ODPA/ODA/BAHPP含羟基共聚聚酰亚胺的合成与性能研究
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摘要
以双酚A为原料,采用先硝化再还原的方法合成出2,2-双(3-氨基-4-羟基苯基)丙烷(BAHPP)。以BAHPP和4,4′-二氨基二苯醚(ODA)为二胺单体,3,3′,4,4′-二苯醚四酸二酐(ODPA)为二酐单体,经低温溶液缩聚反应得到一系列共聚聚酰胺酸,再经热酰亚胺化程序升温制备出一系列含羟基的共聚聚酰亚胺(CPI)薄膜。采用核磁共振波谱仪(NMR)、红外光谱(IR)、紫外-可见分光光度计(UV-Vis)、示差扫描量热仪(DSC)、热重分析(TGA)等对CPI进行结构与性能表征,考察两种二胺单体的摩尔分数对共聚聚酰亚胺光学性能、力学性能、热性能和溶解性的影响。结果表明:随着ODA摩尔分数的增加,CPI薄膜在500 nm处的光透过率逐渐增加,薄膜颜色逐渐变浅。随着BAHPP摩尔分数的增加,CPI的玻璃化转变温度(T_g)、拉伸强度和拉伸模量增加,但热稳定性降低。所有CPI在有机溶剂中均表现出较好的耐化学药品性。
The 2,2-bis(3-amino-4-hydroxyphenyl)propane(BAHPP) was synthesized from 2,2-bis(4-hydroxyphenyl)propane(BHPP) by nitration at first and then reduction. Using the BAHPP and 4,4′-diaminodiphenyl ether(ODA) as diamine monomers, 3,3′,4,4′-diphenyl ether dianhydride(ODPA) as dianhydride monomer, a series of copolymerization polyamide acid was synthesized by low temperature solution condensation polymerization reaction. Then a series of copolyimide(CPI) film containing hydroxyl groups were prepared by thermal imidization. The structure and properties of the CPI were characterized via NMR,IR, UV-vis, DSC, and TGA. The effects of mole fraction of diamine monomers on the optical property,mechanical properties, thermal property, and solubility of the CPI were studied. The results show that with the increase of the mole fraction of ODA, the transmittance at 500 nm of the CPI films increases,and the color of films becomes lighter. With the increase of the mole fraction of BAHPP, the glass transition temperature(T_g), tensile strength, and tensile modulus of the CPI films increase, while the thermal stability decreases. All the CPI films have good chemical resistance in organic solvent.
The 2,2-bis(3-amino-4-hydroxyphenyl)propane(BAHPP) was synthesized from 2,2-bis(4-hydroxyphenyl)propane(BHPP) by nitration at first and then reduction. Using the BAHPP and 4,4′-diaminodiphenyl ether(ODA) as diamine monomers, 3,3′,4,4′-diphenyl ether dianhydride(ODPA) as dianhydride monomer, a series of copolymerization polyamide acid was synthesized by low temperature solution condensation polymerization reaction. Then a series of copolyimide(CPI) film containing hydroxyl groups were prepared by thermal imidization. The structure and properties of the CPI were characterized via NMR,IR, UV-vis, DSC, and TGA. The effects of mole fraction of diamine monomers on the optical property,mechanical properties, thermal property, and solubility of the CPI were studied. The results show that with the increase of the mole fraction of ODA, the transmittance at 500 nm of the CPI films increases,and the color of films becomes lighter. With the increase of the mole fraction of BAHPP, the glass transition temperature(T_g), tensile strength, and tensile modulus of the CPI films increase, while the thermal stability decreases. All the CPI films have good chemical resistance in organic solvent.
引文
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[10]Kim S,Han S H,Lee Y M.Thermally Rearranged(TR)Polybenzoxazole Hollow Fiber Membranes for CO2Capture[J].Journal of Membrane Science,2012,403-404:169-178.
[11]Ma Xiaohua,Swaidan R,Teng Baiyang,et al.Carbon Molecular Sieve Gas Separation Membranes Based on an Intrinsically Microporous Polyimide Precursor[J].Carbon,2013,62(5):88-96.
