CN112321825A - 一种耐热透明聚酰亚胺薄膜及其制备方法 - Google Patents
一种耐热透明聚酰亚胺薄膜及其制备方法 Download PDFInfo
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Abstract
本发明提出了一种耐热透明聚酰亚胺薄膜的制备方法,包括:将二酐与二胺进行缩聚反应得到聚酰胺酸后,在支撑体上流延成膜,得到聚酰胺酸膜;将该聚酰胺酸膜浸渍到含有无机纳米颗粒和酰亚胺试剂的溶液中,取出后,得到聚酰亚胺湿膜;将该聚酰亚胺湿膜进行拉伸,干燥后,得到所述耐热透明聚酰亚胺薄膜。本发明所述制备方法改善了聚酰亚胺和无机氧化物无法有效结合的缺陷,在提高聚酰亚胺薄膜透明性的同时,进一步提升其耐热性。
Description
技术领域
本发明涉及聚酰亚胺技术领域,尤其涉及一种耐热透明聚酰亚胺薄膜及其制备方法。
背景技术
聚酰亚胺(PI)是一类指将芳香族双酐和芳香族二胺或者芳香族二异氰酸酯进行溶液聚合后,在高温下或者酰亚胺试剂作用下,脱水闭环氨化而制备得到的一类树脂。
聚酰亚胺这类树脂具有许多优异的特性,如抗热氧化性、耐热性、抗辐射性、耐低温性以及耐化学性,因而被应用于各种领域,例如作为汽车用材料、航空器材料或航天器材料等先进耐热材料,或者作为基底材料被广泛应用于显示器(FPD:例如液晶显示装置、有机EL显示装置)等领域。
随着人们对材料性能的要求越来越高,特别是在先进光学制造、有机电致发光(OLED)显示领域,往往要求基底材料具有更好的光学性能、力学性能及更低的热膨胀系数等。目前,聚酰亚胺在用于显示器领域时,其透明度、热稳定性等方面的性能已经无法满足此要求。为此材料学家通过将无色透明聚酰亚胺与二氧化硅(SiO2)、二氧化钛(TiO2)、氧化锆(ZrO2)、氧化铝(Al2O3)、碳纳米管(CNT)等无机材料复合得到聚酰亚胺基无机-有机复合材料,从而使复合材料具有高分子本体材料的光学性能,又兼具无机材料的高刚性、低热膨胀系数等优点,以期复合材料的光学性能、力学性能、热性能等方面得到全面提升。
但是考虑到聚酰亚胺和无机氧化物的界面相容性相差甚大,结合难度非常大,目前性能改进效果有限,无法广泛使用。
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热透明聚酰亚胺薄膜的制备方法,该制备方法改善了聚酰亚胺和无机氧化物无法有效结合的缺陷,在提高聚酰亚胺薄膜透明性的同时,进一步提升其耐热性。
本发明提出的一种耐热透明聚酰亚胺薄膜的制备方法,包括:
S1、将二酐与二胺进行缩聚反应得到聚酰胺酸后,在支撑体上流延成膜,得到聚酰胺酸膜;
S2、将该聚酰胺酸膜浸渍到含有无机纳米颗粒和酰亚胺试剂的溶液中,取出后,得到聚酰亚胺湿膜;
S3、将该聚酰亚胺湿膜进行拉伸,干燥后,得到所述耐热透明聚酰亚胺薄膜。
优选地,所述二酐为芳香族或者脂环族四羧酸二酐,所述二胺为芳香族二胺;优选地,所述二酐为含氟取代的芳香族四羧酸二酐,所述二胺为含氟取代的芳香族二胺。
优选地,所述无机纳米颗粒为SiO2、Al2O3、TiO2或ZnO中的至少一种。
优选地,所述无机纳米颗粒为氨基功能化的无机纳米颗粒;优选地,所述氨基功能化的无机纳米颗粒是通过将3-氨丙基三乙氧基硅烷和无机纳米颗粒前体在碱性条件下反应得到。
