BAPP-PBAP-ODPA共聚聚酰亚胺的合成

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和4-苯基-2,6-双(4-氨基苯基)吡啶(PBAP)作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,分别经热亚胺化和化学亚胺化合成了3种聚酰亚胺。用傅里叶变换红外光谱和核磁共振氢谱表征聚合物的结构,结果表明在1 780,1 720,725 cm~(-1)附近出现了聚酰亚胺的特征吸收峰。采用热重分析,溶解性、拉伸性能和吸水率测试表征了产物性能。所合成的聚酰亚胺溶解性和热稳定性良好,在N_2气氛中,起始降解温度超过500℃;800℃质量保持率为46.2%～64.5%(化学亚胺化)和52.6%～64.8%(热亚胺化)。聚酰亚胺膜的拉伸强度、拉伸断裂应变、拉伸模量分别为107.2～109.6 MPa,7.8%～10.5%,2.13～2.28 GPa。膜的吸水率为0.68%～0.75%。     

可溶性BAPP-MDA-ODPA共聚聚酰亚胺的合成与性能

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和4,4′-二氨基二苯甲烷(MDA)作为二胺,3,3,′4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,分别经热亚胺化和化学亚胺化过程合成了可溶性共聚聚酰亚胺。用FT-IR对聚合物的结构进行了表征,FT-IR测试结果表明在1 780 cm-1、1 720 cm-1和725 cm-1左右出现了聚酰亚胺的特征吸收峰。采用溶解性测试、DSC、TGA、拉伸测试和吸水率测试对产物的性能进行了测试。共聚聚酰亚胺在常见有机溶剂中可溶,并且有很好的热稳定性,在氮气氛中,起始降解温度超过500℃,800℃质量保持率为58.2%。共聚聚酰亚胺膜的拉伸强度、拉伸模量、断裂伸长率分别为103.5 MPa,2.36 GPa和11.7%。同时共聚聚酰亚胺膜还有很低的吸水率,为0.87%。     

DABA-BAPP-BPADA共聚聚酰亚胺的合成与性能

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)及3,5-二氨基苯甲酸(DABA)作为二胺,2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,分别经热亚胺化和化学亚胺化过程合成了可溶性共聚聚酰亚胺。用FT-IR对聚合物的结构进行了表征,性能测试采用了溶解性测试、DSC、TGA、拉伸测试和吸水率测试。FT-IR图谱表明,在1 780cm~(-1)、1720 cm~(-1)和740 cm~(-1)左右出现了聚酰亚胺的特征吸收峰。共聚聚酰亚胺在常见有机溶剂中可溶,并且有很好的热稳定性,玻璃化转变温度T_g为226.5℃,在氮气氛中降解起始温度508.5℃,800℃质量保持率为46.5%。共聚聚酰亚胺膜的拉伸强度、拉伸模量、断裂伸长率分别为109.7MPa、2.25GPa和15.2%。     

新型含吡啶环芳香二胺及其可溶性聚酰亚胺的合成与表征

以苯甲醛和3-(4-硝基苯氧基)苯乙酮(NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-苯基-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(PNPP),再用Pd/C和水合肼将PNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-苯基-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(PAPP)。以PAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.59 dL/g和0.56 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(T_g)为230.8℃,氮气氛中10%失重温度为552.0℃,同时,膜还有较好的力学性能,拉伸强度为88.6 MPa,拉伸模量为1.04 GPa,断裂伸长率为8.7%,膜的吸水率为0.89%。     

含氟聚吡啶酰亚胺的合成及性能研究

以4-(4-三氟甲基苯基)-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(m,p-3FPAPP)作为二胺单体,3,3’,4,4’-二苯醚四甲酸二酐(ODPA)和2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)作为二酐单体,通过两步法成功的制备了3种含氟聚吡啶酰亚胺。利用FTIR、XRD、TGA、DSC、UV-vis以及溶解性测试对其结构和性能进行了表征。结果表明,所得聚合物都具有优异的溶解性能,玻璃化转变温度为234～259.3℃,5%失重温度为526.5～558.2℃,800℃下质量保持率为63.6%～64.7%,且聚酰亚胺膜在400～800 nm的可见光区间有很好的透过性能。     

