CN108755104B - 一种表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜的制备方法 - Google Patents
一种表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜的制备方法 Download PDFInfo
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Abstract
一种表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜的制备方法。首先将静电纺丝制备的聚酰亚胺纳米纤维膜放入氢氧化钾溶液中进行刻蚀,随后经过水洗至中性后再浸泡在钛化合物水溶液中处理,最后经水洗、干燥和升温热亚胺化处理,从而制备出表面修饰二氧化钛纳米颗粒层的聚酰亚胺纤维膜。本发明的方法实施过程简单,基体结构保持良好,成本低廉,且二氧化钛纳米颗粒层的厚度可控制在10nm以内,应用前景良好。
Description
技术领域
本发明属于聚酰亚胺纤维膜技术领域,尤其是涉及一种表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜的制备方法。
背景技术
近年来,随着环境问题的日益突出和新能源汽车的迅猛发展,大功率锂离子电池成为当前研究的热点。其中,电池隔膜作为锂离子电池的重要组成部分,直接影响锂离子电池的综合性能,特别是安全性能,所以隔膜也被称为电池的第三电极。目前,商业锂离子电池隔膜主要是聚烯烃隔膜:聚乙烯(PE)和聚丙烯(PP)隔膜。虽然聚烯烃隔膜具有力学性能好、耐化学腐蚀和电池性能稳定的优点,但是其对电解液浸润性差和孔隙率小的缺点会影响其在大功率锂离子电池中的应用,特别是其耐热性差的特点容易引起电池的短路甚至爆炸,给用户带来极大的安全隐患。
聚酰亚胺(PI)是目前高分子材料中综合性能最好的材料之一,它具有优异的机械性能、良好的耐热性能、介电性能、耐腐蚀性能、耐辐射性能和耐化学药品性,在很多领域如家用电器、汽车工业、电子信息、航空航天、军事装备、精密机械、自动化仪器等都得到了迅猛的发展。而采用静电纺丝制备的聚酰亚胺纳米纤维膜结合了聚酰亚胺和静电纺丝两者的优点,具有耐温性好和孔隙率高的特点,有望成为新一代大功率锂离子电池隔膜。同时,为了改善聚酰亚胺纳米纤维膜的浸润性,与无机组分进行复合是当下简单而有效的手段之一。
制备聚酰亚胺基有机/无机复合纤维膜的方法主要有原位聚合法、直接共混法和溶胶-凝胶法。直接共混法是将无机纳米粒子直接与聚酰亚胺或者聚酰亚胺的前驱体进行混合得到的复合材料。如专利CN102277648B曾采用直接共混法成功制备出了无机/有机复合聚酰亚胺基纳米纤维膜。但是这种方法最大的问题是无机纳米颗粒大部分存在于基体纤维的内部,不仅对浸润性的改善有限,而且对基体纤维有很大的破坏作用。溶胶凝胶法是指将无机化合物水解缩合后形成溶胶,再与有机高分子溶液或乳液共混,发生凝胶化后形成聚合物/无机纳米复合材料。如专利CN101301592A曾采用溶胶-凝胶法制备出了聚酰亚胺/二氧化钛复合亚微米纤维膜。此种方法同样存在上述问题。
发明内容
本发明的目的在于提供一种表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜的制备方法。本发明的方法工艺过程简单,绿色环保,且二氧化钛纳米层的厚度可控制在10nm以下,应用前景良好。
一种表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜的制备方法,包括以下步骤:
A:将聚酰胺酸溶液经静电纺丝法制得聚酰胺酸纤维膜;
B:将步骤A制得的聚酰胺酸纤维膜置于热炉中处理,使聚酰胺酸纤维膜转变为聚酰亚胺纤维膜;
C:将步骤B制得的聚酰亚胺纤维膜浸泡在1~5mol/L的KOH溶液中5~30min,随后再放入去离子水中清洗至中性;
D:将步骤C制得的聚酰亚胺纤维膜放入0.1~0.3mol/L的钛化合物水溶液中处理10min~2h,随后放入去离子水中超声清洗1~3次;
E:将步骤D制得的聚酰亚胺纤维膜置于热炉中处理,从而制得表面修饰二氧化钛纳米颗粒的聚酰亚胺纤维膜。
步骤A中的聚酰胺酸溶液的固含量为8%~30%。
步骤B中热炉处理的温度为300~350℃,时间为1~3h;优选地,步骤B中热炉处理的温度为300℃,时间为2h。
