,反应4-6h,然后离心,将得到的固体物质洗涤后分散在溶剂中,在冰浴中超声剥离,得到纳米纤维素悬液,其中TEMPO、NaBr、木浆纤维粉末和NaClO水溶液的比例为(0.01-0.03)g:(0.2-0.4)g:(1-2)g:(100-200)mL,NaClO水溶液的浓度为30-50mg/mL,纳米纤维素悬液的制备过程中超声剥离的功率为200-300W,时间为20-30min。
其中,木浆纤维粉末的平均纤维长度≤0.25mm,其是将针叶木浆、阔叶木浆中的至少一种经过研磨至平均纤维长度≤0.25mm,干燥后得到。
优选地,所述纳米氧化铝的粒径为10-100nm。
优选地,S2中,二胺单体与二酐单体的摩尔比为1:(1-1.05),二胺单体为4,4'-二氨基二苯醚、对苯二胺中的至少一种,二酐单体为均苯四甲酸二酐、3,3',4,4'-联苯四甲酸二酐中的至少一种。
优选地,S2中,聚酰胺酸溶液的固含量为20-30%。
优选地,S3中,纳米分散液与聚酰胺酸溶液的体积比为(0.2-0.5):1。
优选地,S3中,热亚胺化的步骤包括:以2-4℃/min的升温速率升温至320-360℃,保温30-60min。
优选地,所述溶剂为N,N-二甲基乙酰胺。
一种耐磨聚酰亚胺绝缘薄膜,由所述的制备方法制得。
本发明的有益效果如下:
本发明在聚酰亚胺基体中引入适量的二硫化钼纳米片、纳米氧化铝和TEMPO氧化法制备的纳米纤维素作为填充体系,其中二硫化钼纳米片是经过水热法制得的二硫化钼三维纳米材料经过超声剥离制得,具有剥离的二维片层结构和良好的润滑特性,TEMPO氧化法制备的纳米纤维素含大量羧基,具有静电斥力从而能够起到辅助二硫化钼纳米片、纳米氧化铝在聚酰胺酸溶液中分散均匀的作用,使热亚胺化后聚酰亚胺薄膜中的纳米氧化铝和二硫化钼纳米片能够减少团聚,在基体中分布均匀,且纳米纤维素可以在聚酰亚胺薄膜中形成三维网络结构,并与二硫化钼纳米片形成插层,从而使得到的聚酰亚胺薄膜具有优良的机械强度,同时由于纳米纤维素能够提升二硫化钼纳米片和纳米氧化铝在基体中的分散均匀性,使得纳米材料与基体之间的结合力也得到增强,从而有效提高聚酰亚胺薄膜的绝缘性能,使其能够满足绝缘封装材料的绝缘性能要求,且二硫化钼纳米片具有润滑性、纳米氧化铝能够提高硬度,两者协同使用,可以显著改善聚酰亚胺薄膜的耐磨性能。本发明得到的聚酰亚胺薄膜不仅具有优良的绝缘性能,而且机械性能良好,耐磨性能优异,能够有效提高其作为电力电子行业绝缘封装材料的使用性能以及使用寿命。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
下述实施例中,木浆纤维粉末是将针叶木浆在研磨机中研磨至平均纤维长度为0.2mm,干燥后得到。
实施例1
制备耐磨聚酰亚胺绝缘薄膜:
S1、依次将二硫化钼纳米片、纳米氧化铝加入固含量为0.3%的纳米纤维素悬液中超声分散均匀,得到纳米分散液,其中二硫化钼纳米片、纳米氧化铝与纳米纤维素悬液的质量比为1:0.2:100;
S2、将4,4'-二氨基二苯醚加入N,N-二甲基乙酰胺中混合均匀,然后加入均苯四甲酸二酐,于氮气保护下搅拌反应,得到固含量为20%的聚酰胺酸溶液,其中4,4'-二氨基二苯醚与均苯四甲酸二酐的摩尔比为1:1.05;
S3、将所述纳米分散液加入聚酰胺酸溶液中,搅拌分散均匀,然后流延成膜,以2℃/min的升温速率升温至320℃,保温60min进行热亚胺化,得到耐磨聚酰亚胺绝缘薄膜,其中纳米分散液和聚酰胺酸溶液的体积比为0.25:1。