[12]Hodgkin J H,Dao B N.Thermal Conversion of Hydroxy-containing Polyimides to Polybenzoxazoles.Does This Reaction Really Occur?[J].European Polymer Journal,2009,45(11):3081-3092.
[13]Sanders D F,Smith Z P,Ribeiro Jr C P,et al.Gas Permeability,Diffusivity,and Free Volume of Thermally Rearranged Polymers Based on 3,3′-dihydroxy-4,4′-diamino-biphenyl(HAB)and 2,2′-bis-(3,4-dicarboxyphenyl)Hexafluoropropane Dianhydride(6FDA)[J].Journal of Membrane Science,2012,409-410:232-241.
[14]Kim S,Jo H J,Lee Y M.Sorption and Transport of Small Gas Molecules in Thermally Rearranged(TR)Polybenzoxazole Membranes Based on 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane(bis APAF)and 4,4′-hexafluoroisopropylidene Diphthalic Anhydride(6FDA)[J].Journal of Membrane Science,2013,441:1-8.
[2]鲁云华,赵洪斌,迟海军,等.含氟共聚聚酰亚胺的合成与性能研究[J].绝缘材料,2013,46(1):1-3,7.
[3]黄明富,颜善银,陈川,等.可溶性ODA-ODPA-BPADA共聚聚酰亚胺的合成与性能[J].高分子材料科学与工程,2011,27(10):31-34.
[4]郭妙才,李松年,王晓工,等.一种含酚酞结构聚酰亚胺的合成及性能表征[J].高分子学报,2012(3):278-283.
[5]虞鑫海.含酚羟基聚酰亚胺薄膜的研制[J].绝缘材料,2009,42(5):1-6,10.
[6]费斐,徐永芬,傅菊荪,等.3,3′-二氨基-4,4′-二羟基联苯及其聚酰亚胺的合成与性能研究[J].绝缘材料,2009,42(6):12-15,22.
[7]Park S,Kim K,So W,et al.Gas Separation Properties of6FDA-based Polyimide Membranes with a Polar Group[J].Macromolecular Research,2003,11(3):157-162.
[8]张俊伟,牛彦存,邱凯,等.含羟基聚酰亚胺薄膜的制备[J].合成树脂及塑料,2014,31(3):30-33,41.
[9]路庆华,李梅,陶萍,等.含羟基活性基团的聚酰亚胺制备和表征[J].上海交通大学学报,2001,35(4):605-609.
[10]Kim S,Han S H,Lee Y M.Thermally Rearranged(TR)Polybenzoxazole Hollow Fiber Membranes for CO2Capture[J].Journal of Membrane Science,2012,403-404:169-178.
[11]Ma Xiaohua,Swaidan R,Teng Baiyang,et al.Carbon Molecular Sieve Gas Separation Membranes Based on an Intrinsically Microporous Polyimide Precursor[J].Carbon,2013,62(5):88-96.
[12]Hodgkin J H,Dao B N.Thermal Conversion of Hydroxy-containing Polyimides to Polybenzoxazoles.Does This Reaction Really Occur?[J].European Polymer Journal,2009,45(11):3081-3092.
[13]Sanders D F,Smith Z P,Ribeiro Jr C P,et al.Gas Permeability,Diffusivity,and Free Volume of Thermally Rearranged Polymers Based on 3,3′-dihydroxy-4,4′-diamino-biphenyl(HAB)and 2,2′-bis-(3,4-dicarboxyphenyl)Hexafluoropropane Dianhydride(6FDA)[J].Journal of Membrane Science,2012,409-410:232-241.
[14]Kim S,Jo H J,Lee Y M.Sorption and Transport of Small Gas Molecules in Thermally Rearranged(TR)Polybenzoxazole Membranes Based on 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane(bis APAF)and 4,4′-hexafluoroisopropylidene Diphthalic Anhydride(6FDA)[J].Journal of Membrane Science,2013,441:1-8.