Synthesis of high molecular weight poly(ether ketone)s by polycondensation of activated bis(aryl chloride)s with bisphenolates

The ability to achieve high molecular weight poly(ether ketone)s from the polycondensation of bis(aryl chloride)s with bis(phenolate)s has been consistently demonstrated. The polymerizations presented here help to delineate for specific bis(aryl chloride)/bisphenolate pairs the reaction conditions required to obtain high molecular weight polymers. Polycondensation of 1,3-bis(4-chlorobenzoyl)-5-tert-butylbenzene ( 6 ) and 2,2′-bis(4-chlorobenzoyl)-biphenyl ( 15 ) with various bisphenolates as well as of 2,2′-bis(4-hydroxyphenoxy)biphenyl ( 33 ) with 4,4′-dichlorobenzophenone ( 41 ) and 1,3-bis(4-chlorobenzoyl)benzene ( 43 ) were used as representative model systems to select reaction conditions that led to high molecular weight polymers. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(thioether ether sulfone imide)s derived from isomeric bis(chlorophthalimide)s and bis(4-mercaptophenyl) sulfone

A series of isomeric bis(chlorophthalimide)s (BCPIs) were conveniently prepared from 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, and mixtures thereof. Polymerization of BCPIs with bis(4-mercaptophenyl) sulfone (BMPS) proceeded smoothly in the presence of tributylamine, from which a class of isomeric poly(thioether ether sulfone imide)s (PTESIs) with inherent viscosities of 0.45-0.82 dL/g were obtained. The solubility, thermal stability, and mechanical properties of these polymers were characterized. Compared to the PTESIs derived from single BCPIs, i.e., 3,3′-, 3,4′-, or 4,4′-BCPIs, the PTESIs derived from mixed BCPIs showed better solubility and higher storage modulus. These PTESIs also demonstrated good thermal stability, giving only 5% weight loss at temperature of 490 °C in nitrogen atmosphere. The glass transition temperatures (T_gs) of these isomeric PTESIs were between 242 and 265 °C, and were increased with increasing of the ratio of 3-chlorophthalimide unit in the polymer backbone.     

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     

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

Eleven 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.     

Two new cyclic bis(bibenzyl)s,isoriccardinquinone A and B from the liverwort Marchantia paleacea

From the 95% ethanol extract of the Hong Kong liverwort, Marchantiapaleacea, guided by bioactivity directed isolation, two novel isoriccardinquinones A and B were obtained together with previously known marchantin C, isoriccardin C and phenanthrene derivative, 2-hydroxy-3,7-dimethoxyphenanthrene. The structures of the new compounds were established by high field spectroscopic methods, including 2D NMR techniques.     

A new (propylphenyl)bibenzyl from Eria bambusifolia

A new (propylphenyl)bibenzyl, bambusifolol (1), along with six known compounds, batatasin III (2), tristin (3), 3-hydroxy-5-methoxy bibenzyl (4), gigantol (5), 3′,5-dimethoxy-9,9′-diacetyl-4,7′-epoxy-3,8′-bilign-7-ene-4′-methol (6) and balanophonin (7) were isolated from the whole plants of Eria bambusifolia. Their structures were elucidated by the means of extensive spectroscopic analysis. 3–7 were isolated from the genus Eria for the first time and 2 obtained originally from E. bambusifolia. All the compounds isolated were evaluated for their cytotoxicity against human tumour HL-60, SMMC-7721, A-549, MCF-7 and SW-480 cell lines, but none showed significant activity.     

A new bibenzyl derivative with nuclear factor-kappaB inhibitory activity from Schefflera arboricola (Araliaceae)

A new bibenzyl derivative (1), 4-acetoxy-3,5,3′,4′-tetramethoxybibenzyl, along with eight known compounds (2–9), was isolated from the twigs and leaves of Schefflera arboricola (Araliaceae). The isolated compounds were elucidated mainly by means of one-dimensional, two-dimensional NMR and MS, and by comparison with the literature data. Compounds 2–5 and 7–9 are first reported from this plant. In the in vitro assays, compound 1 displayed moderate nuclear factor-kappaB inhibitory activity.     

