Ether Dinitrile Research Articles

A Comparison of Poly(ether imide)s with 3-Phthalimide and 4-Phthalimide Units: Synthesis, Characterization, and Physical Properties

Bis(ether anhydride)s with 3- or 4-phthalimide moieties were prepared by reacting 3- or 4-nitrophthalodinitrile, respectively, with several diols and converting the resulting bis(ether dinitrile)s to bis(ether anhydride)s. Selected dianhydrides were converted into poly(ether imide)s in a two-stage solution polymerization and imidization process. It was found that, in most cases, the dianhydrides with 4-phthalic anhydride units gave high-molecular-weight polymers with any of several aromatic diamines. In contrast, dianhydrides with 3-phthalic anhydride units gave, primarily, low-molecular-weight products. Examination of several low-molecular-weight products by electrospray-ionization mass spectrometry demonstrated that the products consisted of small oligomers, cyclic or linear according to the structure of the diamine. A series of high-molecular-weight polymers were prepared from 4,4‘-bis(4‘ ‘-aminophenoxy)biphenyl (BAPB) and each of several bis(ether anhydride)s with 3- or 4-phthalic anhydride units; the anhydrides had isopropylidine or hexafluoroisopropylidine units or ortho-methyl or ortho-tert-butyl substituents in the diol residues. These polymers were characterized in terms of their molecular weights and glass-transition temperatures. The gas permeabilities, positron annihilation, and dielectric relaxation behaviors of the polymers were investigated and their properties related to their molecular structures. Dielectric relaxation spectroscopy measurements indicate that, in this group of polymers, the rates of the local chain mobility are comparable and are able to facilitate gas diffusion. An apparent linear correlation between the permeation coefficients and free volume as determined by positron annihilation lifetime spectroscopy was observed with certain gases. Comparison of polymers with similar molecular structures indicated that isomeric polymers with 3- and 4-linked phthalimide units have similar properties and that the introduction of branched chains or fluorinated groups leads to an increase in the free volume and consequently increased permeability.

Synthesis and characterization of soluble polyimides derived from 2′,5′-bis(3,4-dicarboxyphenoxy)-p -terphenyl dianhydride

A novel bis(ether anhydride) monomer, 2′,5′-bis(3,4-dicarboxyphenoxy)-p-terphenyl dianhydride, was synthesized from the nitro displacement of 4-nitrophthalonitrile by the phenoxide ion of 2′,5′-dihydroxy-p-terphenyl, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and cyclodehydration of the resulting bis(ether diacid). A series of new poly(ether imide)s bearing laterally attached p-terphenyl 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 or chemical imidization to the poly(ether imide)s. The inherent viscosities of the poly(amic acid) precursors were in the range of 0.62–1.26 dL/g. Most of the poly(ether imide)s obtained from both routes were soluble in polar organic solvents, such as N,N-dimethylacetamide. All the poly(ether imide)s could afford transparent, flexible, and strong films with high tensile strengths. The glass-transition temperatures of these poly(ether imide)s were recorded as between 214 and 276 °C by DSC. The softening temperatures of all the poly(ether imide) films stayed in the 207–265 °C range according to thermomechanical analysis. For all the polymers significant decomposition did not occur below 500 °C in nitrogen or air atmosphere. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1008–1017, 2004

Synthesis and characterization of new highly organosoluble poly(ether imide)s based on 3,3′,5,5′‐tetramethyl‐2,2‐bis[4‐(4‐dicarboxyphenoxy)phenyl]propane dianhydride

AbstractA new bis(ether anhydride), 3,3′,5,5′‐tetramethyl‐2,2‐bis[4‐(4‐dicarboxyphenoxy)phenyl]propane dianhydride (3), was prepared in three steps: the nitro displacement of 4‐nitrophthalonitrile with 2,2‐bis(4‐hydroxy‐3,5‐dimethylphenyl)propane, the alkaline hydrolysis of the intermediate bis(ether dinitrile), and the subsequent dehydration of the resulting bis(ether diacid). A series of new highly soluble poly(ether imide)s with tetramethyl and isopropylidene groups were prepared from the bis(ether anhydride) 3 with various diamines by a conventional two‐stage synthesis including polyaddition and chemical cyclodehydration. The resulting poly(ether imide)s had inherent viscosities of 0.54–0.73 dL g−1. Gel permeation chromatography measurements revealed that the polymers had number‐average and weight‐average molecular weights of up to 54,000 and 124,000, respectively. All the polymers showed typical amorphous diffraction patterns. All of the poly(ether imide)s showed excellent solubility and were readily dissolved in various solvents such as N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, N,N‐dimethylformamide, pyridine, cyclohexanone, tetrahydrofuran, and even chloroform. Most of the polymers could be dissolved with chloroform concentrations as high as 30 wt %. These polymers had glass‐transition temperatures of 244–282 °C. Thermogravimetric analysis showed that all polymers were stable, with 10% weight losses recorded above 463 °C in nitrogen. These transparent, tough, and flexible polymer films were obtained through solution casting from N,N‐dimethylacetamide solutions. These polymer films had tensile strengths of 81–102 MPa and tensile moduli of 1.8–2.0 GPa. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2556–2563, 2002

