Poly(ether imide)s derived from phthalazinone‐containing dianhydrides

An unsymmetrical and noncoplanar heterocyclic dianhydride was synthesized from a bisphenol‐like phthalazinone, 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, and a series of novel poly(ether imide)s based on it, with intrinsic viscosities of 0.67–1.42 dL/g, were obtained by one‐step solution polymerization in m‐cresol at 200 °C for 20 h. The polymers were readily soluble in N‐methyl‐2‐pyrrolidinone and m‐cresol. The poly(ether imide)s derived from 4,4′‐oxydianiline and 4,4′‐methylenedianiline were also very soluble in chloroform, 1,1′,2,2′‐tetrachloroethane, and N,N‐dimethylacetamide. The glass‐transition temperatures were 289–326 °C, as determined by differential scanning calorimetry. All the degradation temperatures for 5% weight loss occurred above 482 °C in nitrogen. The tensile strength of thin films of some of the polymers varied from 103.1 to 121.4 MPa. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6089–6097, 2004     

A new category of thermally stable poly(ether amide ether imide)s with increased solubility

Two new poly(ether amide ether imide)s (PEAEIs) were prepared from a new diamine (DA) containing ether, aliphatic, amide, naphthyl and pyridine functional groups that resulted flexible and thermally stable ultimate polymers. The DA was synthesized via two steps, starting from nucleophilic substitution reaction of 1,8‐diamino‐3,6‐dioxaoctane with 6‐chloronicotinoyl chloride in the presence of propylene oxide which, afforded dichloro‐diamide (DCDA) compound. In the second step for the preparation of DA, reaction of DCDA compound with 5‐amino‐1‐naphthol in the presence of K₂CO₃ was achieved. The new DA was then polycondensed with 2,2'‐bis‐(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride and pyromellitic dianhydride to produce PEAEIs. The precursor, monomer and obtained polymers were entirely characterized by FT‐IR and ¹H‐NMR spectroscopy and elemental analysis techniques. The physical properties of the polymers including solubility, thermal behavior, thermal stability, inherent viscosity, morphology and mechanical properties were studied. The new PEAEIs exhibited favorable balance of physical and thermal properties, and their solubility was improved without sacrificing their thermal stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and characterization of aromatic poly(ether sulfone imide)s derived from sulfonyl bis(ether anhydride)s and aromatic diamines

Two sulfonyl group-containing bis(ether anhydride)s, 4,4′-[sulfonylbis(1,4-phenylene)dioxy]diphthalic anhydride ( IV ) and 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]diphthalic anhydride (Me- IV ), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of the bisphenolate ions of 4,4′-sulfonyldiphenol and 4,4′-sulfonylbis(2,6-dimethylphenol) with 4-nitrophthalonitrile in N,N-dimethylformamide (DMF). High-molar-mass aromatic poly(ether sulfone imide)s were synthesized via a conventional two-stage procedure from the bis(ether anhydride)s and various aromatic diamines. The inherent viscosities of the intermediate poly(ether sulfone amic acid)s were in the ranges of 0.30–0.47 dL/g for those from IV and 0.64–1.34 dL/g for those from Me- IV. After thermal imidization, the resulting two series of poly(ether sulfone imide)s had inherent viscosities of 0.25–0.49 and 0.39–1.19 dL/g, respectively. Most of the polyimides showed distinct glass transitions on their differential scanning calorimetry (DSC) curves, and their glass transition temperatures (T_g) were recorded between 223–253 and 252–288°C, respectively. The results of thermogravimetry (TG) revealed that all the poly(ether sulfone imide)s showed no significant weight loss before 400°C. The methyl-substituted polymers showed higher T_g's but lower initial decomposition temperatures and less solubility compared to the corresponding unsubstituted polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1649–1656, 1998     

Synthesis and Characterization of Poly(ether imide)s Containing m-Methyl and Phthalazinone Moieties

Aromatic polyimides are distinguished for their excellent mechanical and thermal properties in many engineering fields1. However, aromatic polyimides are normally insoluble in common organic solvents, which restricts their applications in some fields. Many efforts have been taken to improve their solubility. Introducing bulky side groups and non-coplanar structure into polymers bone chains is a good way to obtain the polymers with excellent mechanical and thermal properties2. In this paper…     

Synthesis and properties of poly(ether imide)s based on a benzonorbornane bis(ether anhydride)