Synthesis of poly(silyl ether)s containing pendant chloromethyl groups by the polyaddition of bis(oxetane)s with dichlorosilanes

The polyaddition of bis(3‐ethyl‐3‐oxetanylmethyl) terephthalate (BEOT) with dichlorodiphenylsilane (CPS) using tetrabutylammonium bromide (TBAB) as a catalyst proceeded under mild reaction conditions to afford a polymer containing silicon atoms in the polymer main chain. A poly(silyl ether) (P‐1) with a high molecular weight (M_n = 53,200) was obtained by the reaction of BEOT with CPS in the presence of 5 mol % of TBAB in toluene at 0 °C for 1 h and then at 50 °C for 24 h. The structure of the resulting polymer was confirmed by IR and ¹H NMR spectra. Furthermore, it was proved that the polyaddition of certain bis(oxetane)s with dichlorosilanes proceeds smoothly to give corresponding poly(silyl ether)s with TBAB as the catalyst. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2254–2259, 2000     

Synthesis of novel poly(hydroxyether terephthalate) via polyaddition of 2,5-difluoroterephthalic acid with aromatic bis(epoxide)s

A novel and more reliable synthetic route to 2,5-difluoroterephthalic acid was developed. A series of new poly(hydroxyether terephthalate) were prepared by the polyaddition of 2,5-difluoroterephthalic acid with various aromatic bis(epoxide)s catalyzed by tetrabutyl ammonium bromide.     

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

Fifteen 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.     

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII)

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII) were obtained in an aqueous solution and in acetonitriie. The rate constants of their decomposition were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 184–185, January, 1995.This work was carried out with financial support from the International Scientific Foundation (Grant REI 000).     

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 sodium bis(trimethylstannyl) amide and bis(trimethylsilyl) bis(trimethylstannyl) -phospha-tetrazene

Sodium bis(trimethylstannyl)amide NaN(SnMe₃)₂, isolated by the reaction of trimethylstannyldiethylamine with sodium amide, reacts with tris(trimethylsilyl)hydrazino—dichloro-phosphine to form bis(trimethylsilyl)bis(trimethylstannyl)-2-phospha-2-tetrazene, (Me₃Si)₂N-N=P-N(SnMe₃)₂. Both the molecules have been isolated and characterized.     

Synthesis and properties of novel aromatic polyhydrazides and poly(amide–hydrazide)s based on the bis(ether benzoic acid)s from hydroquinone and substituted hydroquinones

4,4′‐(1,4‐Phenylenedioxy)dibenzoic acid as well as the 2‐methyl‐, 2‐tert‐butyl‐, or 2‐phenyl‐substituted derivatives of this dicarboxylic acid were synthesized in two main steps from p‐fluorobenzonitrile and hydroquinone or its methyl‐, tert‐butyl‐, or phenyl‐substituted derivatives. Polyhydrazides and poly(amide–hydrazide)s were prepared from these bis(ether benzoic acid)s or their diacyl chlorides with terephthalic dihydrazide, isophthalic dihydrazide, or p‐aminobenzoyl hydrazide by means of the phosphorylation reaction or low‐temperature solution polycondensation. Most of the hydrazide polymers and copolymers are amorphous and readily soluble in various polar solvents such as N‐methyl‐2‐pyrrolidone (NMP) and dimethyl sulfoxide. They could be solution‐cast into transparent, flexible, and tough films. These polyhydrazides and poly(amide–hydrazide)s had T_gs in the range of 167–237°C and could be thermally cyclodehydrated into the corresponding poly(1,3,4‐oxadiazole)s and poly(amide–1,3,4‐oxadiazole)s approximately in the region of 250–350°C, as evidenced by the DSC thermograms. All the tert‐butyl‐substituted oxadiazole polymers and those derived from isophthalic dihydrazide were organic soluble. The thermally converted oxadiazole polymers exhibited T_gs in the range of 208–243°C and did not show significant weight loss before 450°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1169–1181, 1999     

Synthesis and properties of novel aromatic poly(o-hydroxy amide)s and polybenzoxazoles based on the bis(ether benzoyl chloride)s from hydroquinone and its methyl-, tert-butyl-, and phenyl-substituted derivatives

Four series of poly(o-hydroxy amide)s were prepared by the low-temperature solution polycondensation of the bis(ether benzoyl chloride)s extended from hydroquinone and its methyl-, tert-butyl-, or phenyl-substituted derivatives with three bis(o-aminophenol)s. Most of the poly(o-hydroxy amide)s displayed an amorphous nature, were readily soluble in various polar solvents such as N,N-dimethylacetamide (DMAc), and could be solution-cast into flexible and tough films. These poly(o-hydroxy amide)s had glass transition temperatures (T_g) in the range of 152–185°C and could be thermally cyclodehydrated into the corresponding polybenzoxazoles approximately in the region of 200–400°C, as evidenced by the DSC thermograms. The thermally converted benzoxazole polymers exhibited T_gs in the range of 215–247°C and did not show significant weight loss before 500°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2129–2136, 1999     

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.     

