Preparation and properties of fluorine-containing polyarylates from tetrafluoroisophthaloyl chloride and bisphenols

Fluorine-containing polyarylates having inherent viscosities of 0.2–0.8 dL/g were prepared from tetrafluoroisophthaloyl chloride and various bisphenols by low temperature solution polycondensation in chloroform with triethylamine or by two-phase polycondensation in a dichloromethane-water or nitrobenzene-water system with benzyltriethylammonium chloride as the phase transfer catalyst. These polyarylates were amorphous and were readily soluble in various solvents, including chloroform and N-methyl-2-pyrrolidone. The glass transition temperature of the polymer derived from 2,2-bis(4-hydroxyphenyl) propane was 150°C. These polyarylates started to lose weight around 350°C in an air or nitrogen atmosphere.     

Preparation and properties of polyarylates and copolyarylates from phenylindanedicarbonyl chloride and bisphenols

A series of polyarylates having inherent viscosities of 0.4–1.1 dL/g was prepared by the two phase polycondensation of 1,1,3-trimethyl-3-(4-chloroformylphenyl)indanecarbonyl chloride with various bisphenols in an organic solvent–aqueous alkaline solution system in the presence of a phase transfer catalyst. Similarly, copolyarylates of high molecular weights were prepared from a mixture of the phenylindanedicarbonyl chloride, terephthaloyl chloride, and 2,2-bis(4-hydroxy-phenyl)propane. All the polyarylates were characterized by their amorphous nature and high solubility in organic solvents. They gave transparent and tough films by the solution casting. The films had tensile strength of 33–46 MPa, elongation at break of 3–16%, and tensile modulus of 1.2–1.6 GPa. These polyarylates had glass transition temperatures in the range of 205–310°C, and began to decompose at ca. 350°C in air.     

Preparation and properties of polyarylates both from 2,2′-bibenzoyl chloride and bisphenols and from biphenyl-2,2′-diol and aromatic dicarboxylic acid chlorides

Polyarylates having inherent viscosities up to 1.02 dL/g were synthesized both by the phase-transfer catalyzed two-phase polycondensation of 2,2′-bibenzoyl chloride with various bisphenols and by the high-temperature solution polycondensation of biphenyl-2,2′-diol with aromatic dicarboxylic acid chlorides. All the polyarylates were amorphous and soluble in a variety of organic solvents including N,N-dimethylformamide, N-methyl–2-pyrrolidone, chloroform, m-cresol, and pyridine. Transparent and flexible films of these polymers could be cast from the chloroform solutions. These polyarylates had glass transition temperatures in the range of 120–250°C and began to lose weight at around 380°C in air. © 1992 John Wiley & Sons, Inc.     

Preparation and properties of aromatic polyamides from 5-t-butylisophthalic acid and various aromatic diamines

Aromatic polyamides (aramids) having pendant t-butyl group were synthesized by the direct polycondensation of 5-t-butylisophthalic acid with various aromatic diamines in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The aramids having inherent viscosities of 0.6–2.4 dL/g were obtained in quantitative yields. These polymers were readily soluble in various solvents such as NMP,N,N-dimethylacetamide, dimethyl sulfoxide, and pyridine, and gave transparent, tough and flexible films by casting from the NMP solutions. The aramids had glass transition temperatures between 250 and 330°C, and started to lose weight around 350°C, with 10% weight loss being recorded at about 450°C in air.     

Preparation and characterization of the soluble NLO polyarylates with enhanced electro-optic properties

Three novel nonlinear optical polyarylate polymers were prepared containing one main-chain polymer (mPAR-chr1) and two side-chain polymers (sPAR-chr1, sPAR-chr2) with different kinds of chromophores. The obtained polymers were characterized and evaluated by UV-Vis, ¹H NMR, DSC and TGA. All the polymers exhibited excellent thermal stability, film forming ability and good electro-optic (EO) activity. The relationship between EO coefficients (r ₃₃) and the chromophore concentration of the three polymers had been also characterized and discussed. There were no obvious differences found in EO activity between main-chain and side-chain polyarylates with the same chromophore (chr1). Due to the stronger electron-withdrawing tricyanopyrroline acceptor and the steric effect of the large dendritic groups of chromophore 2 (chr2), polymer sPAR-chr2 showed the largest EO cofficients (64 pm V^?1) in these new polymers.     

Synthesis and properties of self-protecting polyarylates

Self-protective polyesters were synthesized in two ways: by polymer analog transformations on polymers obtained and by introduction of inhibiting groups into the polymer during synthesis. It is shown that the Fries rearrangement takes place in the aromatic polyesters in the presence of the Friedel-Crafts catalysts and on ultraviolet irradiation as well. Thermogravimetric analysis of the rearranged polymers and investigations of the influence of the ultraviolet irradiation on their properties show that the rearrangement markedly increases the photochemical and thermal stability of the polymers. Photostabilization may also be accomplished by the introduction of inhibiting groups, such as hydroxyl, sulfur, or phosphorus into the polymer molecule.     