A novel bis(ether anhydride) monomer, 3,6‐bis(3,4‐dicarboxyphenoxy)benzonorbornane dianhydride, was synthesized from the nitro displacement of 4‐nitrophthalonitrile with 3,6‐dihydroxybenzonorbornane in the presence of potassium carbonate, followed by the alkaline hydrolysis of the intermediate bis(ether dinitrile) and the cyclodehydration of the resulting bis(ether diacid). A series of poly(ether imide)s bearing pendant norbornane groups were prepared from the bis(ether anhydride) with various aromatic diamines via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s followed by thermal imidization to the poly(ether imide)s. The inherent viscosities of the poly(amic acid) precursors were 0.81–1.81 dL/g. The poly(ether imide) with m‐phenylenediamine as a diamine showed good organosolubility. Most of the cast poly(ether imide) films have had high tensile strengths and moduli. The glass‐transition temperatures of these poly(ether imide)s, except for those from rigid p‐phenylenediamine and benzidine, were recorded between 211 and 246 °C by differential scanning calorimetry. The softening temperatures of all the poly(ether imide) films stayed within 210–330 °C according to thermomechanical analysis. No polymers showed significant decomposition before 500 °C in a nitrogen or air atmosphere. A comparative study of the properties with the corresponding poly(ether imide)s without pendant substituents was also made. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1712–1725, 2002     

Poly(aryl ether)s containing o‐terphenyl subunits. III. Random copoly(ether imide)s

The synthesis of a new diamine monomer, N‐n‐butyl 3,12‐diamino‐5,6,9,10‐tetrahydro[5]helicene‐7,8‐dicarboxylic imide (4), that contains a helically locked, U‐shaped 4′,4″‐o‐terphenyl moiety is described. The monomer was polymerized with 3,3′,4,4′‐oxydiphthalic dianhydride and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane to form a series of copoly(ether imide)s (5a–e). The incorporation of 4 into the poly(ether imide)s varied the glass‐transition temperature of the copolymers of which it was a part. There was a tendency to form macrocyclic materials at higher molar percentages of 4 during polymerization. The fluorescence of all the copoly(ether imide)s gradually decreased as the content derived from monomer 4 increased in the polymer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 758–763, 2000     

主链含酰亚胺结构的聚醚醚酮的合成及其性能

以1,4-二苯氧基苯为单体分别与N,N′-(4,4′-二苯甲烷)-双-(3,4-二甲酰亚胺基苯甲酰氯)和N,N′-(4,4′-二苯砜)-双-(3,4-二甲酰亚胺基苯甲酰氯),采用低温溶液缩聚合成了2种主链含酰亚胺结构的聚醚醚酮树脂,聚合物的比浓对数粘度分别为0.98和0.61 dL/g。 用FT-IR、¹H NMR和WAXD进行了结构表征,用DSC和TGA测试了热性能。 结果表明,聚合物有较高的玻璃化转变温度(T_g分别为236和263 ℃),N₂气气氛中热分解温度(5%T_d)分别为529和512 ℃,能溶于N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、氯仿和间甲酚等常见的有机溶剂中。     

Synthesis and properties of poly(ether imide)s based on the bis(ether anhydride)s from hydroquinone and its derivatives

Four bis(ether anhydride)s, 4,4′‐(1,4‐phenylenedioxy)diphthalic anhydride (IV), 4,4′‐(2,5‐tolylenedioxy)‐diphthalic anhydride (Me‐IV), 4,4′‐(2‐chloro‐1,4‐phenylenedioxy)diphthalic anhydride (Cl‐IV), and 4,4′‐(2,5‐biphenylenedioxy)diphthalic anhydride (Ph‐IV), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of 4‐nitrophthalonitrile with the potassium phenoxides of hydroquinone and various substituted hydroquinones such as methylhydroquinone, chlorohydroquinone, and phenylhydroquinone in N,N‐dimethylformamide, followed by alkaline hydrolysis and dehydration. Four series of poly(ether imide)s were prepared from bis(ether anhydride)s with various aromatic diamines by a classical two‐step procedure. The inherent viscosities of the intermediate poly(amic acid)s were in the range of 0.40–2.63 dL/g. Except for those derived from p‐phenylenediamine and benzidine, almost all the poly(amic acid)s could be solution‐cast and thermally converted into transparent, flexible, and tough polyimide films. Introduction of the chloro or phenyl substituent leads to a decreased crystallinity and an increased solubility of the polymers. The glass transition temperatures (T_g) of these polyimides were recorded in the range of 204–263°C. In general, the methyl‐ and chloro‐substituted polyimides exhibited relatively higher T_gs, whereas the phenyl‐substituted ones exhibited slightly lower T_gs compared to the corresponding nonsubstituted ones. Thermogravimetric analysis (TG) showed that 10% weight loss temperatures of all the polymers were above 500°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 665–675, 1999     

