CN105442301B - 一种表面包覆二氧化钛纳米层的聚酰亚胺纤维膜的制备方法 - Google Patents
一种表面包覆二氧化钛纳米层的聚酰亚胺纤维膜的制备方法 Download PDFInfo
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Abstract
一种表面包覆二氧化钛纳米层的聚酰亚胺纤维膜的制备方法。首先将聚酰胺酸溶液通过静电纺丝技术制成聚酰胺酸纤维膜,随后把纤维膜置于放有钛化合物的密闭容器中,在50℃~70℃的真空条件下进行处理,然后经水解和梯度升温热亚胺化处理,最终制得表面包覆二氧化钛纳米层的聚酰亚胺纤维膜。本发明的方法实施过程简单,包覆效率高,对基体无损伤,且二氧化钛纳米层的厚度可调可控,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包覆二氧化钛纳米层的聚酰亚胺纤维膜的制备方法。
背景技术
聚酰亚胺是一类主链上含有酰亚胺环结构的高性能聚合物,具有优异的耐高低温性能、机械性能、介电性能、化学稳定性以及耐紫外耐辐照的独特优势,在航空航天、微电子以及原子能等高科技领域均得到了应用。近年来,随着静电纺丝技术的发展,以聚酰亚胺为基体的纳米纤维膜材料得到了人们的广泛关注。这类材料由于结合了纤维膜比表面积大、孔隙率高的优势和聚酰亚胺耐高温以及化学稳定的特性,在组织工程支架、药物缓释材料、传感器、催化、过滤材料以及电池隔膜等领域都表现出巨大的潜在应用价值。其中,为了赋予聚酰亚胺纤维膜更加优异的表面性能及功能性,对其进行表面无机粒子覆载制备出表面包覆无机纳米层的聚酰亚胺基有机/无机复合纤维膜是当前备受关注的研究领域。
当前,制备聚酰亚胺基有机/无机复合纤维膜的方法主要有直接共混法、原位聚合法和溶胶-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直接进行混合,将无机纳米粒子分散在聚合物基体中,从而得到复合材料。而原位聚合法则是将纳米粒子与有机单体混合均匀后,再在适当的条件下引发单体聚合,从而得到掺杂无机纳米粒子的聚酰亚胺复合材料。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。
上述方法可以实现无机纳米粒子在有机聚合物基体中的均匀分散,因此,在制备无机纳米粒子掺杂的聚酰亚胺纤维膜方面具有很好的效果,成为该领域的常用方法。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;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。然而,这些方法在制备表面包覆无机纳米层的聚酰亚胺纤维膜时却存在较大的不足。这主要是由于无机纳米粒子大部分处于聚酰亚胺基体纤维的内部,仅有很少量的纳米粒子附着在基体纤维表面,导致无机纳米粒子对基体纤维表面的包覆率不高,无法在纤维表面形成连续致密的无机纳米层,并且无机纳米层的厚度不均匀,也很难实现可控。虽然,可以在制备过程中通过大量添加无机纳米粒子或其前驱体的方法来提高无机粒子在基体纤维表面的包覆程度,但是这往往又会导致聚酰亚胺基体纤维本体性能的较大改变;同时,无机纳米粒子或其前驱体的大量加入还会改变聚酰亚胺及其前驱体溶液本身的特性(如粘度、密度和导电性等),从而导致电纺丝工艺参数的大幅改变,甚至出现无法电纺丝制备复合纤维膜的问题。
发明内容
本发明的目的在于解决现有技术的不足,提供一种简单有效的制备表面包覆二氧化钛纳米层的聚酰亚胺纤维膜的工艺方法。本发明的方法工艺过程简单,包覆效率高,对基体无损伤,且二氧化钛纳米层的厚度可调可控,应用前景良好。
1.一种表面包覆二氧化钛纳米层的聚酰亚胺纤维膜的制备方法,其特征在于包括以下步骤:
A:采用固含量为8%~30%的聚酰胺酸溶液,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盛有钛化合物的密闭容器中,在50℃~70℃的真空条件下处理10min~1h;
C:将步骤B制得的聚酰胺酸纤维膜在水蒸气中处理0.5~3min,然后再在室温和常压条件下静置0.5~1h;
D:顺序重复步骤B和步骤C若干次;
E:将步骤D制得的聚酰胺酸纤维膜置于热炉中,以2~6℃/min的升温速度逐步升温至300-350℃,并保持0.5~3h,即得到表面包覆二氧化钛纳米层的聚酰亚胺纤维膜。
F:其中,步骤B中所述的钛化合物为钛酸异丙酯、钛酸四丁酯、钛酸四乙酯、四氟化钛、四氯化钛。
G:其中,步骤D中的重复次数不受限制,二氧化钛纳米层的厚度随重复次数的增加而增加。
与现有技术相比,本方法具有以下优良效果:
1.实施工艺过程简单,条件易满足,步骤简便易重复,并且在处理过程中对聚酰亚胺基体纤维无损伤,适用范围广,可用于所有体系的聚酰亚胺纤维膜。
2.二氧化钛纳米颗粒对聚酰亚胺基体纤维的包覆效率高,形成的二氧化钛无机纳米层的致密性好,粘附性高。
3.二氧化钛纳米层的厚度可以通过改变工艺条件实现可控。
本发明所制得的表面覆载二氧化钛纳米层的聚酰亚胺复合纤维膜具有无机层致密均匀、附着力高、厚度可控的优点,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120min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PMDA/ODA聚酰胺酸纤维膜经过处理(循环1次),并加热至300℃保温120min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20万倍;
