三元共聚无氟芳香族透明聚酰亚胺合成及性能

以N,N-二甲基乙酰胺为溶剂,用芳香族二胺4,4′-二氨基二苯醚(ODA)与不同比例的2个芳香族二酐4,4′-联苯四甲酸二酐(BPDA)、双酚A型二醚二酐(BPADA)制备三元共聚无氟芳香族透明聚酰亚胺(PI)薄膜。用傅里叶变换红外光谱仪(FTIR)表征PI结构,用差示扫描量热仪(DSC)、热重分析仪(TG)、阻抗分析仪、紫外-可见分光光度仪(UV-VIS)研究PI薄膜的热性能、介电性能和透光率。结果表明：三元共聚PI薄膜玻璃化转变温度高于210.0℃;热失重5%的温度高于480.0℃;在可见光范围内透明性良好,PI薄膜在465 nm处透光率均超过80.0%,最高可达85.5%;相对介电常数为1.728 1～2.987 2,介电损耗为0.002 9～0.014 3。     

含烷基取代基柔性聚酰亚胺薄膜的制备

以柔性二胺单体1,3-双(4-氨基苯氧基)苯(134BAPB)和含支链二胺单体3,3′-二乙基-4,4′-二氨基二苯甲烷(DEMMD)与3,3′,4,4′-二苯酮四酸二酐(BTDA)进行三元共聚,制备了一系列聚酰亚胺(PI)薄膜。通过傅里叶红外光谱、差示扫描量热仪、热重分析仪、热机械分析仪及电子万能材料试验机对材料的结构、热性能和力学性能进行了表征。结果表明PI薄膜已经成功制备,热性能与力学性能良好。     

低热膨胀系数共聚型聚酰亚胺薄膜的制备与表征

采用均苯四甲酸二酐(PMDA),4,4′-氧双邻苯二甲酸酐(ODPA)和对苯二胺(PDA)共聚制备了聚酰胺酸(PAA),经热亚胺化得到聚酰亚胺(PI)薄膜。利用红外光谱(FTIR)、力学性能测试、静态热力学分析仪(TMA)、热失重分析仪(TGA)等研究了PI薄膜的性能。结果表明:制备的PI薄膜热膨胀系数较低,当PMDA与ODPA物质的量比为6∶4时,热膨胀系数为1.3×10-5 K-1,小于铜箔的热膨胀系数,说明具有良好的尺寸稳定性;热失重5%的温度(T5%)为582.5℃,热稳定性好。同时薄膜具有较好的力学性能和优异的介电性能。     

含苯并双咪唑高阻燃共聚聚酰亚胺薄膜的制备及其性能研究

以二胺单体2,2′-对苯基双-(5-氨基苯并咪唑)(PBABI)、 1,4-二氨基苯二胺(p-PDA)与二酐单体3,3′,4,4′-联苯四甲酸二酐(BPDA)进行共聚,制备高相对分子质量的聚酰亚胺(PI)前驱体聚酰胺酸(PAA),再通过热酰亚胺化的方式得到含苯并双咪唑重复单元的高阻燃共聚PI薄膜;研究了PI薄膜的聚集态结构、化学结构、热稳定性、阻燃性能和力学性能。结果表明:随着苯并双咪唑单体的增多,PI薄膜逐渐从有序堆积向无定型结构演变;苯并双咪唑结构促进了PI薄膜体系中形成分子间氢键作用;苯并咪唑的引入使PI薄膜的最大热分解温度提高5℃、玻璃化转变温度提升90℃、拉伸强度提高126 MPa,同时含苯并双咪唑的PI薄膜表现出优异的阻燃性能,极限氧指数提高到54%。     

