Synthesis and characterization of polyimides from novel 1-(3′,5′-bis(trifluoromethyl)benzene) pyromelliticdianhydride (6FPPMDA)

Mono-substituted dianhydride monomer, 1-(3′,5′-bis(trifluoromethyl)phenyl) pyromellitic dianhydride (6FPPMDA), was prepared via the Suzuki cross coupling reaction followed by oxidation and cyclodehydration. The monomer was characterized by FT-IR, NMR, elemental analyzer (EA) and melting point apparatus. For comparison, 1-(4′-trifluoromethylphenyl)pyromellitic dianhydride (3FPPMDA) and 1-phenyl pyromellitic dianhydride (PPMDA) were also utilized. The dianhydrides were used to prepare polyimides with aromatic diamines such as bis(3-aminophenyl) 3,4-bis(trifluoromethyl)phenyl phosphine oxide (mDA6FPPO), bis(3-aminophenyl) 4-(trifluoromethyl)phenyl phosphine oxide (mDA3FPPO), bis(3-aminophenyl) phenyl phosphine oxide (mDAPPO) and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (p3FDAm). The polyimides were synthesized via a two-step process; preparation of poly(amic-acid) in p-chlorophenol with isoquinoline, followed by solution imidization at the reflux temperature for 12 h. Polymer characterization was carried out by FT-IR, NMR, GPC, DSC and TGA, and their solubility, solution viscosity, water absorption, CTE, dielectric constant and refractive index were also evaluated.     

Synthesis and characterization of novel fluorinated polyimides derived from bis[4-(4′-aminophenoxy)phenyl]-3,5-bis(trifluoromethyl)phenyl phosphine oxide

A novel fluorinated aromatic diamine, bis[4-(4′-aminophenoxy)phenyl]-3,5-bis(trifluoromethyl)phenyl phosphine oxide, was synthesized. A series of new fluorinated polyimides containing phosphine oxide was prepared from the novel diamine with various commercially available aromatic dianhydrides. All the fluorinated polyimides show high glass transition temperatures, excellent thermal stability, and good solubility in common organic solvents.     

Adhesion property of novel polyimides with 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride

Novel polyimides were synthesized from 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride (6FPPMDA) by a conventional two‐step process: the preparation of poly(amic acid) followed by solution imidization via refluxing in p‐chlorophenol. The diamines used for polyimide synthesis included bis(3‐aminophenyl)‐3,5‐bis(trifluoromethyl)phenyl phosphine oxide, bis(3‐aminophenyl)‐4‐trifluoromethylphenyl phosphine oxide, and bis(3‐aminophenyl)phenyl phosphine oxide. The synthesized polyimides were designed to have a molecular weight of 20,000 g/mol by off‐stoichiometry and were characterized by Fourier transform infrared, NMR, differential scanning calorimetry, and thermogravimetric analysis. In addition, their intrinsic viscosity, solubility, water absorption, and coefficient of thermal expansion (CTE) were also measured. The adhesion properties of the polyimides were evaluated via a T‐peel test with bare and silane/Cr‐coated Cu foils, and the failure surfaces were investigated with scanning electron microscopy. The 6FPPMDA‐based polyimides exhibited high glass‐transition temperatures (280–299°C), good thermal stability (>530°C in air), low water absorption (1.46–2.16 wt %), and fairly low CTEs (32–40 ppm/°C), in addition to good adhesion properties (83–88 g/mm) with silane/Cr‐coated Cu foils. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1801–1809, 2005     

Synthesis and characterization of polyimides from bis(3-aminophenyl)-2,3,5,6-tetrafluoro-4-trifluoromethylphenyl phosphine oxide (mDA7FPPO)

A novel diamine, bis(3-aminophenyl)-2,3,5,6-tetrafluoro-4-trifluoromethylphenyl phosphine oxide (mDA7FPPO), was synthesized via Grignard reaction, followed by nitration and reduction. The monomer was characterized by FT-IR, NMR and melting point apparatus, and utilized to prepare polyimides with 6FDA, BTDA or ODPA via a conventional two-step synthesis; preparation of poly(amic acid), followed by solution imidization. The molecular weight of polyimides was controlled to 20,000 g/mol by off-stoichiometry and the polyimides were characterized by FT-IR, NMR, GPC, TGA and DSC. Solubility, intrinsic viscosity, dielectric constant and refractive index were also evaluated. The novel polyimides exhibited high T_g (229-252 °C), excellent thermal stability (>500 °C), low dielectric constant (2.65-2.81) and low birefringence (0.0019-0.0049).     

