Studies on the synthesis and optical and conducting properties of poly[methyltetraphenylphenylsilylene-co-1,4-bis(methylphenylsilyl)phenylene]

Poly(methyltetraphenylphenylsilylene-co-1,4-bis(methylphenylsilyl)phenylene) (PSP) were synthesized by the cocondensation reaction of methyltetraphenylphenyldichlorosilane and 1,4-bis(chloromethylphenylsilyl)benzene with sodium in toluene. The optical and conducting properties of the polymer were investigated. Because of the introducing of tetraphenylphenyl groups to the Si atoms of the polymer, the ultraviolet (UV) absorption wavelengths of the PSP red-shift significantly in the UV region, and a strong photoluminescence band can be observed at visible region. Treatment of the films of PSP with I₂ vapor afforded conducting films.     

Novel conducting polymer poly[bis(phenylamino)disulfide]: Synthesis,characterization, and properties

A bis(phenylamino)disulfide was prepared through the reaction of S₂Cl₂ with aniline, and its configuration was confirmed with elemental analysis, Fourier transform infrared (FTIR), Fourier transform Raman (FT‐Raman), and ¹H NMR spectroscopy. A novel conducting polymer, poly[bis(phenylamino)disulfide] (PPAD), was synthesized from bis(phenylamino)disulfide by both chemical and electrochemical polymerization. The structure of this polymer, in which the side‐chain disulfide bonds were linked to the nitrogen atoms of the main‐chain polyaniline, was characterized with FTIR, FT‐Raman, gel permeation chromatography, electron spectroscopy, and X‐ray photoelectron spectroscopy. A four‐probe measurement revealed that the electrical conductivity of PPAD was 1.8 × 10^?2 to 2.1 × 10^?3 S cm^?1, depending on the doping agents and the pH of the medium for either chemical synthesis or electrochemical synthesis. The conductivity, molecular weight, and spectroscopic properties of the polymer, in comparison with those of polyaniline, showed decreases in the polaron delocalization, structural order, and doping level of the main chain because of the steric hindrance of side‐chain S? S bonds. The cyclic voltammograms of the polymer and the monomer showed that the redox reactions (doping/undoping processes) of the main chain (π‐conjugated system) occurred in almost the same potential range of ?0.3 to 0.3 V versus an Ag/AgCl (saturated KCl) electrode as that of thiol (thiolate anion)/disulfide of the side chain in PPAD; the bond cleavage (reduction) and formation (oxidation) reactions of the disulfide bond in the polymer became easier and more reversible than those of the monomer. These results suggested that this conducting organodisulfide polymer might be a candidate material for energy‐storage devices such as lithium secondary batteries, proton‐exchange batteries, and electrochemical capacitors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2329–2339, 2004     

Synthesis and reactions of {o-{[bis(dimethylamino)boryl]methyl}phenyl}diphenylphosphane

The new α,ω-[boryl(organyl)]phosphane o-Ph₂PC₆H₄CH₂B (NMe₂)₂ ( 10 ) was obtained in good yields from the reaction of CIB(NMe₂)₂ with o-Ph₂PC₆H₄CH₂Li(tmeda). Five derivatives of 10 were obtained by substituting the boron-bound amino groups by reactions with MeOH, BCl₃, HCl, and LiAlH₄, respectively, in particular, o-Ph₂(HCl)PC₆H₄CH₂BCl₂ (HNMe₂) ( 10 e ) which shows a unique P? H? Cl? H? N unit. Compound 10 and its derivatives were characterized by multinuclear NMR methods, mass spectra, and elemental analyses. In addition, the structure of 10 e · 1.5 C₆H₆ was determined by single crystal X-ray diffraction.     

Synthesis and properties of sulfur‐contained poly(silylene arylacetylene)s

Poly(silylene arylacetylene) (PSA) is a kind of poly(arylacetylene) silicon‐containing resins with excellent heat resistance and good mechanical performances. In this article, the sulfur atom is introduced into the main chain of the PSA molecule to obtain a sulfur‐containing poly(silylene arylacetylene), named S‐PSA. By Williamson and Sonogashira reactions, bis(4‐ethynylphenyl)sulfide and bis(4‐ethynylphenyl)sulfone were synthesized. Thereafter, through Grignard reagent way, the poly(silylene ethynylene phenylene sulfide phenylene ethynylene) (PSESE) and poly(silylene ethynylene phenylene sulfone phenylene ethynylene) (PSESO₂E) were synthesized from bis(4‐ethynylphenyl)sulfide, bis(4‐ethynylphenyl)sulfone, and methylphenyl dichlorosilane. Poly(silylene ethynylene phenylene sulfoxide phenylene ethynylene) (PSESOE) was synthesized by the oxidation of PSESE. The structures and properties of these resins were characterized and the mechanical properties of the T300 reinforced composites were tested. The results show that the novel S‐PSA resins have excellent heat resistance and good mechanical properties, and could be used as resin matrices for high‐performance composites in high‐tech fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2324–2332     

Polymeric organosilicon systems. XVII. Synthesis and photochemical and conducting properties of poly[o-and m-(disilanylene)phenylene]s

Poly[o-(tetramethyldisilanylene)phenylene] ( 2a ), poly[o-(1,2-dimethyldiphenyldisilanylene)-phenylene] ( 2b ), poly[m-(tetramethyldisilanylene)phenylene] ( 2c ), and poly[m-(1,2-dimethyldiphenyldisilanylene)phenylene] ( 2d ) were prepared by the sodium condensation reaction of the corresponding 1,2-and 1,3-bis (chlorosilyl)benzenes in toluene. Irradiation of thin films of 2a-2d in air resulted in a rapid decrease of absorption maxima in the ultraviolet region. The photolysis of 2b and 2d in benzene afforded photodegradation products with low molecular weights. When thin films of 2b and 2d were doped with antimony pentafluoride vapor, films which have conductivities of semi-conductor level were obtained. © 1993 John Wiley & Sons, Inc.     