Synthesis and characterization of new highly organosoluble poly(etherimide)s derived from 1,1‐bis{4‐[4‐(3,4‐dicarboxyphenoxy)phenyl]‐4‐phenylcyclohexane} dianhydride

AbstractA new bulky pendent bis(ether anhydride), 1,1‐bis[4‐(4‐dicarboxyphenoxy)phenyl]‐4‐phenylcyclohexane dianhydride, was prepared in three steps, starting from the nitrodisplacement of 1,1‐bis(4‐hydroxyphenyl)‐4‐phenylcyclohexane with 4‐nitrophthalonitrile to form bis(ether dinitrile), followed by alkaline hydrolysis of the bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). A series of new poly(ether imide)s were prepared from the bis(ether anhydride) with various diamines by a conventional two‐stage synthesis including polyaddition and subsequent chemical cyclodehydration. The resulting poly(ether imide)s had inherent viscosities of 0.50–0.73 dL g−1. The gel permeation chromatography measurements revealed that the polymers had number‐average and weight‐average molecular weights of up to 57,000 and 130,000, respectively. All the polymers showed typical amorphous diffraction patterns. All of the poly(ether imide)s showed excellent solubility in comparison with the other polyimides derived from adamantane, norbornane, cyclododecane, and methanohexahydroindane and were readily dissolved in various solvents such as N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide, pyridine, cyclohexanone, tetrahydrofuran, and even chloroform. These polymers had glass‐transition temperatures of 226–255 °C. Most of the polymers could be dissolved in chloroform in as high as a 30 wt % concentration. Thermogravimetric analysis showed that all polymers were stable up to 450 °C, with 10% weight losses recorded from 458 to 497 °C in nitrogen. These transparent, tough, and flexible polymer films could be obtained by solution casting from DMAc solutions. These polymer films had tensile strengths of 79–103 MPa and tensile moduli of 1.5–2.1 GPa. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2066–2074, 2002

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.

Synthesis and characterization of new highly organosoluble poly(ether imide)s derived from 1,1-bis[4-(4-dicarboxyphenoxy)phenyl]-4- tert-butylcyclohexane dianhydride

A new bulky pendent bis(ether anhydride), 1,1-bis[4-(4-dicarboxyphenoxy)phenyl]-4- tert-butylcyclohexane dianhydride ( 3), was prepared in three steps starting from nitro-displacement of 1,1-bis(4-hydroxyphenyl)-4- tert-butylcyclohexane with 4-nitrophthalonitrile to form bis(ether dinitrile) ( 1), followed by alkaline hydrolysis of the bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). A series of new poly(ether imide)s were prepared from such bis(ether anhydride) ( 3) with various diamines by a conventional two-stage synthesis including the polyaddition and subsequent chemical cyclodehydration. The resulting poly(ether imide)s had inherent viscosities in the range of 0.50–0.79 dl g −1. The GPC measurement revealed that the polymers exhibited number-average and weight-average molecular weight up to 64,000 and 142,000, respectively. All the polymers showed typical amorphous diffraction patterns. All of the poly(ether imide)s showed excellent solubility and were readily soluble in various solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, pyridine, cyclohexanone, tetrahydrofuran and even in chloroform. These polymers had glass transition temperatures in the range of 227–266°C. Most of the polymers could be dissolved in chloroform of as high as 30 wt% concentration. Thermogravimetric analysis showed that all polymers were stable up to 450°C, with 10% weight loss recorded in the range of 470–515°C in nitrogen. These transparent, tough and flexible polymer films could be obtained by solution cast from the DMAc solution. These polymer films had tensile strength in the range of 79–98 MPa and tensile modulus in the range of 1.8–2.0 GPa.