Synthesis and properties of new polyarylates from 1,4‐bis(4‐carboxyphenoxy)naphthyl or 2,6‐bis(4‐carboxyphenoxy)naphthyl and various bisphenols

New 1,4‐naphthyl and 2,6‐naphthyl‐containing polyarylates having inherent viscosities up to 1.28 dL/g were synthesized by the high‐temperature solution polycondensation from the acid chloride of 1,4‐bis(4‐carboxyphenoxy)naphthyl or 2,6‐bis(4‐carboxyphenoxy)naphthyl and various bisphenols. Most of the resulting polyarylates showed amorphous characteristics and were readily soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), o‐chlorophenol, and chloroform. Transparent, flexible, and colorless films of these polymers could be cast from the DMAc solutions. Their cast films had tensile strengths ranging from 54.9 to 84.2 MPa, elongations at break from 5.3% to 19.0%, and initial modulus from 2.0 to 2.8 GPa. These polymers had glass transition temperatures in the range of 172–280°C and began to lose weight around 400°C, with 10% weight loss being recorded at about 450°C in air. Dynamic mechanical analysis (DMA) reveals that the polyarylates containing isopropylidene linkages have three transitions on the temperature scale between −100 and 300°C. However, only two transitions were observed in the other polyarylates without isoproylidene linkage. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 645–652, 1999     

Synthesis and characterization of new soluble polyesters derived from various cardo bisphenols by solution polycondensation

A series of new polyesters was prepared from terephthaloyl (or isophthaloyl) chloride acid with various cardo bisphenols on solution polycondensation in nitrobenzene using pyridine as hydrogen chloride quencher at 150 °C. These polyesters were produced with inherent viscosities of 0.32–0.49 dL · g⁻¹. Most of these polyesters exhibited excellent solubility in a variety of solvents such as N,N‐dimethylformamide, tetrahydrofuran, tetrachloroethane, dimethyl sulfoxide, N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidinone, m‐cresol, and o‐chlorophenol. The polyesters containing cardo groups including diphenylmethylene, tricyclo[5.2.1.0^2,6]decyl, tert‐butylcyclohexyl, phenylcyclohexyl, and cyclododecyl groups exhibited better solubility than bisphenol A–based polyesters. These polymers showed glass transition temperatures (T_g's) between 185 °C and 243 °C and decomposition temperatures at 10% weight loss ranging from 406 °C to 472 °C in nitrogen. These cardo polyesters exhibited higher T_g's and better solubility than bisphenol A‐based polyesters. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4451–4456, 2000     

Copolycondensation of various compositions of isophthalic acid and terephthalic acid with hydroquinones or bisphenols by tosyl chloride/dimethylformamide/pyridine

The polycondensation of isophthalic acid (IPA)/terephthalic acid (TPA) with aromatic diols by tosyl chloride/dimethylformamide/pyridine in solution was examined through changes in the IPA/TPA compositions, the kinds of dihydroxyl components, the periods of their addition, and the reaction temperatures. The reaction proceeded favorably at IPA/TPA ratios of 70/30 to 50/50, similarly to an earlier report on the interfacial reaction. The effects of the compositions were significant in the reactions with monosubstituted hydroquinones. The results were examined from distributions of the resulting oligomers prepared at a reaction extent of 0.7, determined by gel permeation chromatography. The reaction producing better results exhibited distributions closer to the theoretical ones. The period of addition also favorably affected the distributions as well as the results of the polycondensation. These results were attributed to the change in the reaction method, in which the diols reacted with the aggregates that formed from the activated IPA and TPA. The change was likely caused by the degree of association of IPA and TPA in the aggregates, on the basis of melting points and IR spectra of mixtures of dimethyl esters of IPA and TPA prepared by the quenching of the aggregates with methanol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2321–2328, 2004     

Synthesis and properties of a novel perfluorononenyloxy group containing polyarylates

A series of novel perfluorononenyloxy group containing polyarylates were synthesized by a high-temperature solution condensation of 5-(perfluorononenyloxy)-isophthaloyl chloride ( II ) with various aromatic diols in o-dichlorobenzene. All the polyarylates were amorphous and readily soluble in many organic solvents such as o-chlorophenol, o-dichlorobenzene, chloroform, and polar aprotic solvents at room temperature or on heating. Transparent, tough, and flexible films of these polymers could be cast from the o-chlorophenol solutions. The polymers having inherent viscosity of 0.61–1.63 dL/g were obtained in quantitative yields. These polymers were thermally quite stable. The glass transition temperatures of these polyarylates were in the range of 219–242°C by DSC and 224–251°C by DMA, and the 10% weight loss temperatures in nitrogen and air were above 415 and 397°C, respectively. Moreover, these polymers maintained good mechanical properties (G′ ∼ 10⁸ Pa) up to 220°C and had lower moisture absorption than common polyarylates. The dielectric constants of these polymers ranged from 3.23 to 3.75. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 645–653, 1998     