Synthesis and characterization of polyimides from 4‐(diphenyl phosphine oxide)phenyl pyrromellitic dianhydride

A novel rigid‐rod type dianhydride monomer with phosphine oxide moiety, 4‐(diphenyl phosphine oxide)phenyl pyrromellitic dianhydride (POPPMDA), was synthesized via the Suzuki coupling reaction of 4‐(diphenyl phosphine oxide)phenyl boronic acid (POBB) and 1‐bromo‐2,3,5,6‐tetramethyl benzene (B4MB), followed by oxidation and cyclodehydration. The monomer was characterized by FTIR, NMR, EA, and melting point analyzer and utilized to synthesize polyimides with diamines such as bis(3‐aminophenyl)phenyl phosphine oxide (mDAPPO) and p‐phenylene diamine (pPDA) by varying their ratio. The polyimides were prepared via a conventional two‐step synthesis: preparation of poly(amic‐acid), followed by solution imidization. The polyimides were characterized by FTIR, NMR, DSC, TGA, and TMA, and their solubility, intrinsic viscosity, and adhesive properties were also evaluated. The polyimides exhibited high T_g (342–362°C), good thermal stability (>500°C), excellent adhesive property (134–107 g/mm), and low CTE (28–17 ppm/°C). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of a new diamine and its effect on the residual stress of colorless polyimide

A new diamine was designed and synthesized to improve the flexibility of colorless polyimides by reducing residual stress. Four variations of colorless polyimides with the same dianhydride (4,4′-(hexafluoroisopropylidene)-diphthalic) and four different diamines (bis[4-(3-aminophenoxy)-phenyl] sulfone, bis(3-aminophenyl) sulfone, 2,2′-bis(trifluoromethyl)benzidine, and 2,2-bis(4-aminophenyl)-hexafluoropropane) were used. A series of colorless polyimides were prepared by adding the new diamine. The carbon and ether bonds between the benzene rings of the new diamine affected the flexibility and optical properties of colorless polyimide. The synthesis of the new diamine was confirmed by NMR measurements. Furthermore, the decrease in residual stress at room temperature and the glass transition temperature was confirmed. The effect of the new diamine was most evident for polyimide with a bulky and rigid structure. Though a slight yellow color appears because of the broken charge transfer complex balance, controlling the content of the new diamine will allow application of polyimides in flexible display.     

Synthesis and characterization of soluble copolyimides containing chalcone and phosphine oxide moieties in the main chain

The functional diamines 3,3′‐diaminochalcone and bis(3‐aminophenyl)‐3,5‐bis(trifluoromethyl)phenyl phosphine oxide were successfully prepared by simple and convenient procedures with short reaction times, and the overall yields were 78 and 70%, respectively. Copolyimides prepared from 3,3′‐diaminochalcone, bis(3‐aminophenyl)‐3,5‐bis(trifluoromethyl)phenyl phosphine oxide, and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride exhibited excellent solubility in several organic solvents, such as dimethyl sulfoxide, N,N‐dimethylformamide, N‐methyl pyrrolidone, tetrahydrofuran, and acetone. They also showed very good thermal stability even up to 450°C for 5% weight loss (by thermogravimetric analysis) in nitrogen and a high glass‐transition temperature up to 274°C (by differential scanning calorimetry) in nitrogen. The copolymers' adhesive and photoreactive properties were also investigated, and it was confirmed that the copolyimide containing chalcone and phosphine oxide moieties in the main chain had good adhesiveness and photoreactivity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Soluble polyimides containing trans-diaminotetraphenylporphyrin: Synthesis and photoinduced electron transfer

