Aromatic Bis Research Articles

Syntheses of [5]-helicene by McMurry or carbenoid couplings

Short syntheses of [5]-helicene have been accomplished under thermal conditions, without using photochemistry and high dilution. Key reactions comprised a McMurry coupling of a dialdehyde or a carbenoid-type coupling of aromatic bis(bromomethyl) moieties. The last coupling provided a 7290 yield of [5]-helicene on a gram-scale (15 min., 0°C).

Synthesis, Characterization, and Studies of Heat-Resistant Poly(ether benzimidazole)s

The present necessity to use heat-resistant materials in electronics justified the scientific interest in different heterocyclic polymers. This paper is especially concerned with the preparation of novel heat-resistant materials having benzimidazole moieties in the main chain. The poly(ether benzimidazole)s were prepared by the nucleophilic displacement reaction of 1,6-hexanediol with activated aliphatic and aromatic bis(nitrobenzimidazole) compounds in N-methylpyrrolidone at 190 °C in the presence of anhydrous potassium carbonate. All polybenzimidazoles were obtained in high-to-quantitative yields and with varying molecular weights (inherent viscosities from 0.24 to 0.77 dL/g), which in some cases were in the fiber-forming range. The polymers exhibited glass transition temperatures ranging from 150 to 300 °C.

Photosensitive Polyimides with Second-Order Nonlinear Optical Property.

NLO side-chain polyamic acid was prepared by the ring-opening polyaddition of aromatic dianhydrides, bis(4-aminophenyl) ether, and diamines containing a nonlinear optical chromophore, [4, 4′-diamino-4″-(4-nitrophenyl)diazenyl]triphenylamine. The polymers con- taining 30wt% of 2, 3, 4-tris[1-oxo-2-diazonaphthoquinone-5-sulfonyloxy]benzophenone (5- DNQ) functioned as an alkaline developable photosensitive resist, and converted to polyimides by thermal treatment. The resists showed a sensitivity of 1J•m-2 and a high contrast with UV light when they were developed with 0.5% tetramethylammonium hydroxide solution.

A novel polyaddition of bifunctional acetylenes containing electron-withdrawing groups: 4. Synthesis of polymers having enone moieties by the reaction of ynones with bifunctional heteronucleophiles

Phosphine-catalysed polyaddition of bifunctional ynones with diols or with dithiols is described. By the tri-n-butylphosphine-catalysed polyaddition of aromatic bis(ynone) having benzene ring as a spacer (without methylene group adjacent to carbonyl groups) or aliphatic bis(ynone) having octamethylene group as a spacer with p-xylene glycol, polymers having β-alkoxyenone moieties in the main chain were obtained in high yield. The polyaddition of the aromatic bis(ynone) gave a polymer composed of specifically E-unit, while that of the aliphatic bis(ynone)s produced a polymer containing both E- and Z-units. Further, the polyaddition with dithiols with bifunctional ynones was also carried out under similar conditions to yield the corresponding polymer composed of both E- and Z-units in almost quantitative yield. © 1997 Elsevier Science Ltd.

A facile route to aromatic ring-annelated bis(ethylenedithio)tetrathiafulvalene derivatives

The synthesis of bis(benzo)- and bis(naphtho)-fused derivatives of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) is easily achieved by employing the (4+2) cycloaddition reaction of oligo(1,3-dithiole-2,4,5-trithione) with appropriate olefins as the key step.

New poly(amide-imide)s syntheses. XVII. Preparation and properties of poly(amide-imide)s derived from 3,3-Bis[4-(4-aminophenoxy)phenyl]phthalimidine and various bis(trimellitimide)s

A series of novel bis(phenoxy)phthalimidine-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 3,3-bis[4-(4-aminophenoxy)phenyl]phthalimidine (BAPP) with various aromatic bis(trimellitimide)s in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III, having inherent viscosities up to 1.36 dL/g, were obtained in quantitative yields. All resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 267–322°C and the 10% weight loss temperatures were above 490°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III′ prepared from 3,3-[4-(4-trimellitimidophenoxy)phenyl]-phthalimidine and various aromatic diamines. © 1996 John Wiley & Sons, Inc.