新型含吡啶环二胺及其可溶透明性氟化聚酰亚胺的合成与表征

以4-三氟甲基苯甲醛和3-(4-硝基苯氧基)苯乙酮(m,p-NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-(4-三氟甲基苯基)-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(m,p-3FPNPP),再用Pd/C和水合肼将m,p-3FPNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-(4-三氟甲基苯基)-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(m,p-3FPAPP)。以m,p-3FPAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.78 dL/g和0.65 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(Tg)为234.4℃,氮气氛中10%失重温度为575.3℃,膜有很好的光学透明性,截止波长为369 nm,同时,膜还有较好的力学性能,拉伸强度为96.4 MPa,拉伸模量为1.63 GPa,断裂伸长率为9.2%,膜的吸水率为0.68%。     

化学亚胺化合成含吡啶环共聚聚酰亚胺

用2,2-双[4-（4-氨基苯氧基）苯基]丙烷（BAPP）和4-苯基-2,6-双（4．氨基苯基）吡啶（PBAP）作为二胺,3,3’,4,4＇-二苯酮四酸二酐（BTDA）作为二酐,以N,N-二甲基甲酰胺（DMF）为溶剂,合成了3种聚酰亚胺。先用BAPP和PBAP同BTDA反应生成一系列聚酰胺酸（PAA）,然后将得到的PAA用化学亚胺化制备相应的聚酰亚胺。用FT-IR、^1H—NMR、粘度测试、溶解性测试和TGA对聚合物的结构和性能进行了表征。结果表明,FT—IR测试在1780cm^-1、1720cm^-1和725cm^-1左右出现了聚酰亚胺的特征吸收峰,所得聚酰胺酸的特性粘数为0．32～0．46dL／g,大部分聚酰亚胺在常见有机溶剂NMP中可溶,它们有很好的热稳定性,氮气氛中,在500℃以前没有明显的降解。     

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%。     

双酚A型二胺和二酐与含吡啶环二胺共聚改性

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和4-苯基-2,6-双(4-氨基苯基)吡啶(PBA P)作为二胺,双酚A型二酐(BPADA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法.分别经热亚胺化和化学亚胺化过程合成了3种聚酰亚胺(PI).用傅里叶变换红外光谱表征聚合物的结构.结果表...     

含吡啶环二胺及其可溶性聚酰亚胺的制备与表征

以对羟基苯乙酮和苯甲醛为原料,通过亲核取代反应、改进的Chichibabin反应和水合肼催化还原合成了一种新型含吡啶环的芳香二胺4-苯基-2,6-双[4-(4-胺基苯氧基)苯]吡啶(ρ-PAPP),以N,N-二甲基甲酰胺(DMF)为溶剂,将ρ-PAPP与双酚A型二酐（BPADA）通过2步法合成了含吡啶环的新型聚酰亚胺。用红外光谱、差示扫描量热分析、热重分析、X射线衍射、溶解性测试等对聚合物的结构和性能进行了表征。结果表明,所得聚合物在1780、1723、1376 cm-1左右出现了聚酰亚胺的特征吸收峰;实验所得的聚酰亚胺能很好地溶解在常见有机溶剂中;玻璃化转变温度为191.2 °C;氮气气氛中,热失重10 %时的温度为473.8 °C,800 °C的残炭率为43 %;同时还有较好的力学性能,拉伸强度为98.5 MPa,拉伸模量为1.24 GPa,吸水率为0.67 %。     

双酚A型二胺和二酐合成可溶性聚酰亚胺的研究

采用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)为单体,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,并分别经热亚胺化和化学亚胺化过程合成了双酚A型聚酰亚胺(PI).用FTIR、DSC、TGA等对聚合物的结构和性能进行了表征.F...     

Preparation and Properties of Cyano-Containing Polyimide Films Based on 2,6-Bis(4-aminophenoxy)- benzonitrile

Summary A series of cyano-containing polyimides were synthesized from 2,6-bis(4-amino- phenoxy)benzonitrile and some aromatic dianhydride monomers by solution polycondensation. The poly(amic acid) films could be obtained by solution-cast from N-methyl-2-pyrrolidinone solutions and thermally converted into tough polyimide films. Structure and physical properties of thin films of those polyimides were measured by FTIR, TGA, dynamic mechanical analysis and LCR hitester et al. Results showed that the polyimides prepared from 2,6-bis(4-aminophenoxy)- benzonitrile and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride or 4,4’-(hexafluoropropylidene)diphthalic anhydride exhibited more excellent energy-damping characteristic and excellent solubility in NMP, DMF, DMAc, DMSO, THF and CHCl₃, whereas the polyimides from 2,6-bis(4-aminophenoxy)benzonitrile and 3,3’,4,4’-biphenyltetracarboxylic dianhydride or Pyromellitic dianhydride were insoluble in polar and nonpolar organic solvents. All polyimides indicated higher glass transition temperatures, excellent thermal stability and tensile properties. Incorporating a nitrile group into the polyimide backbone would enhance the dielectric constant of the polyimide films.     