优选地,所述无机纳米颗粒前体为正硅酸乙酯或异丙醇铝中的至少一种。
优选地,所述酰亚胺试剂包括催化剂和脱水剂;优选地,所述催化剂为吡啶、p-吡咯啉、二甲基吡啶、三甲基吡啶或喹啉中的至少一种,所述脱水剂为三氟乙酸酐、乙酸酐或丙酸酐中的至少一种。
优选地,所述拉伸包括:在140-170℃下,纵向拉伸至1.01-1.5倍,并横向拉伸至1.01-1.3倍。
优选地,所述干燥包括:在200-400℃下干燥10-40min。
本发明还提出一种耐热透明聚酰亚胺薄膜,其是通过上述制备方法制备得到。
本发明所述耐热透明聚酰亚胺薄膜的制备方法,通过将聚酰胺酸成膜后再浸渍含有无机纳米颗粒和酰亚胺试剂的溶液,这样使得无机纳米颗粒和酰亚胺剂可以均匀分布在聚酰胺酸膜表面,此后利用酰亚胺剂使得聚酰胺酸膜发生亚胺化反应,促进无机纳米颗粒能够对聚酰亚胺膜进行有效附着,改善了聚酰亚胺薄膜的光学和耐热性能。
与此同时,本发明中为了进一步增强无机纳米颗粒对聚酰亚胺薄膜的附着效果,通过限定所述无机纳米颗粒为氨基功能化的无机纳米颗粒,由于该氨基功能化的无机纳米颗粒表面接枝有氨基,因此该氨基功能化的无机纳米颗粒可以和酰亚胺试剂中的有机胺化合物(吡啶、p-吡咯啉、二甲基吡啶等)复配,从而对聚酰胺酸膜形成反应,从而进一步提高聚酰亚胺与无机纳米颗粒之间的界面结合性能,使无机纳米颗粒能够更加有效、均匀地分散在聚酰亚胺薄膜上,使所得聚酰亚胺薄膜的耐热性和透光率都得到有效提高。
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,但是应该明确提出这些实施例用于举例说明,但是不解释为限制本发明的范围。
实施例1
一种耐热透明聚酰亚胺薄膜的制备方法,具体包括:
(1)在N2保护的环境下,向反应器中加入0.16kg(0.5mol)4,4′-二氨基-2,2′-双三氟甲基联苯(TFDB)和1500mL脱水N,N-二甲基乙酰胺,搅拌溶解完全后,加入0.076kg(0.26mol)3,3′,4,4′-联苯四甲酸二酐(BPDA)和0.11kg(0.25mol)4,4'-(六氟异丙烯)二酞酸酐(6FDA),加料完毕后在30℃下以300rpm的搅拌速率搅拌反应3h,得到聚酰胺酸溶液;
将该聚酰胺酸溶液通过刮刀控制湿膜厚度为100μm,在光滑钢带上流延成膜,氮气保护下升温至80℃后热处理5min,得到聚酰胺酸膜;
(2)将上述聚酰胺酸膜从钢带上剥离后,浸渍到由0.08kgSiO2纳米颗粒(平均粒径80nm)、350mL醋酸酐、200mL吡啶和1500mL N,N-二甲基乙酰胺组成的浸渍液中,加热至50℃后保持30min,取出后再浸渍到1500mL N,N-二甲基乙酰胺中保持20min,取出后,得到聚酰亚胺湿膜;
(3)将上述聚酰亚胺湿膜的在150℃热风中干燥15min后,除去大部分溶剂,再在160℃下经过1.3倍的纵向拉伸和1.2倍的横向拉伸,接着在热风炉中,升温至320℃后热处理20min,即得到所述耐热透明聚酰亚胺薄膜。
实施例2
一种耐热透明聚酰亚胺薄膜的制备方法,具体包括:
(1)在N2保护的环境下,向反应器中加入0.16kg(0.5mol)4,4′-二氨基-2,2′-双三氟甲基联苯(TFDB)和1500mL脱水N,N-二甲基乙酰胺,搅拌溶解完全后,加入0.076kg(0.26mol)3,3′,4,4′-联苯四甲酸二酐(BPDA)和0.11kg(0.25mol)4,4'-(六氟异丙烯)二酞酸酐(6FDA),加料完毕后在30℃下以300rpm的搅拌速率搅拌反应3h,得到聚酰胺酸溶液;