图3是PMDA/ODA聚酰胺酸纤维膜经过处理(循环4次),并加热至300℃保温120min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20万倍;
图4是PMDA/ODA聚酰胺酸纤维膜经过处理(循环20次),并加热至320℃保温120min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20万倍;
图5是PMDA/ODA聚酰胺酸纤维膜经过处理(循环30次),并加热至300℃保温60min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6是PMDA/ODA聚酰胺酸纤维膜经过处理(循环50次),并加热至300℃保温60min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;
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。
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包覆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放有钛酸四丁酯的密闭容器中,在真空,60℃条件下处理0.5小时;(3)将聚酰胺酸纤维膜置于水蒸气中处理1min后在室温和常压条件下静置0.5小时。(4)将经过处理的聚酰胺酸纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得聚酰亚胺/二氧化钛复合纤维膜,所得的纤维膜的形貌如附图2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包覆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放有钛酸四丁酯的密闭容器中,在真空,60℃条件下处理1小时;(3)将聚酰胺酸纤维膜置于水蒸气中处理1min后在室温和常压条件下静置0.5小时。(4)顺序重复步骤(2)和(3)4次。(5)将经过处理的聚酰胺酸纤维膜置于热炉中,以4℃/min的升温速度逐步升温至300℃,并保持2h,从而制得聚酰亚胺/二氧化钛复合纤维膜,所得的纤维膜的形貌如附图3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包覆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放有钛酸四丁酯的密闭容器中,在真空,65℃条件下处理1小时;(3)将聚酰胺酸纤维膜置于水蒸气中处理2min后在室温和常压条件下静置1小时。(4)顺序重复步骤(2)和(3)20次。(5)将经过处理的聚酰胺酸纤维膜置于热炉中,以4℃/min的升温速度逐步升温至320℃,并保持2h,从而制得聚酰亚胺/二氧化钛复合纤维膜,所得的纤维膜的形貌如附图4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包覆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放有钛酸异丙酯的密闭容器中,在真空,70℃条件下处理1小时;(3)将聚酰胺酸纤维膜置于水蒸气中处理2min后在室温和常压条件下静置0.5小时。(4)顺序重复步骤(2)和(3)30次。(5)将经过处理的聚酰胺酸纤维膜置于热炉中,以5℃/min的升温速度逐步升温至300℃,并保持1h,从而制得聚酰亚胺/二氧化钛复合纤维膜,所得的纤维膜的形貌如附图5所示。
实施例5
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包覆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放有钛酸四丁酯的密闭容器中,在真空,70℃条件下处理1小时;(3)将聚酰胺酸纤维膜置于水蒸气中处理1min后在室温和常压条件下静置1小时。(4)顺序重复步骤(2)和(3)50次。(5)将经过处理的聚酰胺酸纤维膜置于热炉中,以5℃/min的升温速度逐步升温至300℃,并保持1h,从而制得聚酰亚胺/二氧化钛复合纤维膜,所得的纤维膜的形貌如附图6所示。
Claims (1)
1.一种表面包覆二氧化钛纳米层的聚酰亚胺纤维膜的制备方法,其特征在于包括以下步骤:
A:采用固含量为8%~30%的聚酰胺酸溶液,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放有钛化合物的密闭容器中,在50℃~70℃的真空条件下处理10min~1h;
C:将步骤B制得的聚酰胺酸纤维膜在水蒸气中处理0.5~3min,然后再在室温和常压条件下静置0.5~1h;
D:顺序重复步骤B和步骤C若干次;
E:将步骤D制得的聚酰胺酸纤维膜置于热炉中,以2~6℃/min的升温速度逐步升温至300-350℃,并保持0.5~3h,即得到表面包覆二氧化钛纳米层的聚酰亚胺纤维膜。
F:其中,步骤B中所述的钛化合物为钛酸异丙酯、钛酸四丁酯、钛酸四乙酯、四氟化钛、四氯化钛。
G:其中,步骤D中的重复次数不受限制,二氧化钛纳米层的厚度随重复次数的增加而增加。
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