Synthesis and characterization of novel polyimides derived from 2,6-bis[4-(3,4-dicarboxyphenoxy)benzoyl]pyridine dianhydride and aromatic diamines

A novel pyridine-containing aromatic dianhydride monomer, 2,6-bis[4-(3,4-dicarboxyphenoxy)benzoyl]pyridine dianhydride, was synthesized from the nitro displacement of 4-nitrophthalonitrile by the phenoxide ion of 2,6-bis(4-hydroxybenzoyl)pyridine, followed by acidic hydrolysis of the intermediate tetranitrile and cyclodehydration of the resulting tetraacid. A series of new polyimides holding pyridine moieties in main chain were prepared from the resulting dianhydride monomer with various aromatic diamines via a conventional two-stage process, i.e. ring-opening polycondensation forming the poly(amic acid)s and further thermal or chemical imidization forming polyimides. The inherent viscosities of the resulting polyimides were in the range of 0.51-0.68 dL/g, and most of them were soluble in aprotic amide solvents and cresols, such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc. Meanwhile, some strong and flexible polyimide films were obtained, which have good thermal stability with the glass transition temperatures of 221-278 °C, the temperature at 5% weight loss of 512-540 °C, and the residue at 800 °C of 60.4-65.3% in nitrogen, as well as have outstanding mechanical properties with the tensile strengths of 72.8-104.4 MPa and elongations at breakage of 9.1-11.7%. The polyimides also were found to possess low dielectric constants.     

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and 1 afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in m-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 °C and 526 to 565 °C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 °C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.     

3,5-双(4-氨基苯氧基)苯甲酸的合成及其聚酰亚胺薄膜的性能研究

合成3,5-双(4-氨基苯氧基)苯甲酸(35BAPBA)。其方法为3,5-二羟基苯甲酸(35DHBA)和对氯硝基苯(PCNB)通过缩合反应,合成得到了3,5-双(4-硝基苯氧基)苯甲酸(35BNPBA);然后,进一步还原,得到3,5-双(4-氨基苯氧基)苯甲酸(35BAPBA),基于35BAPBA单体,制得多种结构的含羧基芳香族聚酰亚胺薄膜,并对这些薄膜的性能进行研究。制得的3,5-双(4-氨基苯氧基)苯甲酸(35BAPBA)的熔点为245.8℃,且纯度高。各类薄膜的透过率均可达80%以上,具有良好的紫外吸收性能;吸水性均小于3%,具有优异的疏水性能;其拉伸强度在15~56MPa之间。     

Novel organosoluble fluorinated polyimides derived from 1,6-bis(4-amino-2-trifluoromethylphenoxy)naphthalene and aromatic dianhydrides

A novel trifluoromethyl-substituted bis(ether amine) monomer, 1,6-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, was prepared through the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and 1,6-dihydroxynaphthalene in the presence of potassium carbonate in dimethyl sulfoxide, followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new fluorinated polyimides were synthesized from the diamine with various commercially available aromatic tetracarboxylic dianhydrides via a conventional two-stage process with the thermal or chemical imidization of the poly(amic acid) precursors. Most of the polyimides obtained from both routes were soluble in many organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide. All the polyimides could afford transparent, flexible, and strong films with low moisture absorptions of 0.12–0.52% and low dielectric constants of 2.75–3.13 at 10 kHz. Thin films of these polyimides showed an UV–vis absorption cutoff wavelength at 376–428 nm, and those of polyimides from 4,4′-oxydiphthalic dianhydride (ODPA) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) were essentially colorless. The polyimides exhibited excellent thermal stability, with decomposition temperatures (at 10% weight loss) above 530 °C in both air and nitrogen atmospheres and glass transition temperatures (T_gs) in the range of 241–298 °C. For a comparative study, some properties of the present fluorinated polyimides were compared with those of structurally related ones prepared from 1,6-bis(4-aminophenoxy)naphthalene and 2,6-bis(4-amino-2-trifluoromethylphenoxy)naphthalene.