Synthesis and properties of new adamantane‐based poly(ether imide)s

A new adamantane‐based bis(ether anhydride), 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]adamantane dianhydride, was prepared in three steps starting from nitrodisplacement of 4‐nitrophthalonitrile with the potassium phenolate of 2,2‐bis(4‐hydroxyphenyl)adamantane. A series of adamantane‐containing poly(ether imide)s were prepared from the adamantane‐based bis(ether anhydride) and aromatic diamines by a conventional two‐stage synthesis in which the poly(ether amic acid)s obtained in the first stage were heated stage‐by‐stage at 150–270°C to give the poly(ether imide)s. The intermediate poly(ether amic acid)s had inherent viscosities between 0.56 and 1.92 dL/g. Except for those from p‐phenylenediamine, m‐phenylenediamine, and benzidine, all the poly(ether amic acid) films could be thermally converted into transparent, flexible, and tough poly(ether imide) films. All the poly(ether imide)s showed limited solubility in organic solvents, although they were amorphous in nature as evidenced by X‐ray diffractograms. Glass transition temperatures of these poly(ether imide)s were recorded in the range of 242–317°C by differential scanning calorimetry and of 270–322°C by dynamic mechanical analysis. They exhibited high resistance to thermal degrdation, with 10% weight loss temperatures being recorded between 514–538°C in nitrogen and 511–527°C in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1619–1628, 1999     

Synthesis and Characterization of Poly (ether imide)s Containing Phthalazinone and Isopropyl Moieties

Uses for aromatic polyimides have developed rapidly in recent years due to their outstanding properties1,2. However, their applications have been limited in many fields because aromatic polyimides are normally insoluble and infusible. The poly (ether imide)s (PEI) prepared by the polymerization of bisphenol-A diphthalic anhydride (BPA dianhydride) and m-phenylenediamine (m-PDA) ,developed by General Electric Plastics and marketed under the trade name Ultem 1000, has excellent processabili…     

Synthesis and characterization of hyperbranched aromatic poly(ether imide)s with terminal amino groups

We synthesized an AB₂‐type monomer, 4‐{4‐[di(4‐aminophenyl)methyl]phenoxy}phthalic acid, which contained one phthalic acid group and two aminophenyl functionalities. The direct self‐polycondensation of the AB₂‐type monomer in the presence of triphenylphosphite as an activator afforded a hyperbranched poly(ether imide) with a large number of terminal amino groups. This polymer was characterized with ¹H NMR and IR spectroscopy. The degree of branching of the hyperbranched poly(ether imide) was approximately 56%, as determined by a combination of model compound studies and an analysis of ¹H NMR spectroscopy integration data. The terminal amino groups underwent functionalization readily. The solubility and thermal properties of the resulting polymers depended on the nature of the chain end groups. In addition, the hyperbranched poly(ether imide) was grafted with polyhedral oligomeric silsesquioxane (POSS). Transmission electron microscopy analysis revealed that the grafted POSS molecules aggregated to form a nanocomposite material. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3726–3735, 2003     

磺化聚醚酰亚胺/聚醚砜共混型质子交换膜的制备及其性能

以磺化聚醚酰亚胺(SPEI)和聚醚砜(PES)为原料, 采用溶液共混法成功制备出了SPEI/PES共混型质子交换膜,并经热重分析、AFM、SEM等对膜的结构和性能进行了表征. 结果表明, 共混膜较纯SPEI膜具有更高的热稳定性和较低的溶胀性; 在室温环境下, 共混膜在干态和湿态时均具有优异的机械性能; 与纯SPEI膜相比, 共混膜的形态结构更为致密, 这将有利于降低甲醇的渗透性. 采用交流阻抗法和隔膜扩散法分别考察了膜的质子传导性和阻醇性能, 对于共混质量比为50/50的膜来说, 其质子传导率达到了5.5 mS·cm-1的水平, 能满足质子交换膜的需求, 但其甲醇渗透系数明显降低, 仅为市用Nafion 112膜的5%, 这表明该共混膜有望作为一种新型的直接甲醇燃料电池用质子交换膜.     