Synthesis and Characterization of New Highly Organosoluble Poly(ether imide)s Bearing a Noncoplanar 2,2‘-Dimethyl-4,4‘-biphenyl Unit and Kink Diphenylmethylene Linkage

Two new bis(ether anhydride)s, 2,2‘-dimethyl-4,4‘-bis[4-(3,4-dicarboxyphenoxy)]biphenyl dianhydride (4A) and bis[4-(3,4-dicarboxy phenoxy)phenyl]diphenylmethane dianhydride (4B), were prepared in three steps starting from nitrodisplacement of 4-nitrophthalonitrile with 2,2‘-dimethylbiphenyl-4,4‘-diol and bis(4-hydroxyphenyl)diphenylmethane, respectively, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile)s and subsequent dehydration of the resulting bis(ether diacid)s. A series of new highly organosoluble poly(ether imide)s were prepared from the bis(ether anhydride)s and various diamines by conventional two-stage synthesis. The resulting poly(ether imide)s had inherent viscosities in the range of 0.55−0.81 dL·g-1. GPC measurement revealed that the polymers exhibited number-average molecular weight and weight-average molecular weight up to 45 000 and 82 000, respectively. All the polymers showed typical amorphous diffraction patterns. Almost all the poly(ether imide)s showed excellent solubility and readily dissolved in various solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, pyridine, cyclohexanone, tetrahydrofuran, and chloroform. These polymers had glass transition temperatures in the range of 224−256 °C. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 489 °C in nitrogen. The isothermal gravimetric analysis results demonstrated that these poly(ether imide)s showed weight losses of 7.0−10.5% after isothermal aging at 350 °C in static air for 20 h. These tough and flexible polymer films could be easily obtained by solution cast from the DMAc solution. These polymer films had tensile strength of 84−116 MPa and tensile modulus of 1.9−2.7 GPa.

Syntheses and properties of organosoluble poly(ether imide)s from 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]cyclohexane dianhydride and aromatic diamines

A bis(ether anhydride) monomer, 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]cyclohexane dianhydride (IV-A), was synthesized from the nitro displacement of 4-nitrophthalodinitrile by the phenoxide ion of 1,1-bis(4-hydroxyphenyl)cyclohexane (I-A), followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and dehydration of the resulting bis(ether acid). A novel series of organosoluble poly(ether imide)s (VIa–i)(PEIs) bearing cyclohexylidene cardo groups was prepared from the bis(ether anhydride) IV-A with various aromatic diamines Va–i via a conventional two-stage process. The PEIs had inherent viscosities in the range of 0.48–1.02 dL/g and afforded flexible and tough films by solution-casting because of their good solubilities in organic solvents. Most PEIs showed yield points in the range of 89–102 MPa at stress-strain curves and had tensile strengths of 78–103 MPa, elongations at breaks of 8–62%, and initial moduli of 1.8–2.2 GPa. The glass-transition temperatures (Tg's) of these PEIs were recorded between 200–234 °C. Decomposition temperatures of 10% weight loss all occurred above 490 °C in both air and nitrogen atmospheres, and their residues were more than 43% at 800 °C in nitrogen atmosphere. The cyclohexane cardo-based PEIs exhibited relatively higher Tg's, better solubilities in organic solvents, and better tensile properties as compared with the corresponding Ultem® PEI system. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 788–799, 2001

Organosoluble optically transparent poly(ether imide)s based on atert-butylhydroquinone bis(ether anhydride)

Full Paper: A novel bis(ether anhydride) monomer, 1,4-bis(3,4-dicarboxyphenoxy)-2-tert-butylbenzene dianhydride, was synthesized from the nitro displacement of 4-nitrophthalodinitrile by the phenoxide ion of tert-butylhydroquinone, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and dehydration of the resulting bis(ether diacid). A series of colorless and organosoluble poly(ether imide)s (PEIs) bearing pendent tert-butyl 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 chemical or thermal cyclodehydration to the PEIs. The inherent viscosities of these PEIs are in the range of 0.70-1.44 dL/g. Most PEIs show excellent solubilities in amide polar solvents, m-cresol and chlorohydrocarbons. The glass transition temperatures (T g ) of these PEIs were recorded between 217-278°C, and the decomposition temperatures at 10% weight loss are all above 460°C in air or nitrogen atmosphere. Solvent-cast films have high tensile moduli and strengths. The PEIs obtained from long chain diamines exhibit high extension to break.