步骤C中聚酰亚胺纤维表面产生羧基,便于后续与钛离子发生配位反应;优选浸泡在1mol/L的KOH溶液中10min。
步骤D中所述的钛化合物为硫酸氧钛或硫酸钛,钛化合物一边发生水解反应,同时与聚酰亚胺纤维表面的羧基发生配位反应。采用1mol/L的KOH溶液浸泡10min的聚酰亚胺纳米纤维膜效果最佳,并且因为其表面致密的TiO2层的存在使其拉伸强度有一定的提高。
步骤D中热炉处理的温度为300~350℃,时间为1~3h;优选地,步骤D中热炉处理的温度为300℃,时间为2h;优选地以2℃/min的升温速度逐步升温至300~350℃。
与现有技术相比,本方法具有以下优良效果:
1.采用简单的钛盐水溶液体系为前驱体即可实现聚酰亚胺纳米纤维表面TiO2纳米层的修饰,工艺过程简单,条件易满足,成本低廉,适用范围广,可用于所有体系的聚酰亚胺纤维膜。
2.本发明制备的表面修饰TiO2的聚酰亚胺纤维膜同时结合了静电纺丝纤维膜、聚酰亚胺和二氧化钛三者的优点,得到的纤维膜具有比表面积大、耐高温和表面浸润性好的特点。
3.纤维膜的断面电镜图片显示,二氧化钛纳米层的厚度在10nm以下,实现了超薄TiO2层的表面修饰,效果可以媲美原子层沉积法。
本发明所制得的表面修饰二氧化钛纳米层的聚酰亚胺复合纤维膜具有TiO2层致密均匀、厚度可控、催化活性高的优点,可应用于光催化材料、电池隔膜、抗紫外材料和自清洁材料中。
附图说明
图1是均苯四酸二酐/4,4’-二氨基二苯醚(PMDA/ODA)聚酰胺酸纤维膜直接加热至300℃并保温2h酰胺化得到的聚酰亚胺纤维膜的SEM形貌图,图中放大倍数为10万倍;
图2是均苯四酸二酐/4,4’-二氨基二苯醚(PMDA/ODA)聚酰胺酸纤维膜直接加热至300℃并保温2h酰胺化得到的聚酰亚胺纤维膜的SEM断面图,图中放大倍数为10万倍;
图3是PMDA/ODA聚酰胺酸纤维膜经过1mol/L的KOH溶液浸泡10min后再经过后续处理得到的聚酰亚胺纤维膜的SEM形貌图,图中放大倍数为3万倍;
图4是PMDA/ODA聚酰胺酸纤维膜经过1mol/L的KOH溶液浸泡10min后再经过后续处理得到的聚酰亚胺纤维膜的SEM断面图,图中放大倍数为10万倍;
图5是PMDA/ODA聚酰胺酸纤维膜经过1mol/L的KOH溶液浸泡20min后再经过后续处理得到的聚酰亚胺纤维膜的SEM断面图,图中放大倍数为10万倍;
图6是PMDA/ODA聚酰胺酸纤维膜经过2mol/L的KOH溶液浸泡30min后再经过后续处理得到的聚酰亚胺纤维膜的SEM断面图,图中放大倍数为10万倍;
图7是PMDA/ODA聚酰胺酸纤维膜经过3mol/L的KOH溶液浸泡20min后再经过后续处理得到的聚酰亚胺纤维膜的SEM断面图,图中放大倍数为10万倍;
图8是PMDA/ODA聚酰胺酸纤维膜分别经过不同浓度的KOH溶液浸泡后再经过后续处理得到的聚酰亚胺纤维膜的拉伸强度图。
具体实施方式
下面结合具体实施例,进一步阐述发明。应该说明的是:以下实施例仅用以说明本发明而并非限制本发明所描述的技术方案。因此,尽管本说明书参照下述的实施例对本发明已进行了详细的说明,但是,本领域的技术人员应当理解,仍然可以对本发明进行修改或等同替换;而一切不脱离本发明的精神和范围的技术方案及其改进,其均应涵盖在本发明的权利要求范围当中。
比较例1
(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;(2)将聚酰胺酸纤维膜置于热炉中,升温至300℃,并保持2h,从而制得聚酰亚胺纤维膜。所得的纤维膜的形貌图如附图1所示,断面图如附图2所示。
实施例1
制备PMDA/ODA体系聚酰胺酸纤维膜,经过处理,然后经热亚胺化后得到表面修饰二氧化钛纳米层的聚酰亚胺纤维膜。(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;(2)将聚酰胺酸纤维膜置于热炉中,升温至300℃,并保持2h,从而制得聚酰亚胺纤维膜;(3)将聚酰亚胺纤维膜浸泡在1mol/L的KOH溶液10min,随后再放入去离子水中清洗至中性;(4)将聚酰亚胺纤维膜放入0.3mol/L的硫酸氧钛水溶液中处理1h,随后放入室温下的去离子水中超声清洗3次;(5)将经过处理的聚酰亚胺纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得表面修饰二氧化钛层的聚酰亚胺纤维膜,所得的纤维膜的形貌图如附图3所示,断面图如附图4所示。