Preparation of tricyclohexyltin chloride from dicyclohexylaluminum chloride and SnCl4

Conclusions A new simple method was developed for the synthesis of tricyclohexyltin chloride from SnCl₄ and dicyclohexylaluminum chloride. The latter was obtained by reacting diisobutylaluminum chloride with cyclohexene in the presence of the binary Cp₂ZrCl₂/Ti(OBu)₄ catalyst and a catalytic amount of (i-C₄H₉)₂AlH.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1171–1173, May, 1984.     

Preparation and properties of high transition temperature aromatic polyphosphonates by phase-transfer-catalyzed polycondensation of phenylphosphonic dichloride with bisphenols

Aromatic polyphosphonates of high molecular weights were prepared from phenylphosphonic dichloride and bisphenols having rigid ring structures by the two-phase polycondensation in organic solvent–aqueous alkaline solution system with phase-transfer catalyst at 0°C or below. The effects of reaction solvent and catalyst on the inherent viscosities of the polymers formed are studied. The glass transition temperatures of the polyphosphonates with biphenyl, phenylindane, and diphenylfluorene units are 120, 124, and 188°C, respectively. These polymers are self-extinguishing and are readily soluble in solvents such as N,N-dimethylacetamide, pyridine, tetrahydrofuran, and chloroform. They began to lose weight above 300°C in air. Copolyphosphonates from combinations of bisphenols and phenylphosphonic dichloride are also prepared and characterized.     

Preparation and properties of dicyclopentadienylniobium(III) chloride

The preparation of an air-sensitive 16-electron complex, Cp₂NbCl, is described. Its main property is easy transformation to 18-electron mononuclear compounds. Cp₂Nb(=O)Cl and Cp₂Nb(CO)Cl are obtained in oxidation and carbon monoxide gas addition processes, respectively. The physical properties of these complexes are described.     

Synthesis and photoluminescence properties of novel polyarylates bearing pendent naphthylamine chromophores

A new series of blue photoluminescent aromatic polyesters (polyarylates) were synthesized from 1-[N,N-di(4-carboxyphenyl)amino]naphthalene with various bisphenols by the diphenylchlorophosphate (DPCP) activated direct polycondensation in a medium of pyridine and lithium chloride. The synthesis, basic characterizations, photoluminescence and electrochemical properties of this series of novel polyarylates bearing pendent naphthylamine chromophores were investigated. All polymers not only had good solubility in many polar aprotic solvents and excellent thin-film-forming ability, but also exhibited high T_g values, good thermal stability and lower highest occupied molecular orbital (HOMO) level. Thus, these naphthylamine-containing polyarylates may be widely applied in P-LED as hole-transporting layer and blue light-emitting materials due to their proper HOMO level, excellent thermal stability and fluorescence quantum efficiency.     

Preparation and examination of properties of lanthanide chloride salts with hexamethylenetetramine

Summary New complex salts of lanthanide chlorides with hexamethylenetramine of the general formulaLnCl₃·2HMTA·nH₂O [Ln=La, Pr, Nd, Sm, Dy, Er;HMTA-hexamethylenetetramine N₄(CH₂)₆;n=8, 10, 12] have been obtained. On the basis of IR IR spectra (4000-200cm^–1) and Raman spectra (3000-300 cm^–1), changes in the coordination sphere structure of the salts occurring in the course of thermal dehydration have been determined.

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Darstellung und Untersuchung der Eigenschaften von Komplexsalzen der Lanthanidchloride mit Hexamethylentetramin

Zusammenfassung Neue Komplexsalze der Lanthanidchloride mit Hexamethylentetramin mit der allgemeinen FormelLnCl₃·2HMTA·nH₂O [Ln=La, Pr, Nd, Sm, Dy, Er;HMTA — Hexamethylentetramin N₄(CH₂)₆;n=8, 10, 12] wurden dargestellt. Die Änderungen in der Struktur der Koordinationssphäre während der thermischen Dehydration der Salze wurden mittels Infrarot-(4 000–200 cm^–1) und Ramanspektroskopie (3 000–300 cm^–) bestimmt.

     

Preparation of fragrant substances from bornyl chloride

Organocuprate reagents were used for introducing bornane (1,7,7-trimethylbicyclo[2.2.1]heptane) moiety into the carbon skeleton of α,β-unsaturated carbonyl compounds. Prospects for use of the products obtained as fragrant substances were assessed.