2L-FCCL用聚酰亚胺复合膜的制备与性能

采用2,2′-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、4,4′-二氨基二苯醚(ODA)和3,3′,4,4′-二苯酮四酸二酐(BTDA)合成BAPP/ODA/BTDA型聚酰亚胺(PI)的前驱体聚酰胺酸(PAA)溶液,将该溶液涂覆于3,3′,4,4′-联苯四甲酸二酐(BPDA)/ODA型PI基膜上,通过去溶剂和热亚胺化制备PI复合膜,将复合膜的热塑面与铜箔复合,热压制得二层挠性覆铜板(2L-FCCL)。研究了BAPP/ODA/BTDA型PI、BPDA/ODA型PI、PI复合膜及2L-FCCL的性能。结果表明:BAPP/ODA/BTDA型PI薄膜的玻璃化转变温度为238℃,耐热性能优异,PI复合膜在280℃,15MPa下与铜箔层压50~60min制得的2F-FCCL剥离强度大于0.8N/mm,且经360℃焊锡浴测试未分层、未起泡,耐热性能和剥离强度均满足工业要求。     

含苯并噁唑结构共聚酰亚胺的合成及其性能

联苯四羧酸二酐(BPDA)与4,4′-二氨基二苯醚(ODA)及自制的2,6-二(对氨基苯)苯并[1,2-d;5,4-d']二噁唑(DAPBBO)在二甲基乙酰胺中共聚,然后进行铺膜和热酰亚胺化,得到了含有双苯并噁唑的共聚酰亚胺薄膜,对其结构、热性能、力学性能及光学性能进行了表征。结果表明:杂环单体的引入提高了聚酰亚胺的力学性能,增加了聚酰亚胺的玻璃化转变温度,并且使聚酰亚胺薄膜具有良好的紫外吸收能力。     

BPDA/ODA和PMDA/ODA共混聚酰亚胺薄膜

采用3,3′,4,4′-联苯四甲酸二酐/4,4′-二氨基二苯醚（BPDA/ODA）和1,2,4,5-均苯四甲酸二酐（PMDA）/ODA聚酰胺酸共混的方法制备了聚酰亚胺（PI）薄膜,研究了共混体系中共混比对薄膜的力学性能、动态力学性能、介电性能等的影响。用万能材料试验机、动态力学分析仪和阻抗分析仪研究了其力学性能、热性能和电性能与共混比例之间的关系。结果表明,这种共混PI薄膜可以保持良好的力学性能,特别是当选择了合适的共混比例时,PI薄膜的断裂伸长率会得到明显的提高,同时仍然保持其良好的耐热性能,介电损耗陡升温度在250 ℃以上,有望在240级以上漆包线的生产中得到广泛应用。     

脂环二酐与不同二胺制备浅色透明聚酰亚胺薄膜

使用两步法,以环丁烷四甲酸二酐(CBDA)为二酐,分别与4,4′-二氨基二苯醚(ODA)、4,4′-亚甲基双(2-乙基)苯胺(M-OEA)、4,4′-亚甲基双(2,6-二乙基苯胺)(M-DEA)、4,4′-二氨基苯酰替苯胺(DABA)、4,4′-二氨基-2,2′-二甲基-1,1′-联苯(M-Tol)合成一系列浅色透明的聚酰亚胺。通过红外光谱仪、紫外可见光谱仪、X射线衍射仪、差示扫描量热仪、静态热机械分析仪、热失重分析仪和万能材料试验机对薄膜进行表征分析。结果表明：薄膜已亚胺化完全,整体为无定形结构,玻璃化转变温度(T_g)最高可达259.18℃,初始分解温度在450℃以上,800℃的质量残留率最高为58.98%,热膨胀系数(CTE)最低为22.31×10^-6℃^-1,断裂伸长率在2.21%～10.62%范围内,具有良好的力学性能,薄膜在450 nm处的紫外光透过率最高可达89.07%。     

BAMPM基高可溶高透光聚酰亚胺的制备及表征

将3,3',5,5'-四甲基-4,4'-二胺基苯基-4'-甲基甲苯(BAMPM)与均苯四甲酸二酐(PMDA)、联苯四甲酸二酐(BPDA)、联苯醚二酐(ODPA)、六氟二酐(6FDA)通过一步高温缩聚法制备了四种新型聚酰亚胺(PI)。所得聚酰亚胺在普通有机溶剂中具有优异的溶解性。聚酰亚胺的玻璃化转变温度(Tg)超过332℃,10%热失重温度为530～537℃。溶液浇铸法制备的聚酰亚胺薄膜具有高光学透明性,UV截止波长为312～366 nm,80%透过率波长为382～436 nm。该薄膜的拉伸强度为60.5～84.7 MPa,弹性模量为1.7～2.4 GPa,断裂伸长率为5.9%～10.2%。     