实施例2
制备PMDA/ODA体系聚酰胺酸纤维膜,经过处理,然后经热亚胺化后得到表面修饰二氧化钛纳米层的聚酰亚胺纤维膜。(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;(2)将聚酰胺酸纤维膜置于热炉中,升温至300℃,并保持2h,从而制得聚酰亚胺纤维膜;(3)将聚酰亚胺纤维膜浸泡在1mol/L的KOH溶液20min,随后再放入去离子水中清洗至中性;(4)将聚酰亚胺纤维膜放入0.3mol/L的硫酸氧钛水溶液中处理1h,随后放入室温下的去离子水中超声清洗3次;(5)将经过处理的聚酰亚胺纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得表面修饰二氧化钛层的聚酰亚胺纤维膜,所得的纤维膜的断面如附图5所示。
实施例3
制备PMDA/ODA体系聚酰胺酸纤维膜,经过处理,然后经热亚胺化后得到表面修饰二氧化钛纳米层的聚酰亚胺纤维膜。(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;(2)将聚酰胺酸纤维膜置于热炉中,升温至300℃,并保持2h,从而制得聚酰亚胺纤维膜;(3)将聚酰亚胺纤维膜浸泡在2mol/L的KOH溶液30min,随后再放入去离子水中清洗至中性;(4)将聚酰亚胺纤维膜放入0.3mol/L的硫酸氧钛水溶液中处理1h,随后放入室温下的去离子水中超声清洗3次;(5)将经过处理的聚酰亚胺纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得表面修饰二氧化钛层的聚酰亚胺纤维膜,所得的纤维膜的断面如附图6所示。
实施例4
制备PMDA/ODA体系聚酰胺酸纤维膜,经过处理,然后经热亚胺化后得到表面修饰二氧化钛纳米层的聚酰亚胺纤维膜。(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;(2)将聚酰胺酸纤维膜置于热炉中,升温至300℃,并保持2h,从而制得聚酰亚胺纤维膜;(3)将聚酰亚胺纤维膜浸泡在3mol/L的KOH溶液20min,随后再放入去离子水中清洗至中性;(4)将聚酰亚胺纤维膜放入0.3mol/L的硫酸氧钛水溶液中处理1h,随后放入室温下的去离子水中超声清洗3次;(5)将经过处理的聚酰亚胺纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得表面修饰二氧化钛层的聚酰亚胺纤维膜,所得的纤维膜的断面如附图7所示。
Claims (8)
1.一种表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜的制备方法,其特征在于,包括以下步骤:
A:将聚酰胺酸溶液经静电纺丝法制得聚酰胺酸纤维膜;
B:将步骤A制得的聚酰胺酸纤维膜置于热炉中处理,使聚酰胺酸纤维膜转变为聚酰亚胺纤维膜;
C:将步骤B制得的聚酰亚胺纤维膜浸泡在1~3mol/L的KOH溶液中10~30min,随后再放入去离子水中清洗至中性;
D:将步骤C制得的聚酰亚胺纤维膜放入0.1~0.3mol/L的钛化合物水溶液中处理10min~2h,随后放入去离子水中超声清洗1~3次;
E:将步骤D制得的聚酰亚胺纤维膜置于热炉中处理,从而制得表面修饰二氧化钛纳米颗粒的聚酰亚胺纤维膜;
其中步骤A中聚酰胺酸溶液的固含量为8%~30%,步骤D中所述的钛化合物为硫酸氧钛或硫酸钛。
2.按照权利要求1所述的制备方法,其中步骤B中热炉处理的温度为300~350℃,时间为1~3h。
3.按照权利要求1所述的制备方法,其中步骤B中热炉处理的温度优选为300℃,时间为2h。
4.按照权利要求1所述的制备方法,其中步骤C中优选浸泡在1mol/L的KOH溶液中10min。
5.按照权利要求1所述的制备方法,其中步骤E中热炉处理的温度为300~350℃,时间为1~3h。
6.按照权利要求1所述的制备方法,其中步骤E中热炉处理的温度优选为300℃,时间为2h。
7.按照权利要求1所述的制备方法,其中步骤E中以2℃/min的升温速度逐步升温至300~350℃。
8.权利要求1-7任一项所述的方法制备得到的表面修饰二氧化钛纳米颗粒聚酰亚胺纤维膜。
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