Manufacture of aromatic bis(alkyl carbonates)

Manufacture of aromatic bis(alkyl carbonates)

New poly(amide‐imide) syntheses, 19. Preparation and properties of poly(amide‐imide)s derived from N‐phenyl‐3,3‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐oxoisoindoline and various bis(trimellitimide)s

AbstractA series of novel bis(phenoxy)‐1‐oxoisoindoline‐containing poly(amide‐imide)s 3 were synthesized by the direct polycondensations of N‐phenyl‐3,3‐bis[4‐(4‐aminophenoxy)‐phenyl]‐1‐oxoisoindoline (1m, NPBA) with various aromatic bis(trimellitimide)s 2 in N‐methyl‐2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide‐imide)s 3 having inherent viscosities up to 1,06 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvent such as NMP and N,N‐dimethylacetamide. All of the soluble poly(amide‐imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 277–327°C, and the 10% weight loss temperatures were above 500°C in nitrogen. The properties of poly(amideimide)s 3 were compared with those of the corresponding isomeric poly(amide‐imide)s 3′ prepared from NPBA and various aromatic diamines.

New poly(amide‐imide)s synthesis, 16. Preparation and properties of poly(amide‐imide)s derived from 3,3‐bis[4‐(4‐aminophenoxy) phenyl]phthalide and various bis(trimellitimide)s

AbstractA series of novel bis(phenoxy)phthalide‐containing poly(amide‐imide)s 3 were synthesized via direct polycondensation of 3,3‐bis[4‐(4‐aminophenoxy)phenyl]phthalide (BAPP) with various aromatic bis(trimellitimide)s 2 in N‐methyl‐2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide‐imide)s 3 having inherent viscosities up to 1,68 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N‐dimethylacetamide. All the soluble poly(amide‐imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 237–292°C and the 10% weight loss temperatures were above 500°C in nitrogen. The properties of poly(amide‐imide)s 3 were compared with those of the corresponding isomeric poly(amide‐imide)s 3′ prepared from 3,3‐[4‐(4‐trimellitimido‐phenoxy)phenyl]‐phthalide and various aromatic diamines.

New poly(amide‐lmide)s syntheses. XV. Preparation and properties of poly(amide‐imide)s derived from 9, 9‐bis[4‐(4‐aminophenoxy) phenyl]fluorene and various bis(trimellitimide)s

AbstractFifteen bis(phenoxy) fluorene‐containing poly(amide‐imide)s III were synthesized by the direct polycondensation of 9,9‐bis[4‐(4‐aminophenoxy)phenyl]fluorene (BAPPF) with var‐ious aromatic bis(trimellitimide)s II in N‐methyl‐2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide‐imide)s III having inherent vis‐cosities up to 1.45 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N‐dimethylacetamide. All the soluble poly(amide‐imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 263–315°C and the 10% weight loss temperatures were above 510°C in nitrogen. Some properties of poly(amide‐imide)s III were compared with those of the corresponding isomeric poly(amide‐imide)s III′ prepared from 9,9‐[4‐(4‐trimellitimidophenoxy)phenyl]fluorene and various aromatic diamines. © 1995 John Wiley & Sons, Inc.

New poly(amide‐imide)s syntheses, 14. Preparation and properties of poly(amide‐imide)s based on 3, 3‐bis[4‐(4‐trimellitimidophenoxy)phenyl]‐1‐oxoisoindoline

AbstractAn imide ring‐containing dicarboxylic acid, 3,3‐bis[4‐(4‐trimellitimidophenoxy)phenyl]‐1‐oxoisoindoline, was prepared via condensation of 3,3‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐oxoisoindoline and trimellitic anhydride. A series of new aromatic bis(phenoxy)‐1‐oxo‐isoindoline‐containing poly(amide‐imide)s were prepared via direct polycondensation of this diimide‐diacid with various aromatic diamines using triphenyl phosphite and pyridine as condensing agents in N‐methyl‐2‐pyrrolidone (NMP) in the presence of calcium chloride. Most of the resulting polymers are of amorphous nature and readily soluble in polar solvents such as NMP and N,N‐dimethylacetamide. All soluble poly(amide‐imide)s afford transparent, flexible, and tough films. The glass transition temperatures of the polymers are in the range of 267–305°C and show almost no weight loss up to 450°C in nitrogen atmosphere. The properties of 1‐oxoisoindoline containing poly(amide‐imide)s are compared with those of the corresponding analogous poly(amide‐imide)s derived from 3,3‐bis[4‐(4‐trimellitimidophenoxy)phenyl]phthalide.