二硫化钼纳米片的制备方法为:将钼酸铵和硫脲加入去离子水中,得到钼酸铵的浓度为0.01mmol/L、硫脲的浓度为0.2mmol/L的混合溶液,然后用硫酸溶液将pH调至1,在180℃下水热反应20h,离心后将得到的固体物质洗涤后分散在N,N-二甲基乙酰胺中,在冰浴下于300W的条件下超声剥离4h,干燥后得到二硫化钼纳米片。
纳米纤维素悬液的制备方法为:将TEMPO、NaBr和木浆纤维粉末加入浓度为40mg/mL的NaClO水溶液中,用氢氧化钠溶液将pH调至10,反应5h,然后离心,将得到的固体物质洗涤后分散在N,N-二甲基乙酰胺中,在冰浴中超声剥离,得到纳米纤维素悬液,其中TEMPO、NaBr、木浆纤维粉末和NaClO水溶液的比例为0.02g:0.25g:1.5g:150mL,NaClO水溶液的,纳米纤维素悬液的制备过程中超声剥离的功率为250W,时间为25min。
纳米氧化铝的粒径为30-60nm。
实施例2
制备耐磨聚酰亚胺绝缘薄膜:
S1、依次将二硫化钼纳米片、纳米氧化铝加入固含量为0.4%的纳米纤维素悬液中超声分散均匀,得到纳米分散液,其中二硫化钼纳米片、纳米氧化铝与纳米纤维素悬液的质量比为2:0.4:100;
S2、将4,4'-二氨基二苯醚加入N,N-二甲基乙酰胺中混合均匀,然后加入均苯四甲酸二酐,于氮气保护下搅拌反应,得到固含量为30%的聚酰胺酸溶液,其中4,4'-二氨基二苯醚与均苯四甲酸二酐的摩尔比为1:1;
S3、将所述纳米分散液加入聚酰胺酸溶液中,搅拌分散均匀,然后流延成膜,以3℃/min的升温速率升温至330℃,保温50min进行热亚胺化,得到耐磨聚酰亚胺绝缘薄膜,其中纳米分散液和聚酰胺酸溶液的体积比为0.2:1。
二硫化钼纳米片的制备方法为:将钼酸铵和硫脲加入去离子水中,得到钼酸铵的浓度为0.02mmol/L、硫脲的浓度为0.4mmol/L的混合溶液,然后用硫酸溶液将pH调至1.2,在220℃下水热反应15h,离心后将得到的固体物质洗涤后分散在N,N-二甲基乙酰胺中,在冰浴下于400W的条件下超声剥离2h,干燥后得到二硫化钼纳米片。
纳米纤维素悬液的制备方法为:将TEMPO、NaBr和木浆纤维粉末加入浓度为30mg/mL的NaClO水溶液中,用氢氧化钠溶液将pH调至9.5,反应6h,然后离心,将得到的固体物质洗涤后分散在N,N-二甲基乙酰胺中,在冰浴中超声剥离,得到纳米纤维素悬液,其中TEMPO、NaBr、木浆纤维粉末和NaClO水溶液的比例为0.01g:0.2g:1g:100mL,NaClO水溶液的,纳米纤维素悬液的制备过程中超声剥离的功率为200W,时间为30min。
纳米氧化铝的粒径为30-60nm。
实施例3
制备耐磨聚酰亚胺绝缘薄膜:
S1、依次将二硫化钼纳米片、纳米氧化铝加入固含量为0.5%的纳米纤维素悬液中超声分散均匀,得到纳米分散液,其中二硫化钼纳米片、纳米氧化铝与纳米纤维素悬液的质量比为1.5:0.3:100;
S2、将4,4'-二氨基二苯醚加入N,N-二甲基乙酰胺中混合均匀,然后加入均苯四甲酸二酐,于氮气保护下搅拌反应,得到固含量为25%的聚酰胺酸溶液,其中4,4'-二氨基二苯醚与均苯四甲酸二酐的摩尔比为1:1.02;
S3、将所述纳米分散液加入聚酰胺酸溶液中,搅拌分散均匀,然后流延成膜,以4℃/min的升温速率升温至360℃,保温30min进行热亚胺化,得到耐磨聚酰亚胺绝缘薄膜,其中纳米分散液和聚酰胺酸溶液的体积比为0.5:1。
二硫化钼纳米片的制备方法为:将钼酸铵和硫脲加入去离子水中,得到钼酸铵的浓度为0.015mmol/L、硫脲的浓度为0.3mmol/L的混合溶液,然后用硫酸溶液将pH调至1.5,在200℃下水热反应18h,离心后将得到的固体物质洗涤后分散在N,N-二甲基乙酰胺中,在冰浴下于350W的条件下超声剥离3h,干燥后得到二硫化钼纳米片。