5,15-Bis(4-aminophenyl)-10,20-diphenylporphyrin (trans-DATPP) was synthesized via the condensation of meso-(4-nitrophenyl)dipyrromethane and benzaldehyde. The further reaction with zinc acetylacetonate hydrate afforded zinc 5,15-bis(4-aminophenyl)-10,20-diphenylporphyrin (trans-ZnDATPP). A series of soluble polyimides based on trans-DATPP or trans-ZnDATPP, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB) and 4,4′-hexafluoroisopropylidenediphthalic anhydride (6FDA) at various ratios was then prepared. Some physical properties of these polyimides were measured. It was found that every polyimide containing either trans-DATPP or trans-ZnDATPP had higher viscosity than the polyimide without porphyrin unit. Furthermore, the polyimides with trans-ZnDATPP showed lower viscosity than the ones without trans-ZnDATPP at approximately the same porphyrin content. Glass transition temperatures (T_gs) of polyimides containing trans-ZnDATPP were higher than polyimides containing trans-DATPP, and both were higher than polyimide without porphyrin. Steady state fluorescence spectroscopy of these polymers revealed that the quantum yield of polymers increased with higher content of free base porphyrin in the polymer chain. Time-correlated single photon counting experiments indicated these polyimides could be used in photonic applications.     

Phosphorus-containing epoxy for flame retardant. III: Using phosphorylated diamines as curing agents

Two phosphorus-containing diamine compounds, bis(4-aminophenoxy)-phenyl phosphine oxide and bis(3-aminophenyl)phenyl phosphine oxide, were synthesized for use as curing agents of epoxy resins. Phosphorylated epoxy resins were obtained by curing Epon 828 and Eponex 1510 with these two diamine agents. For raising the phosphorus contents of the resulting epoxy resins, the phosphorus-containing epoxy, bis(glycidyloxy)phenyl phosphine oxide (BGPPO), was also used. These two diamine agents showed similar reactivity toward epoxies. Their reactivities were higher than DDS and lower than DDM. High char yields in TGA evaluation were found for all the phosphorylated epoxy resins, implying their high flame retardancy. The excellent flame-retardant properties of these phosphorylated epoxy resins were also demonstrated by the high limiting oxygen index (LOI) values of 33 to 51. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 895–901, 1997     

Addition polyimides. IV. Effect of structure on thermal characteristics

Chain extension reaction of bis(m-maleimido phenyl) methyl phosphine oxide (BP) with 4,4′-diaminodiphenylmethane (BP–M), 4,4′-diaminodiphenyl ether (BP–E), 3,3′- and 4,4′-diaminodiphenyl sulfone (BP–DDS_m and (BP-DDS_m respectively), tris (m-aminophenyl) phosphine oxide (BP–TAP), and 9,9-bis(p-aminophenyl) fluorene (BP–BAF) was carried out by refluxing 1:0.3 molar solution of BP:diamine. The melting temperature and exothermic peak associated with curing of BP decreased by such chain extension. The thermogravimetric analysis indicated more than 60% residual weight at 800°C in nitrogen atmosphere in BP–DDS_m, BP–DDS_p, and BP–TAP resins. These resins can be processed at low temperature and can be used for fabrication of composites with improved properties.     

含氟和氧膦共缩聚型聚酰亚胺的合成与表征

以水合肼-六水合三氯化铁-活性炭为还原体系, 3, 5 二(三氟甲基)溴苯和二苯基次膦酰氯为原料,经格氏反应、硝化和还原合成了含氟和氧膦的二胺,总收率达 50%。并用FTIR、1HNMR和熔点测试技术对其结构进行了鉴定。该反应具有操作简便,条件温和,收率高易于纯化的优点。然后用常规的二步法,使该二胺和 4, 4′ 二胺基二苯醚与六氟异丙叉基 (3, 4 邻苯二甲酸酐)进行共缩聚,并经化学酰亚胺化制得了共缩聚型聚酰亚胺,收率为 93%。该共缩聚型聚酰亚胺在非质子强极性溶剂中均具有良好的溶解性,玻璃化温度 (Tg)大于 250℃,10%的热分解温度(Td)为 519 7℃。实验表明,氧膦的引入提高了聚酰亚胺的附着力。     