将该聚酰胺酸溶液通过刮刀控制湿膜厚度为100μm,在光滑钢带上流延成膜,氮气保护下升温至80℃后热处理5min,得到聚酰胺酸膜;
(2)将上述聚酰胺酸膜从钢带上剥离后,浸渍到由0.08kg氨基功能化SiO2纳米颗粒、350mL醋酸酐、200mL吡啶和1500mL N,N-二甲基乙酰胺组成的浸渍液中,加热至50℃后保持30min,取出后再浸渍到1500mL N,N-二甲基乙酰胺中保持20min,得到聚酰亚胺湿膜;
其中,所述氨基功能化SiO2纳米颗粒是通过下述方法制备得到:将体积比为5:2的正硅酸乙酯和3-氨丙基三乙氧基硅烷加入到乙醇中,搅拌条件下加入0.8倍正硅酸乙酯体积的氨水(1mol/L),室温下搅拌反应6h,将所得固体粉末过滤,洗涤,干燥,即为氨基功能化SiO2纳米颗粒;
(3)将上述聚酰亚胺湿膜的在150℃热风中干燥15min后,除去大部分溶剂后,再在160℃下经过1.3倍的纵向拉伸和1.2倍的横向拉伸,接着在热风炉中升温至320℃后热处理20min,即得到所述耐热透明聚酰亚胺薄膜。
实施例3
一种耐热透明聚酰亚胺薄膜的制备方法,具体包括:
(1)在N2保护的环境下,向反应器中加入0.16kg(0.5mol)4,4′-二氨基-2,2′-双三氟甲基联苯(TFDB)和1500mL脱水N,N-二甲基乙酰胺,搅拌溶解完全后,加入0.076kg(0.26mol)3,3′,4,4′-联苯四甲酸二酐(BPDA)和0.11kg(0.25mol)4,4'-(六氟异丙烯)二酞酸酐(6FDA),加料完毕后在30℃下以300rpm的搅拌速率搅拌反应3h,得到聚酰胺酸溶液;
将该聚酰胺酸溶液通过刮刀控制湿膜厚度为100μm,在光滑钢带上流延成膜,氮气保护下升温至80℃后热处理5min,得到聚酰胺酸膜;
(2)将上述聚酰胺酸膜从钢带上剥离后,浸渍到由0.08kg氨基功能化Al2O3纳米颗粒、350mL醋酸酐、200mL吡啶和1500mL N,N-二甲基乙酰胺组成的浸渍液中,加热至50℃后保持30min,取出后再浸渍到1500mL N,N-二甲基乙酰胺中保持20min,得到聚酰亚胺湿膜;
其中,所述氨基功能化Al2O3纳米颗是通过下述方法制备得到:将体积比为5:2的异丙醇铝和3-氨丙基三乙氧基硅烷加入到乙醇中,400rpm的搅拌速率下加入0.8倍异丙醇铝体积的氨水(1mol/L),室温下搅拌反应6h,将所得固体粉末过滤,洗涤,干燥,即为氨基功能化Al2O3纳米颗粒;
(3)将上述聚酰亚胺湿膜的在150℃热风中干燥15min后,除去大部分溶剂后,再在160℃下经过1.4倍的纵向拉伸和1.2倍的横向拉伸,接着在热风炉中升温至320℃后热处理20min,即得到所述耐热透明聚酰亚胺薄膜。
对比例1
一种耐热透明聚酰亚胺薄膜的制备方法,具体包括:
(1)在N2保护的环境下,向反应器中加入0.16kg(0.5mol)4,4′-二氨基-2,2′-双三氟甲基联苯(TFDB)和1500mL脱水N,N-二甲基乙酰胺,搅拌溶解完全后,加入0.076kg(0.26mol)3,3′,4,4′-联苯四甲酸二酐(BPDA)和0.11kg(0.25mol)4,4'-(六氟异丙烯)二酞酸酐(6FDA),加料完毕后在30℃下以300rpm的搅拌速率搅拌反应3h,得到聚酰胺酸溶液;