脂环二胺浅色透明聚酰亚胺薄膜的制备及性能表征

采用二步法,在冰浴的条件下,以含脂环结构的二胺单体5-氨基-1,3,3-三甲基环己甲胺(IPDA)和4,4′-二氨基二环己基甲烷(PACM)与二酐单体4,4′-(4,4′-异丙基二苯氧基)双(邻苯二甲酸酐)(BPADA),制备六种不同二胺比例的聚酰亚胺(PI)薄膜。通过红外光谱、X射线衍射(XRD)分析、紫外可见光谱、热机械分析、差示扫描量热(DSC)测试、热失重测试和力学性能测试对薄膜进行表征分析。结果表明,PI薄膜已经完全亚胺化,整体为无定型形态,在可见光范围内具有较高的紫外透过率,最大透过率均在87%以上,450 nm最高透过率为83.26%,力学性能表现出柔性,玻璃化转变温度(T_g)均在200℃左右,初始分解温度均在388℃以上,在未到初始分解温度之前,几乎不发生质量损失,热稳定性良好。     

Synthesis and characterization of organosoluble polyfluorinated polyimides derived from 3,3′,5,5′‐tetrafluoro‐4,4′‐diaminodiphenylmethane and various aromatic dianhydrides

A polyfluorinated aromatic diamine, 3,3′, 5,5′‐tetrafluoro‐4,4′‐diaminodiphenylmethane (TFDAM), was synthesized and characterized. A series of polyimides, PI‐1–PI‐4, were prepared by reacting the diamine with four aromatic dianhydrides via a one‐step high‐temperature polycondensation procedure. The obtained polyimide resin had moderate inherent viscosity (0.56–0.68 dL/g) and excellent solubility in common organic solvents. The polyimide films exhibited good thermal stability, with an initial thermal decomposition temperature of 555°C–621°C, a 10% weight loss temperature of 560°C–636°C, and a glass‐transition temperature of 280°C–326°C. Flexible and tough polyimide films showed good tensile properties, with tensile strength of 121–138 MPa, elongation at break of 9%–12%, and tensile modulus of 2.2–2.9 GPa. The polyimide films were good dielectric materials, and surface and volume resistance were on the order of a magnitude of 10¹⁴ and 10¹⁵ Ω cm, respectively. The dielectric constant of the films was below 3.0 at 1 MHz. The polyfluorinated films showed good transparency in the visible‐light region, with a cutoff wavelength as low as 302 nm and transmittance higher than 70% at 450 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1442–1449, 2007     

均苯型共聚聚酰亚胺薄膜的制备及其性能

以2,2′-双[3-苯基-4(4-氨基苯氧基)苯基]丙烷(BPAPOPP)、4,4′-二胺基二苯醚和均苯四甲酸酐为原料,采用两步法共缩聚制备了一系列共聚聚酰亚胺薄膜.采用红外光谱仪、差示扫描量热仪等分析了薄膜的结构,利用静态热机械分析仪分析了薄膜的性能.结果表明:制备的聚酰亚胺薄膜具有较低的玻璃化转变温度;随着BPAP...     

Novel low‐dielectric‐constant copolyimide thin films composed with SiO2 hollow spheres

A series of copolyimide/SiO₂ hollow sphere thin films were prepared successfully based on bis[3,5‐dimethyl‐4‐(4‐aminophenoxy)phenyl]methane and 9,9‐bis(4‐(4‐aminophenoxy)phenyl)fluorene (molar ratio = 3 : 1) as diamine, and 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride) as dianhydride, with different wt % SiO₂ hollow sphere powder with particle size 500 nm. Some films possessed excellent dielectric properties, with ultralow dielectric constants of 1.8 at 1 MHz. The structures and properties of the thin films were measured with Fourier transform infrared spectra, scanning electron microscope, thermogravimetric analysis, and dynamic mechanical thermal analysis. The polyimide (PI) films exhibited glass‐transition temperatures in the range of 209– 273°C and possessed initial thermal decomposition temperature reaching up to 413–477°C in air and 418–472°C in nitrogen. Meanwhile, the composite films were also exhibited good mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of highly transparent and colorless semi-aromatic polyimide films derived from alicyclic dianhydride and aromatic diamines