含杂萘联苯结构聚醚酰亚胺共聚物的物理性能

二氮杂萘酮;含杂萘联苯结构聚醚酰亚胺共聚物的物理性能     

New light‐colored poly(ether imide)s based on 2,5‐di‐tert‐butylhydroquinone bis(ether anhydride) and aromatic diamines

A series of poly(ether imide)s (PEIs), III _a–k , with light color and good physical properties were prepared from 1,4‐bis(3,4‐dicarboxypheoxy)‐2,5‐di‐tert‐butylbenzene dianhydride ( I ) with various aromatic diamines ( II _a–k ) via a conventional two‐stage procedure that included a ring‐opening polyaddition to yield poly(amic acid)s (PAA), followed by thermal imidization to the PEI. The intermediate PAA had inherent viscosities in the range of 1.00–1.53 dL g^?1. Most of the PEIs showed excellent solubility in chlorinated solvents such as dichloromethane, chloroform, and m‐cresol, but did not easily dissolve in dimethyl sulfoxide and amide‐type polar solvents. The III series had tensile strengths of 96–116 MPa, an elongation at break of 7–8%, and initial moduli of 2.0–2.5 GPa. The glass‐transition temperatures (T_g) and softening temperatures (T_s's) of the III series were recorded between 232 and 285 °C and 216–279 °C, respectively. The decomposition temperatures for 10% weight loss all occurred above 511 °C in nitrogen and 487 °C in air. The III series showed low dielectric constants (2.71–3.54 at 1 MHz), low moisture absorption (0.18–0.66 wt %), and was light‐colored with a cutoff wavelength below 380 nm and a low yellow index (b^*) values of 7.3–14.8. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1270–1284, 2005     

Synthesis and Properties of Novel Poly（amine ether）s

Using aromatic bis（4-bromophenyl） ether and various aromatic diamines as the monomers, a series of novel poly（amine ether）s （PAEs） have been synthesized via palladium-catalyzed aryl amination, which is the Hartwig-Buchwald polycondensation reaction. Their structures were characterized by means of elemental analysis, FT-IR, 1^H NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structures. Their general properties were studied by DSC and TG and it＇s obvious that they show high glass transition temperatures （Tg〉200 ℃）, good thermal stability with high decomposition temperatures （TD〉500℃） and excellent solubility. The mechanical behavior of these polymers suggested that they could be considered a new class of high-performance polymers.     

Hyperbranched aromatic poly(ether imide)s: Synthesis,characterization, and modification

The synthesis and characterization of hyperbranched aromatic poly(ether imide)s are described. An AB₂ monomer, which contained a pair of phenolic groups and an aryl fluoro moiety activated toward displacement by the attached imide heterocyclic ring, was prepared. The nucleophilic substitution of the fluoride with the phenolate groups led to the formation of an ether linkage and, subsequently, to the hyperbranched poly(ether imide), which contained terminal phenolic groups. A similar one‐step polymerization involving a monomer that contained silyl‐protected phenols yielded a hyperbranched poly(ether imide) with terminal silylated phenols. The degree of branching of these hyperbranched polymers was approximately 55%, as determined by a combination of model compound studies and ¹H NMR integration experiments. End‐capping reactions of the terminal phenolic groups were readily accomplished with a variety of acid chlorides and acid anhydrides. The nature of the chain‐end groups significantly influenced physical properties, such as the glass‐transition temperature and the solubility of the hyperbranched poly(ether imide)s. As the length of the acyl chain of the terminal ester groups increased, the glass‐transition temperature value for the polymer decreased, and the solubility of the polymer in polar solvents was reduced, becoming more soluble in nonpolar solvents. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2536–2546, 2001     

Poly(ether imide) membranes modified with poly(ethylene imine) as potential carriers for epidermal substitutes

Poly(ether imide) (PEI) membranes were modified with a linear low-molecular weight (PETIM_0.6) and a branched high-molecular weight poly(ethylene imine) (PETIM_60). The membrane surfaces became more hydrophilic and the zeta potentials were shifted from negative to positive zeta values after immobilisation of both PETIM. These measurements also indicated the presence of a swollen surface layer in the case of PETIM_60, while a regular structuring of the surface was observed with scanning force microscopy for PETIM_0.6. A human keratinocyte cell line HaCaT was cultured on the different membranes. It was found that HaCaT cell growth was stimulated by PETIM_0.6. Cells reached earlier confluence on this substratum, while their growth was inhibited on a PEI membrane modified with PETIM_60, which makes PEI membranes modified with PETIM_0.6 a promising material for in vitro culture of epidermal transplants.     