Effect of structure on the thermal behaviour of ethynyl-terminated imide resins

A series of ethynyl-terminated aromatic imide monomers containing phosphine oxide in the backbone were synthesized by the reaction of tris(3-aminophenyl) phosphine oxide (TAP) or bis(3-aminophenyl)methyl phosphine oxide (BAP) with pyromellitic dianhydride (PMDA) or 3, 3′,4, 4′-benzophenone tetracarboxylic acid dianhydride (BTDA) or 4, 4′-perfluoroisopropylidenebis(phthalic anhydride), and 3-ethynyl aniline. Structural characterization was done by infrared, nuclear magnetic resonance spectroscopy and elemental analysis. Thermal characterization was done by differential scanning calorimetry and thermogravimetric analysis. The decomposition temperatures of cured resins were above 500°C in nitrogen atmosphere. Char yield at 800°C ranged from 52–63.5%.     

Synthesis and characterization of novel polyimides derived from 1,1-bis[4-(4′-aminophenoxy)phenyl]-1- [3″,5″-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane

A novel fluorinated aromatic diamine monomer, 1,1-bis[4-(4′-aminophenoxy)phenyl]-1-[3″,5″-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane(9FTPBA), was synthesized by coupling 3′,5′-bis(trifluoromethyl)-2,2,2-trifluoroacetophenone with 4-nitrophenyl phenyl ether under the catalysis of trifluoromethanesulfonic acid, followed reduced by reductive iron and hydrochloric acid. A series of new fluorine-containing polyimides having inherent viscosities of 0.96-1.23 dl/g was synthesized from the novel diamine with various commercially available aromatic dianhydrides using a standard two-stage process with thermal imidization and chemical imidization of poly(amic acid) films. All the fluorinated polyimides were soluble in many polar organic solvents such as NMP, DMAc, DMF, and m-cresol, as well as some of low boiling point organic solvents such as chloroform and acetone. The polymer films have good thermal stability with the glass transition temperature of 223-225 °C, the temperature at 5% weight loss of 535-568 °C in nitrogen, and have outstanding mechanical properties with the tensile strengths of 68-89 MPa, initial moduli of 2.14-2.19 GPa, and elongations at breakage of 3.2-10.5%.     

Preparation and characterization of organosoluble polyimides based on 1,1-bis[4-(3,4-aminophenoxy)phenyl]cyclohexane and commercial aromatic dianhydrides

A bis(ether amine) III-A containing a cyclohexane cardo group, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, was synthesized and used as a monomer to prepare polyimides VI-A with six commercial dianhydrides via three different procedures. The intermediate poly(amic acid)s had inherent viscosities of 0.83–1.69 dL g⁻¹ and were thermally or chemically converted into polyimides. Polyimides were also prepared by high-temperature direct polymerization in m-cresol and had inherent viscosities higher than the thermally or chemically cyclodehydrated ones. To improve the solubility of polyimides, six copolyimides were also synthesized from bis(ether amine) III-A with a pair of dianhydrides, which contained 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride or 4,4′-hexafluoroisopropylidenediphthalic anhydride. Series VI-A polyimides were characterized by the good physical properties of their film-forming ability, thermal stability, and tensile properties. A comparative study of the properties, with the corresponding polyimides derived from 2,2-bis[4-(4-aminophenoxy)phenyl]propane, is also presented. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2750–2759, 2001     

Polyimides. I. Preparation and properties of phosphorus-containing polyimides

Phosphorus-containing polyimide resins were prepared by reacting benzophenone tetracarboxylic acid dianhydride with (3-aminophenyl) methyl phosphine oxide (DAP). Copolyimides were also prepared using DAP and 4,2′,4′-triaminobenzanilide (TAB) and tris(3-aminophenyl) phosphine oxide (TAP) and pyromellitic dianhydride (PMDA). The homopolymer showed good thermal properties and little degradation below 400°C. The lapshear strengths of these polyimides depended on the backbone structure. Copolymerization improved thermal and mechanical properties. The glass-fabric-reinforced laminate prepared from one of the copolymer resins had a tensile strength of 43,430 psi.     

