含苯并噁唑结构聚酰亚胺薄膜的制备与性能研究
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摘要
为了制备满足新型电子封装材料相关性能要求的联苯型聚酰亚胺(PI)薄膜,将含有苯并噁唑结构单元的2-(4-氨基苯基)-5-氨基苯并噁唑(DAPBO)引入到以3,3′,4,4′-联苯四甲酸二酐(s-BPDA)、对苯二胺(PDA)和4,4′-二氨基二苯醚(ODA)为单体合成的分子结构中,通过无规共聚法制备聚酰胺酸(PAA),再进行亚胺化得到PI薄膜,并表征其相关性能。结果表明:通过引入DAPBO二胺单体,该系列PI薄膜的多项物理性能得到显著改善。其中,DAPBO含量的增加促使该系列PI薄膜的力学性能和热学性能提高,而热膨胀系数(CTE)减小。当二胺单体中DAPBO的含量达到100%时,PI薄膜的拉伸强度可达278 MPa,CTE可降至7.47×10-6/K。
In order to meet the requirements of new electronic packaging materials on the polyimide(PI)film, a serial of biphenyl-type PI films were prepared and their properties were characterized. At first,polyamide acids(PAA) were synthesized via random copolymerization from 2-(4-aminophenyl)-5-aminobenzoxazole(DAPBO) containing benzoxazole unit, 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA),p-phenylenediamine(PDA), and 4,4′-diaminodiphenyl ether(ODA, And then, PI films were obtained through imidization. The results show that several physical properties of the PI films were improved significantly by introducing the diamine monomer of DAPBO. With the increase of DAPBO content, the mechanical and thermal properties increase, while the thermal expansion coefficient(CTE) decreases. When the content of DAPBO in the diamine monomers is 100%, the tensile strength of the PI film attains 278 MPa, and the CTE decreases to 7.47×10-6/K.
In order to meet the requirements of new electronic packaging materials on the polyimide(PI)film, a serial of biphenyl-type PI films were prepared and their properties were characterized. At first,polyamide acids(PAA) were synthesized via random copolymerization from 2-(4-aminophenyl)-5-aminobenzoxazole(DAPBO) containing benzoxazole unit, 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA),p-phenylenediamine(PDA), and 4,4′-diaminodiphenyl ether(ODA, And then, PI films were obtained through imidization. The results show that several physical properties of the PI films were improved significantly by introducing the diamine monomer of DAPBO. With the increase of DAPBO content, the mechanical and thermal properties increase, while the thermal expansion coefficient(CTE) decreases. When the content of DAPBO in the diamine monomers is 100%, the tensile strength of the PI film attains 278 MPa, and the CTE decreases to 7.47×10-6/K.
引文
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[2]刘京妮.具有低膨胀系数的聚酰亚胺材料制备与性能研究[D].北京:北京化工大学,2015.
[3]包建勋.高体分SiC/Al与若干电子封装基板材料的对比[J].电子测试,2015(19):121-122.
[4]韩艳霞,张俊丽,董占林,等.低热膨胀系数聚酰亚胺薄膜的研究进展[J].绝缘材料,2014,47(6):10-12.
[5] ELSNER G. Residual stress and thermal expansion of spun-on polyimide films[J]. Journal of Applied Polymer Science,2010,34(2):815-828.
[6]段秀红,姚海波,郭海泉.刚性聚酰亚胺的分子堆积和热膨胀性能研究[J].计算机与应用化学,2015,32(8):917-920.
[7] EBISAWA S, ISHII J, SATO M, et al. Spontaneous molecular orientation of polyimides induced by thermal imidization(5). Effect of ordered structure formation in polyimide precursors on CTE[J]. European Polymer Journal,2010,46(2):283-297.
[8] ZHUANG Y B, LIU X Y, GU Y. Molecular packing and properties of poly(benzoxazole-benzimidazole-imide)copolymers[J]. Polymer Chemistry,2012,3(6):1517-1525.
[9] SONG G, WANG D, ZHAO X, et al. Synthesis and properties of polyimides-containing benzoxazole units in the main chain[J]. High Performance Polymers,2013,25(3):354-360.
[10]韩松锋,唐必连,马传国,等. BPDA/ODA/PDA型PI薄膜的制备及性能研究[J].绝缘材料,2018,51(1):17-21.
[11]宋广亮.含苯并咪唑和苯并噁唑基团的高性能聚酰亚胺薄膜[D].长春:吉林大学,2014.
[12]青双桂,白小庆,刘鑫雨,等.无规共聚法及共混法制备PMDA-ODA/PDA薄膜及其性能研究[J].绝缘材料,2016,49(11):51-54.
[13] MA X, QIU X, JIN R, et al. Synthesis and properties of fluorescence poly(benzoxazole-imide)s containing naphthalene[J]. High Performance Polymers,2015,27(6):4463-71.