Synthesis and properties of poly(ether imide)s derived from 2,7-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride and various aromatic diamines

A naphthalene unit-containing bis(ether anhydride), 2,7-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, was prepared in three steps starting from the nucleophilic nitrodisplacement reaction of 2,7-dihydroxynaphthalene and 4-nitrophthalonitrile in N,N-dimethylformamide (DMF) solution in the presence of potassium carbonate followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aromatic poly(ether imide)s were synthesized using a conventional two-stage polymerization process from the bis(ether anhydride) and ten aromatic diamines. The intermediate poly(ether amic acid)s had inherent viscosities of 0.95–2.67 dL/g. The films of poly(ether imide)s derived from two rigid diamines, that is, p-phenylenediamine and benzidine, crystallized and embrittled during the thermal imidization process. The other poly(ether imide)s belonged to amorphous materials and could be fabricated into transparent, flexible, and tough films. These poly(ether imide) films had yield strengths of 91–115 MPa, tensile strengths of 89–136 MPa, elongation to break of 11–45%, and initial moduli of 1.7–2.2 GPa. The T_gs of poly(ether imide)s were recorded in the range of 222–256°C depending on the nature of the diamine moiety. All polymers were thermally stable up to 500°C, with 10% weight loss being recorded above 540°C in air and nitrogen atmospheres. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2281–2287, 1997     

Highly soluble and optically transparent poly (ether imide)s based on 2,6‐ or 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and aromatic bis(ether amine)s bearing trifluoromethyl groups

Two series of novel fluorinated poly(ether imide)s (coded IIIA and IIIB ) were prepared from 2,6‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride, respectively, with various trifluoromethyl‐substituted aromatic bis(ether amine)s by a standard two‐step process with thermal or chemical imidization of the poly(amic acid) precursors. These fluorinated poly(ether imide)s showed good solubility in many organic solvents and could be solution‐cast into transparent, flexible, and tough films. These films were nearly colorless, with an ultraviolet–visible absorption edge of 364–386 nm. They also showed good thermal stability with glass‐transition temperatures of 221–298 °C, 10% weight loss temperatures in excess of 489 °C, and char yields at 800 °C in nitrogen greater than 50%. The 2,7‐substituted IIIB series also showed better solubility and higher transparency than the isomeric 2,6‐substituted IIIA series. In comparison with nonfluorinated poly (ether imide)s, the fluorinated IIIA and IIIB series showed better solubility, higher transparency, and lower dielectric constants and water absorption. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5909–5922, 2006     

Synthesis and properties of poly(ether imide)s derived from 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride and aromatic diamines

A new naphthalene unit-containing bis(ether anhydride), 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, was synthesized in three steps starting from the nucleophilic nitrodisplacement reaction of 2,6-dihydroxynaphthalene and 4-nitrophthalonitrile in N,N-dimethylformamide (DMF) solution in the presence of potassium carbonate, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aromatic poly(ether imide)s were prepared using a conventional two-step polymerization process from the bis(ether anhydride) and various aromatic diamines. The intermediate poly(ether amic acid)s had inherent viscosities of 0.65–2.03 dL/g. The films of poly(ether imide)s derived from two rigid diamines, i.e. p-phenylenediamine and benzidine, crystallized during the thermal imidization process. The other poly(ether imide)s belonged to amorphous materials and could be fabricated into transparent, flexible, and tough films. These aromatic poly(ether imide) films had yield strengths of 104–131 MPa, tensile strengths of 102–153 MPa, elongation to break of 8–87%, and initial moduli of 1.6–3.2 GPa. The glass transition temperatures (T_g's) of poly(ether imide)s were recorded in the range of 220–277°C depending on the nature of the diamine moiety. All polymers were stable up to 500°C, with 10% weight loss being recorded above 550°C in both air and nitrogen atmospheres. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1657–1665, 1998