Synthesis and characterization of extended poly(phenylquinoxalines) containing carbonyl, ether and sulphide linking groups

A series of eight novel extended poly(phenylquinoxalines) (PPQs) containing carbonyl, ether and sulphide linking groups were prepared by polycondensation of 4,4'-bis(phenylglyoxalyl-4-phenoxy-4'-benzoyl)diphenyl sulphide, I-D, and 4,4'-bis(phenyl glyoxalyl-4-phenylthio-4'-benzoyl)diphenyl sulphide, 2-D, with four aromatic bis(o-diamines) in m-cresol. The primary objective of this study was to correlate the effect of these linkages on the various properties such as solubility, thermal stability and glass transition temperature of the PPQs. Polymerization of 1-D was carried out in an oil bath maintained at 195-200C whereas polymerization of 2-D was performed at ambient temperature. The polymers prepared were soluble in m-cresol. dimethylsulphoxide, N,N-dimethylacetamide, I-methyl-2-pyrrolidinone and chlorinated hydrocarbon solvents, and formed tough transparent, yellow fingernail-creasable films from chloroform solutions. The inherent viscosities ranged between 0.44 and 0.96 dl g' '. The glass transition temperatures were nearly identical for both systems and ranged from 217-231 'C for polymers prepared from l-D and from 215-233"C for polymers prepared from 2-D. The PPQs having carbonyl and stJlphide linking groups had higher thermal stability in comparison to PPQs having carbonyl, ether and sulphide linkages. The temperature of 10% weight loss for I-D ranged from 484-496 'C in air and 485-516"C in helium whereas those for 2-D ranged from 538-579 XC in air and 522-549 in helium.

Preparation of bis(chloroformate)s for use in cyclization reactions

AbstractCyclic oligomeric carbonates are prepared by a hydrolysis/condensation reaction from aromatic bis(chloroformate)s. Three methods for convenient preparation of bis(chloroformate)s have been developed: (1) use of diethylaniline to scavenge HCl, in a modification of an earlier procedure; (2) low pH, low temperature interfacial condensation of bisphenols with phosgene; and (3) use of Ca(OH)2 in interfacial condensation with phosgene. Reaction parameters which control formation of monomeric bis(chloroformate)s versus higher oligomerization include temperature, pH, and rate of phosgene addition. For water‐soluble bisphenols such as hydroquinone, the phase ratio of water to CH2Cl2 can also be important.

Palladium Catalysis of Ditriflates for the Preparation of Soluble Poly(phenylene) Derivatives

A new polymerization reaction for the preparation of alkyl-substituted poly(phenylene)s is described based on the coupling of alkyl-substituted aromatic bis(trifluoromethanesulfonate) (triflate) with 1,4-bis(trimethylstannyl)benzene in the presence of a palladium catalyst. Aromatic triflates, readily prepared from the corresponding hydroquinone, were discovered to be excellent substrates in the preparation of soluble poly(phenylene) derivatives with alkyl substituents on alternating aromatic rings. Analysis of the poly(phenylene) derivatives by SEC revealed a near-Gaussian molecular weight distribution curve with degree of polymerization of 11 and polydispersity from 1.3 to 1.7. Analysis by 31 P-NMR revealed the presence of phosphorus, the presence of which limits the catalytic efficiency of palladium leading to a decrease in the degree of polymerization.

Syntheses of new poly(amide-imide)s: 13. Preparation and properties of poly(amide-imide)s based on the diimide-diacid condensed from 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide and trimellitic anhydride

An imide ring-containing dicarboxylic acid, 3,3-bis[4-trimellitimidophenoxy)phenyl]phthalide, was prepared by the condensation of 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide and trimellitic anhydride. A series of new aromatic bis(phenoxy)phthalide-containing poly(amide-imide)s having inherent viscosities of 0.84–1.10 dl g −1 were prepared by the direct polycondensation of this diimide-diacid with various aromatic diamines using triphenyl phosphite and pyridine as condensing agents in N-methyl-2-pyrrolidone (NMP) in the presence of calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible and tough films. The glass transition temperature of these polymers were in the range of 250–318°C and showed almost no weight loss up to 450°C under air or nitrogen atmosphere.

New poly (amide‐imide) syntheses. IX. Preparation and properties of poly(amide‐imide)s derived from 2,7‐bis (4‐aminophenoxy) naphthalene and various bis (trimellitimide)s

AbstractEleven bis(phenoxy) naphthalene‐containing poly(amide‐imide)s IIIa–k were synthesized by the direct polycondensation of 2,7‐bis (4‐aminophenoxy) naphthalene (DAPON) with various aromatic bis (trimellitimide)s IIa–k in N‐methyl‐2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly (amide‐imide)s IIIa–k having inherent viscosities of 0.70–1.12 dL/g were obtained in quantitative yields. The polymers containing p‐phenylene or bis(phenoxy) benzene units exhibited crystalline x‐ray diffraction patterns. Most of the polymers were readily soluble in various solvents such as NMP, N, N‐dimethylacetamide, dimethyl sulfoxide, m‐cresol, o‐chlorophenol, and pyridine, and gave transparent, and flexible films cast from DMAc solutions. Cast films showed obvious yield points in the stress‐strain curves and had strength at break up to 87 MPa, elongation to break up to 11%, and initial modulus up to 2.10 GPa. These poly(amide‐imide)s had glass transition temperatures in the range of 255–321°C, and the 10% weight loss temperatures were recorded in the range of 529–586°C in nitrogen. The properties of poly(amideimide)s IIIa–k were compared with those of the corresponding isomeric poly (amide‐imide)s III′ prepared from 2,7‐bis(4‐trimellitimidophenoxy) naphthalene and aromatic diamines. © 1994 John Wiley & Sons, Inc.