(2)搅拌条件下向上述聚酰胺酸溶液中加入0.08kg无机纳米颗粒、350mL醋酸酐、200mL吡啶和1500mL N,N-二甲基乙酰胺,加热至50℃后保温搅拌30min,过滤后得到聚酰亚胺溶液;
(3)将上述聚酰亚胺溶液通过刮刀控制湿膜厚度为100μm,在光滑钢带上流延成膜,氮气保护下升温至80℃后热处理5min,剥离后得到聚酰亚胺湿膜;将上述聚酰亚胺湿膜的在150℃热风中干燥15min后,除去大部分溶剂,再在160℃下经过1.3倍的纵向拉伸和1.2倍的横向拉伸,接着在热风炉中,升温至320℃后热处理20min,即得到所述聚酰亚胺薄膜。
对上述实施例和对比例所得的聚酰亚胺薄膜进行下述方法所示的性能测试,其结果如下表1所示:
透光率:紫外-可见光谱测定可见光透射率。
线性热膨胀系数:使用热机械式分析装置,在氮气氛围下,施加50mN的荷重,以10℃/min的升温速度进行测定,求出平均值。
玻璃化转变温度:使用差式扫描热量计装置,在氮气氛围下,以10℃/min的升温速度条件下进行DSC测定,求出玻璃化转变温度。
黄度指数:以ASTM E313标准测定黄度指数。
表1实施例1-3和对比例1的性能测试结果
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 (9)
1.一种耐热透明聚酰亚胺薄膜的制备方法,其特征在于,包括:
S1、将二酐与二胺进行缩聚反应得到聚酰胺酸后,在支撑体上流延成膜,得到聚酰胺酸膜;
S2、将该聚酰胺酸膜浸渍到含有无机纳米颗粒和酰亚胺试剂的溶液中,取出后,得到聚酰亚胺湿膜;
S3、将该聚酰亚胺湿膜进行拉伸,干燥后,得到所述耐热透明聚酰亚胺薄膜。
2.根据权利要求1所述耐热透明聚酰亚胺薄膜的制备方法,其特征在于,所述二酐为芳香族或者脂环族四羧酸二酐,所述二胺为芳香族二胺;优选地,所述二酐为含氟取代的芳香族四羧酸二酐,所述二胺为含氟取代的芳香族二胺。
3.根据权利要求1或2所述耐热透明聚酰亚胺薄膜的制备方法,其特征在于,所述无机纳米颗粒为SiO2、Al2O3、TiO2或ZnO中的至少一种。
4.根据权利要求3所述耐热透明聚酰亚胺薄膜的制备方法,其特征在于,所述无机纳米颗粒为氨基功能化的无机纳米颗粒;优选地,所述氨基功能化的无机纳米颗粒是通过将3-氨丙基三乙氧基硅烷和无机纳米颗粒前体在碱性条件下反应得到。
5.根据权利要求4所述耐热透明聚酰亚胺薄膜的制备方法,其特征在于,所述无机纳米颗粒前体为正硅酸乙酯或异丙醇铝中的至少一种。
6.根据权利要求1-5任一项所述耐热透明聚酰亚胺薄膜的制备方法,其特征在于,所述酰亚胺试剂包括催化剂和脱水剂;优选地,所述催化剂为吡啶、p-吡咯啉、二甲基吡啶、三甲基吡啶或喹啉中的至少一种,所述脱水剂为三氟乙酸酐、乙酸酐或丙酸酐中的至少一种。
7.根据权利要求1-6任一项所述耐热透明聚酰亚胺薄膜的制备方法,其特征在于,所述拉伸包括:在140-170℃下,纵向拉伸至1.01-1.5倍,并横向拉伸至1.01-1.3倍。
8.根据权利要求1-7任一项所述耐热透明聚酰亚胺薄膜的制备方法,其特征在于,所述干燥包括:在200-400℃下干燥10-40min。
9.一种耐热透明聚酰亚胺薄膜,其特征在于,其是权利要求1-8任一项所述方法制备得到。
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