纳米纤维素悬液的制备方法为:将TEMPO、NaBr和木浆纤维粉末加入浓度为50mg/mL的NaClO水溶液中,用氢氧化钠溶液将pH调至10.5,反应4h,然后离心,将得到的固体物质洗涤后分散在N,N-二甲基乙酰胺中,在冰浴中超声剥离,得到纳米纤维素悬液,其中TEMPO、NaBr、木浆纤维粉末和NaClO水溶液的比例为0.03g:0.4g:2g:200mL,NaClO水溶液的,纳米纤维素悬液的制备过程中超声剥离的功率为300W,时间为20min。
纳米氧化铝的粒径为30-60nm。
试验例
对实施例1-3制得的聚酰亚胺薄膜进行性能测试,测试结果如表1所示:
表1
由此可见,本发明制得的聚酰亚胺薄膜具有绝缘性以及优良的机械性能,能够满足JB/T 2726-1996相关标准,同时兼具优良的耐磨性能,适合用作电力电子行业绝缘封装材料。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (5)
1.一种耐磨聚酰亚胺绝缘薄膜的制备方法,其特征在于,包括以下步骤:
S1、依次将二硫化钼纳米片、纳米氧化铝加入纳米纤维素悬液中超声分散均匀,得到纳米分散液;
S2、将二胺单体加入溶剂中混合均匀,然后加入二酐单体,于惰性气体保护下搅拌反应,得到固含量为20-30%的聚酰胺酸溶液;二胺单体与二酐单体的摩尔比为1:(1-1.05);
S3、将所述纳米分散液加入聚酰胺酸溶液中,搅拌分散均匀,然后流延成膜,经过热亚胺化得到耐磨聚酰亚胺绝缘薄膜;纳米分散液与聚酰胺酸溶液的体积比为(0.2-0.5):1;
S1中,所述二硫化钼纳米片、纳米氧化铝与纳米纤维素悬液的质量比为(1-2):(0.2-0.4):100,所述纳米纤维素悬液的固含量为0.3-0.5%;
所述纳米纤维素悬液的制备方法为:将TEMPO、NaBr和木浆纤维粉末加入NaClO水溶液中,用氢氧化钠溶液将pH调至9.5-10.5,反应4-6h,然后离心,将得到的固体物质洗涤后分散在溶剂中,在冰浴中超声剥离,得到纳米纤维素悬液,其中TEMPO、NaBr、木浆纤维粉末和NaClO水溶液的比例为(0.01-0.03)g:(0.2-0.4)g:(1-2)g:(100-200)mL,NaClO水溶液的浓度为30-50mg/mL,纳米纤维素悬液的制备过程中超声剥离的功率为200-300W,时间为20-30min;
所述纳米氧化铝的粒径为10-100nm。
2.根据权利要求1所述的耐磨聚酰亚胺绝缘薄膜的制备方法,其特征在于,所述二硫化钼纳米片的制备方法为:将钼酸铵和硫脲加入去离子水中,得到混合溶液,然后用硫酸溶液将pH调至1-1.5,在180-220℃下水热反应15-20h,离心后将得到的固体物质洗涤后分散在溶剂中,在冰浴下超声剥离,干燥后得到二硫化钼纳米片,所述混合溶液中,钼酸铵的浓度为0.01-0.02mmol/L,硫脲的浓度为0.2-0.4mmol/L,二硫化钼纳米片的制备过程中超声剥离的功率为300-400W,时间为2-4h。
3.根据权利要求1所述的耐磨聚酰亚胺绝缘薄膜的制备方法,其特征在于,S2中,二胺单体为4,4'-二氨基二苯醚、对苯二胺中的至少一种,二酐单体为均苯四甲酸二酐、3,3',4,4'-联苯四甲酸二酐中的至少一种。
4.根据权利要求1所述的耐磨聚酰亚胺绝缘薄膜的制备方法,其特征在于,S3中,热亚胺化的步骤包括:以2-4℃/min的升温速率升温至320-360℃,保温30-60min。
5.一种耐磨聚酰亚胺绝缘薄膜,其特征在于,由权利要求1-4任一项所述的制备方法制得。
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