New organo-soluble aromatic polyimides based on 3,3?,5,5?-tetrabromo-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and aromatic diamines

New aromatic tetracarboxylic dianhydride, having isopropylidene and bromo-substituted arylene ether structure 3,3′,5,5′-tetrabromo-2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with 3,3′,5,5′-tetrabromobisphenol A, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). The novel aromatic polyetherimides having inherent viscosities up to 1.04 dL g−1 were obtained by either a one-step or a conventional two-step polymerization process starting from the bis(ether anhydride) and various aromatic diamines. All the polyimides showed typical amorphous diffraction patterns. Most of the polyimides were readily soluble in common organic solvents such as N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), pyridine, and even in less polar solvents like chloroform and tetrahydrofuran (THF). These aromatic polyimides had glass transition temperatures in the range of 256–303°C, depending on the nature of the diamine moiety. Thermogravimetric analysis (TGA) showed that all polymers were stable, with 10% weight loss recorded above 470°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1673–1680, 1999

Synthesis and properties of soluble aromatic polyimides from 2,2?-bis(3,4-dicarboxyphenoxy)-1,1?-binaphthyl dianhydride and aromatic diamines

Aromatic tetracarboxylic dianhydride having crank and twisted noncoplanar structure, 2,2′-bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with 2,2′-dihydroxy-1,1′-binaphthyl, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). Binaphthyl-2,2′-diyl–containing novel aromatic polyimides having inherent viscosities up to 0.67 dL/g were obtained by the one-step polymerization process starting from the bis(ether anhydride) and various aromatic diamines. All the polyimides showed typical amorphous diffraction patterns. Most of the polyimides were readily soluble in common organic solvents such as N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and pyridine. These aromatic polyimides had glass transition temperatures in the range of 280–350°C, depending on the nature of the diamine moiety. All polymers were stable up to 400°C, with 10% weight loss being recorded above 485°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1937–1943, 1998

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-di- carboxyphenoxy)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 potas- sium carbonate, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aro- matic poly(ether imide)s were prepared using a conventional two-step polymerization process from the bis(ether anhydride) and various aromatic diamines. The intermedi- ate 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 benzi- dine, 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 (Tg's) of poly(ether imide)s were recorded in the range of 220-2777C depending on the nature of the diamine moiety. All polymers were stable up to 5007C, with 10% weight loss being recorded above 5507C in both air and nitrogen atmospheres. q 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1657-1665, 1998

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 Tgs 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

The synthesis of a 1,1′-bi-2-naphthol-based bis(ether anhydride) and aromatic polyimides derived therefrom

2,2′-Bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride was used as a new monomer with various aromatic diamines to obtain polyimides by the usual two-step method. The bis(ether anhydride) was prepared by a nucleophilic substitution of 1,1′-bi-2-naphthol with N-phenyl-4-chlorophthalimide, N-methyl-4-nitrophthalimide or 4-nitrophthalonitrile in aprotic polar solvent, and subsequent hydrolysis of the resulting bis(ether imide)s or bis(ether dinitrile), and then dehydration of the corresponding tetracarboxylic acid to afford the dianhydride. Most of the obtained polyimides were soluble in chloroform, pyridine, DMF, etc. The polyimide prepared from p-phenylene diamine was partial crystalline, whereas the others showed amorphous patterns in a WAXD study. These polymers have glass transition temperatures between 255–294°C and 5% weight loss temperatures in the range of 502–541°C in nitrogen and 473–537°C in air. © 1997 Elsevier Science Ltd.

Nitrodisplacement reactions and the synthesis of bis (ether anhydride) s from dihydroxynaphthalenes

Nitrodisplacement reactions between all ten dihydroxynaphthalenes and 4-nitrophthalodinitrile have been studied. Apart from 1,8-dihydroxynaphthalene, all dihydroxynaphthalenes undergo nitrodisplacement but only 1,5-, 2,3-, 2,6- and 2,7-dihydroxynaphthalenes give high yields of pure bis(ether dinitrile). The bisfether dinitrile's produced in high yield were hydrolysed and converted to bis(ether anhydride) for subsequent synthesis of poly(ether imide)s. Success in nitrodisplacement correlates with high redox potentials for the dihydroxynaphthalenes, except for 1,8-dihydroxynaphthalene which probably fails to react because of steric constraints at the peri positions.