New Coagents in Peroxide Vulcanization of EPM

Abstract In a previous study, the mechanism of EPM peroxide vulcanization in the presence of various aromatic bis(allyl)esters was elucidated. It was concluded that the elastomer-coagent blend was phase separated and that during vulcanization chemical crosslinks are formed between the elastomer matrix and coagent domains. In this study the effect of the chemical structure of the coagent on the ultimate properties of the vulcanizate is reported. For this purpose a series of new coagents has been synthesized. It was found that bis(allyl) coagents with relatively flexible interlinking segments provide vulcanizates with improved mechanical properties.

Synthesis and Characterization of N-Phenylated Wholly Aromatic Non-Cyclic Polyimides from N,N′-Diphenylphthalimidoyl Chlorides and Phthalic Acids

A novel class of polyimides, N-phenylated wholly aromatic non-cyclic polyimides, was synthesized by the low-temperature solution and two-phase phase-transfer catalyzed polycondensations of new aromatic bis(imidoyl chloride)s, N,N′-diphenylisophthalimidoyl chloride and N,N′-diphenylterephthalimidoyl chloride, with aromatic dicarboxylic acids, isophthalic acid and terephthalic acid. The resulting polyimides were all white in color and had reduced viscosities of 0.11–0.14 dl g−1. Compared with the conventional polyimides having cyclic imide structures, these N-phenylated non-cyclic polyimides exhibited better solubility in various organic solvents, reduced crystallinity and lower glass transition temperatures and thermal stability. The reduced viscosity of a typical polyimide decreased rapidly upon UV light irradiation, indicating the occurrence of photodegradation. Before the polymer synthesis, the effects of reaction medium, organic and inorganic bases and phase-transfer catalyst were studied on the solution and two-phase reactions of N,N′-diphenylisophthalimidoyl chloride with benzoic acid.

Extended Poly(Phenylquinoxalines) Containing Earbonyl and Sulfide Connecting Groups

Novel poly(phenylquinoxalines) (PPQs) containing carbonyl and sulfide connecting groups between the aromatic rings were prepared by condensation of various aromatic bis(o-diamines) with novel extended bis(phenyl-1.2-diketones) in m-cresol. An objective of the work was to determine the effect of replacing oxygen by sulfur in extended PPQs. The polymers prepared were soluble in m-cresol, dimethylsulfoxide, N,Ndimethylacetamide, 1-methyl-2-pyrrolidinone and chlorinated hydrocarbon solvents, and had inherent viscosities as high as 1.23 dl g-1. The PPQs exhibited glass transition temperatures ranging from 217 to 245 C and polymer decomposition temperatures (10% weight loss) as measured by thermogravimetric analysis of 526-568 in air and 510-549 CC in helium. A tough transparent yellow fingernail creasable film with a tensile strength of 94.7 MPa, a tensile modulus of 2562 MPa and elongation at break of 6.4% at 25 "C was cast from a chloroform solution of the polymer prepared from 1,3-bis(phenylglyoxalyl-4phenylthio-4'-benzoyl)benzene and 3,3'-diaminobenzidine. Little difference in properties was observed in the PPQs prepared as compared to the PPQs containing carbonyl and ether connecting groups between the aromatic rings, in spite of the difference in the bonding characteristics of carbon to sulfur and to oxygen.

FT-IR Spectroscopy, a Major Tool for the Analysis of Peroxide Vulcanization Processes in the Presence of Coagents. I. Mechanism of EPM Peroxide Vulcanization with Aromatic bis(Allyl)Esters as Coagents

Abstract In this paper the results of investigations on the mechanism of EPM peroxide vulcanizations in the presence of various bis(allyl)esters of aromatic diacids—as coagents—are presented. These coagents are commonly used in the rubber industry to increase the crosslinking efficiency, however, until now the mechanism of this process remained unclear. In our studies it is demonstrated that when using FT-IR spectroscopy in combination with equilibrium swelling techniques and atomic force scanning microscopy, the role of the coagents can be elucidated.