A novel meta-substituted aromatic diamine containing trifluoromethyl and sulfonyl groups in the backbone, i.e., 2,2′-bis[4-(3-amino-5-trifluoromethylphenoxy)phenyl]sulfone (m-6FBAPS), was synthesized and characterized. A series of semi-aromatic polyimides were prepared from 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA) and various aromatic diamines. These polymers exhibited excellent solubility, high thermal stabilities and good mechanical properties. All semi-aromatic polyimide films showed considerably improved optical transparency as comparing with traditional aromatic ones due to the incorporation of alicyclic moieties. They gave the UV cutoff wavelengths of 292–314 nm, transmittance at 450 nm > 91% and yellowness indices <3.8. The extremely transparent and entirely colorless films were obtained from the polymers incorporated with bulky electron-withdrawing trifluoromethyl and sulfonyl groups in diamine moieties, such as PI-2, PI-5 and PI-6. Their excellent optical properties are attributed to the distorted molecular conformation combined with the weakened electron-accepting and electron-donating properties of dianydride and diamines, which significantly restrained the formation of inter-/intra-molecular charge transfer interactions.     

Organosoluble and light-colored fluorinated semialicyclic polyimide derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride

In this study, the alicyclic dianhydrides 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) was polymerized with seven kinds of fluorinated aromatic diamines, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (1), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (2), 1,4-bis(4-amino-2-trifluoromethylphenoxy)diphenyl (3), 1,4-bis(4-amino-2-trifluoromethylphenoxy) diphenyl ether (4), 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane (5), 4,4′-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone (6), and 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene (7), via a two-step polycondensation procedure to prepare seven kinds of fluorinated semialicyclic polyimides (PI) PI-1 ∼ PI-7. The structures of these polyimides were confirmed by infrared spectroscopy (IR). Solubility of the polyimides was tested in various organic solvents and their thermal properties were investigated by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). Ultraviolet-visible spectra (UV-vis) and near infrared absorption spectra (NIR) were obtained to evaluate the optical properties of these polyimides. The obtained polyimides PI-1 ∼ PI-7 displayed excellent solubility in a variety of organic solvents; they were readily soluble in amide-type polar solvent. These polyimide films exhibited good optical transparency in the visible light region (400–700 nm) with the transmittance higher than 80% at 450 nm, and these polyimide films showed little absorption at the optocommunication wavelengths of 1.30 and 1.55 μm. These polyimides showed good thermal stability with the 10% thermal decomposing temperatures higher than 443°C in nitrogen and the glass transition temperatures higher than 265°C. In addition, the effect of the structure of fluorinated diamines on the properties of polyimide films was also compared. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Construction of fluorenyl-modified low dielectric constant polyimide films with excellent mechanical properties and optical transparency

In order to meet the requirements of highly integrated and miniaturized electronic components, there is an urgent need for low dielectric materials with high mechanical properties and optical transparency in the field of microelectronics. In this study, a series of novel polyimide films (FPI) containing fluorenyl were prepared, and the effects of the fluorenyl content on the thermal, mechanical, and dielectric properties of the copolymerized films were investigated and discussed. The results demonstrate a significant decrease in the dielectric constant of the FPI films following the introduction of fluorenyl into polyimide (PI) chain segment. The FPI films also exhibited high mechanical properties, including tensile strengths between 92 and 106 MPa and elongation at break in the range of 8.4%–13.0%. Additionally, the introduction of the noncoplanar fluorenyl considerably improved the optical transparency and solubility of the FPI film. It is noteworthy that the FPI-3 has the best dielectric properties, with a low dielectric constant of 2.61 at 10 MHz and shows low water absorption (0.49%). The results show that we have prepared a novel low dielectric PI material film with excellent mechanical properties and optical transparency by introducing fluorenyl into the PI chain segment. These FPI films with satisfactory properties may be good candidates for dielectric materials for electronic components.     