Copolymerization of bis(2-oxazoline)s,anhydrides, and diols or diamines. Reaction mechanisms and polymer properties

The preparation of linear poly(ester-amide)s from monoanhydrides, bis(2-oxazoline)s (namely 2,2′-(1,4-phenylene)bis(2-oxazoline)) and a third comonomer is discussed. The polymerization reactions were carried out in bulk between 150 and 200°C. When the third monomer is a diol, poly(ester-ester-amide)s are obtained. Diols of different structure were used: α,ω-diols having up to 12 carbon atoms, ethylene glycol oligomers (two or three repeating units), cyclic diols, etc.; glutaric, 3,3-dimethylglutaric and maleic anhydrides were used as monoanhydrides. The polymers were studied from the point of view of thermal properties, finding a substantial agreement between the structure of the monomers and the glass transition temperature of the polymers. By using primary diamines as a third comonomer, the reaction does not lead to the formation of a polymeric product. The failure of the polymerization was attributed to a competitive reaction that prevents the polymerization. After the amine group has reacted with the anhydride, cyclization of the so-formed carboxyalkylamide occurs, giving an imide derivative, unable to react further. Therefore, only a mixture of low molecular weight compounds is obtained in this case. When the diamine is secondary, the imidization reaction is not possible, and linear poly(amide-ester-amide)s are obtained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3241–3248, 1997     

Preparation,characterization, and properties of poly(thioether ether ketone imide)s from isomeric bis(chlorophthalimide)s

A series of novel poly(thioether ether ketone imide)s (PTEKIs) bearing the thioether and ketone groups with high molecular weights (M_w: 87,800–150,100 g/mol) were synthesized by aromatic nucleophilic substitution reaction. The polymers were characterized by Fourier transform infrared spectra (FT‐IR), ¹H NMR, GPC, and elemental analysis. The composition of the copolymers varied systematically in order to study its relation with polymer properties. Increase in the content of 3‐substituted phthalimide moiety in the polymer backbone improves the solubility in tested solvents, and increases the glass transition temperature (T_g), whereas copolymers with high content of 3‐substituted phthalimide demonstrated to be inferior thermal stability. The PTEKI films also exhibited good optical transparency, including the cutoff wavelengths lower than 400 nm and transmittances higher than 77% at 450 nm. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of a tetra(maleimide) as intermediate compound in a linear Diels–Alder polyaddition of bismaleimides with bis(2-pyrone)s

The tetrafunctional products 3 and 6 were synthesized via Diels-Alder reaction of bis(2-pyrone) with bismaleimides in mol ratio 1:7. The chemical structure of these products was determined by ¹H-NMR spectroscopy; the high degree of purity was confirmed by means of elemental analysis. The cyclization of the tetraimide 3 with 2 mol monopyrone 7 to the bicycle 8 was carried out. © 1995 John Wiley & Sons, Inc.     

Synthesis of novel bis(chromenes) and bis(chromeno[3,4-C]pyridine) incorporating piperazine moiety

Novel bis(2-oxo-2H-chromene) as well as bis(2-imino-2H-chromene) derivatives incorporating piperazine moiety were prepared by the cyclocondensation reaction of bis(2-hydroxybenzaldehyde) with two equivalents of each of the appropriate β-ketoesters or acetonitrile derivatives. The bis(2-imino-2H-chromene-3-carbothioamide) derivative was used as a key synthon for construction of novel bis(3-(4-substituted thiazol-2-yl)-2H-chromen-2-one) derivatives via its cyclocondensation with a series of the appropriate α-halocarbonyl derivatives. Moreover, the bis(2-hydroxybenzaldehyde) reacted with four equivalents of the appropriate acetonitrile derivatives to afford the corresponding bis(3H-chromeno[3,4-c]pyridine) derivatives. Elucidation of the structure of the novel bis(chromenes) bearing piperazine nucleus was established by the spectral data and elemental analyses.