Synthesis and characterization of phosphorus-containing methacrylate-based difunctional crosslinkers and their use in UV-curable resin systems

Two new phosphorus-containing methacrylate-based difunctional crosslinking agents [bis(4-(2-methacryloyloxy)ethyl carboxyl)phenyl phosphine oxide (BEPPPO) and bis(4-(2-methacryloyloxy)ethylcarbonylaminophenyl)phenyl phosphine oxide (BUPPPO)], which can be good candidates for UV-curable coating applications, were synthesized by reacting either a phosphorus-containing diisocyanate [bis(4-isocyanatophenyl)phenyl phosphine oxide] or a phosphorus-containing diacid chloride [bis(4-chloroformylphenyl)phenyl phosphine oxide] with hydroxyethyl methacrylate. The structures of the monomers thus obtained were characterized by FTIR, mass, and ¹H-NMR spectroscopies. The contents of the new crosslinking agents in the UV-cured polymeric films were varied between 10 and 30% by weight. Mechanical, physical, and thermal characterizations of the UV-cured films were investigated. An increase in crosslinking agent content caused an increse in mechanical properties. Films containing BUPPPO had higher tensile strength values compared to the films containing BEPPPO. Thermogravimetric analysis of phosphorus-containing crosslinking agents revealed that incorporating phosphorus into the structure resulted in a high char yield up to 24.5% at 600°C. Water absorption values of UV-cured films were also affected by the amount and type of crosslinking agent. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2575–2585, 1999     

Phosphine oxide containing aromatic polyester

A phosphine oxide containing aromatic polyester has been synthesized by the direct polycondensation reaction of bis[4-(m-carboxyphenoxy)phenyl]phenylphosphine oxide (m-BCPPO) and 4,4′-isopropylidene-diphenol (bisphenol A). The presence of phosphine oxide linkages in the backbone gives this polymer superior properties: namely thermo-oxidative stability, high char yield and solubility in common organic solvents.     

Synthesis and characterization of soluble polyimides and its ultrafiltration membrane performances

Soluble polyimides were synthesized and characterized from two diamines and four dianhydrides by the two- and the one-step method. Most of the polyimides could be soluble by one-step method except α,α′-bis(4-aminophenyl)-1,4-diisopropyl benzene/3,3′,4,4′-benzophenonetetracarboxylic dianhydride system in limited organic solvents. Glass transition temperatures ranged from 186 to 233°C and crystalline melt temperatures were not observed. All the soluble polyimides showed good thermal, mechanical, and electrical properties. The polyimides did not have crystalline structure and limited solubilities. The effective solvent had a medium dispersion component associated with weak polar and hydrogen components. The polymer from one-step polymerization had a narrower molecular weight distribution than the two-step method. Polyimide synthesized with 4,4′-oxydiphthalic anhydride and bis[4-(3-aminophenoxy)phenyl]sulfone by two-step method could only be prepared by the typical phase inversion method. Other membranes except this polyimide membrane could not be prepared by the typical phase-inversion method because of poor solubility about polar solvents. The flux of this ultrafiltration membrane was very high, and this membrane could especially retain polymer having a molecular weight 20,000 to above 90%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 907–918, 1999     

Addition polyimides. I

Crosslinking of 4,4′(bismaleimido)diphenyl ether (BM) was investigated in presence of bis(m-aminophenyl)methylphosphine oxide (BAP), tris(m-aminophenyl)phosphine oxide (TAP), diaminodiphenyl ether (E) and 3,3-bis(p-aminophenyl)phthalide (AP). These crosslinked resins were examined for thermal stability by thermogravimetric analysis. A slight decrease in initial decomposition temperature, the temperature of maximum rate of weight loss, was observed, though the char yield in nitrogen atmosphere at 800°C did not change appreciably. Glass-cloth-reinforced laminates were fabricated from BM and amine mixtures. An improvement in mechanical properties was observed in the presence of phosphorus-containing di- and triamines.     

2,2-双(3-氨基苯基)六氟丙烷聚酰亚胺单体的合成及表征

以2,2-双(3-硝基苯基)六氟丙烷为原料,在三氯化铁/炭(FeCl3/C)、水合肼的作用下,还原得到了2,2-双(3-氨基苯基)六氟丙烷聚酰亚胺单体,并对其进行了分析表征。然后,2,2-双(3-氨基苯基)六氟丙烷与4,4’-2-六氟亚异丙基-2-邻苯二甲酸酐(6FDA)在N,N-二甲基甲酰胺(DMF)中缩聚制得聚酰亚胺聚合物。