聚酰亚胺热熔胶粘剂的合成与性能研究

制备了挠性印制电路中铜箔与聚酰亚胺基材间的聚酰亚胺粘接材料,由醚酐、脂肪族二胺和4,4’-二氨基二苯醚(ODA)或杂环芳香二胺共聚得到的聚酰亚胺薄膜的成膜性很好。通过红外分析,含ODA聚酰亚胺和含杂环聚酰亚胺薄膜已酰亚胺化完全。其力学性能较好。通过DSC分析,含ODA聚酰亚胺的玻璃化转变温度为141℃,结晶熔融温度为212℃;含杂环聚酰亚胺的玻璃化转变温度为136℃,并在225℃出现了一个吸热峰。采用含ODA或杂环聚酰亚胺胶粘剂制备的双面挠性印制电路基板的平均剥离强度为828．66N／m及710．98N／m。     

Novel phenylethynyl‐endcapped polyimide oligomers: Synthesis and characterization

A series of novel phenylethynyl‐endcapped polyimide oligomers were prepared by polycondensation of an aromatic diamine mixture of 1,3‐bis(4‐aminophenoxy) benzene (1,3,4‐APB) and 3,4′‐oxydianiline (3,4′‐ODA) with different aromatic dianhydrides including 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐(hexafluoro isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐[2,2,2‐trifluoro‐1‐(3′,5′‐bis‐(trifluoro‐methyl)phenyl)ethylidene]diphthalic anhydride (9FDA) in the presence of 4‐phenyl‐ethynylaniline (PEA) as endcapping agent in aprotic solvent at elevated temperature. The chemical structures, thermal behavior, and melt rheological properties of the synthesized polyimide oligomers were investigated. Experimental results indicated that the fluorinated polyimide oligomers derived from 6FDA (PI‐2) and 9FDA (PI‐4) are amorphous solid resins and exhibited lower melt viscosities than those prepared from the unfluorinated aromatic dianhydrides such as BPDA and ODPA. The BPDA‐based polyimide oligomers with a molar ratio of 1,3,4‐APB/3,4′‐ODA = 50:50 (PI‐5) showed lower melt viscosity than those derived from a mixture of 1,3,4‐APB and 3,4′‐ODA with molar ratios of 75:25 and 100:0, respectively. In addition, the melt viscosity of the polyimide oligomers increased obviously with increasing of the polymer calculated molecular weights. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Highly soluble and thermally stable copolyimides modified with trifluoromethyl and siloxane

A series of highly soluble aromatic polyimides with excellent thermal properties were fabricated by traditional two‐step polycondensation reaction of dianhydride monomer 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride) or 4,4‐(hexafluoroisopropylidene)diphthalic anhydride with diamine monomer 1,3‐bis(4‐aminophenoxy)benzene or 1,3‐bis(3‐aminopropyl) tetramethyldisiloxane in N,N‐dimethylacetylamide solvent. Results revealed that copolyimide of PI‐4 containing trifluoromethyl and tetramethyldisiloxane possessed excellent solubility and remarkable thermal properties. PI‐4 could dissolve well in common low boiling point solvents such as THF of up to 80 mg/mL and acetone of 40 mg/mL. Moreover, the 10% weight loss temperature of the PI‐4 was 539°C and the T_g value of the PI‐4 was 311°C. PI‐4 might be easily cast into flexible and tough films applied in optoelectronic devices. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41713.     

Development of gallic acid sensors based on polyimide-modified platinum electrode

A series aromatic polyimide (PI) membranes in the form of permselective films was synthesised from different dianhydrides with two diamine monomers for gallic acid (GA) measurement. The obtained PI films were examined by Spectroscopic techniques, Scanning Electron Microscopy (SEM) and thermal analysis techniques and then used to fabricate the selective films on the modified electrode. Because of their excellent film properties, as the permselective polymeric membranes were used for determination of GA in the presence of various interferences and real sample. The PI-1-modified Pt electrode showed a very high R-value (0.9935) and reproducibility for GA determination, as well as high selectivity.