Synthesis and properties of novel heat-resistant fluorescent conjugated polymers with bisindolylmaleimide

Novel conjugated polymers with bisindolymaleimide were synthesized via simple metal-free condensation polymerization. The polymers exhibited high glass transition temperatures and decomposition temperatures with considerable luminescent properties.     

Synthesis, characterization and properties of heat-resistant and soluble poly(aryl ether)s containing s-triazine units in the main chain

Soluble and heat-resistant s-triazine-containing poly(aryl ether)s have been prepared for their potent utilities as high-temperature membranes and composite matrix materials. They have been synthesized by the nucleophilic displacement polymerization of 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine (BFPT) with each of resorcinol (RS), 4,4′-dihydroxydiphenyl sulfone (DS), and bisphenol-like 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one (HP). The presence of meta-ether linkages, sulfone groups or phthalazinone moieties in the polymer chain results in an improvement in the solubility of s-triazine-containing poly(aryl ether)s in common organic solvents (e.g., N,N′-dimethylacetamide, N-methyl-2-pyrrolidinone). The new polymers are amorphous and exhibit excellent thermal stability. The apparent activation energy values (E_a) as determined by using Kissinger method are respectively 268.1, 245.9 and 215.1 kJ/mol under N₂ flow in dynamic heating conditions, for the first degradation stage of RS-PE, DS-PE and HP-PE, which are in well agreement with those values (272.6, 249.9 and 239.1 kJ/mol) determined by using Flynn-Wall-Ozawa method. The thermal stability classification among the polymers is made on the basis of the E_a values, and it follows the decreasing order: RS-PE > DS-PE > HP-PE. The properties of these polymers have been also compared with those of corresponding poly(aryl ether)s.     

Novel heat-resistant and organosoluble poly(amide-imide)s containing laterally-attached phenoxy phenylene groups

In this research a new diimide-diacid monomer, 2,2′-bis(4-phenoxyphenyl)-4,4′-bis(N-trimellitoyl)diphenyl ether (BPDPE) containing two laterally-attached phenoxy phenylene groups was prepared by the reaction of 2,2′-bis[(p-phenoxy phenyl)]-4,4′-diaminodiphenyl ether (PPAPE) with trimellitic anhydride in refluxing glacial acetic acid. Ether-hinged wholly aromatic poly(amide-imide)s with limited viscosity number values of 0.61–0.87 dL g⁻¹ were prepared by triphenyl phosphate (TPP)-activated polycondensation of BPDPE with diamines including PPAPE and 4,4′-diaminodiphenyl ether (DADPE). For comparative purposes, reference poly(amide-imide)s were also prepared by reacting diimide-diacid monomer lacking phenoxy phenylene lateral groups namely 4,4′-bis(N-trimellitoyl)diphenyl ether (BTDPE) with the same diamines under similar conditions. A model compound MODEL was also synthesized by the reaction of BTBPE with two mole equivalents of aniline to compare the spectral characteristics results. Number and weight average molecular weights were determined by gel permeation chromatography (GPC) technique. The phenoxy phenylene-containing poly(amide-imide)s (all, except that of resulted from BTDPE and DADPE) had excellent organosolubility in common polar solvents. A low crystallinity extent was only observed using their wide-angle X-ray diffractograms (WAXD). A qualitative study showed the prepared polymers could also be cast into optically-transparent and flexible thin films. The ether-containing lateral groups attached to the ether-hinged macromolecular main chains had no substantial diminishing effect on the thermal stability of these structurally-modified poly(amide-imide)s.     

Heat-resistant aromatic S-triazine-containing ring-chain polymers based on bis(ether nitrile)s: Synthesis and properties

A novel series of aromatic s-triazine-containing ring-chain polymers, which typically require high pressures to produce, were prepared by the bulk polymerization of low-melting bis(ether nitrile)s (BENs) with or without the presence of terephthalonitrile (TPH) in the catalysis of ZnCl₂ under normal pressure. Four kinds of BENs were readily synthesized by the nucleophilic displacement reaction of 4-chlorobenzonitrile with commercially available aromatic bisphenols or bisphenol-like monomers. Chemical structure of the obtained BENs and their polymers was characterized by FT-IR, WAXD and elemental analysis. Conversion studies indicate that cyano concentration, mobility and reactivity are all important factors for the polymerization, while among of them the cyano reactivity plays a dominant role. The addition of a small mount of TPH is found to be effective in promoting s-triazine forming reaction of the BENs. The synthesized polymers are insoluble, and exhibit good chemical-resistant property towards strong acids and bases together with good hydrolysis-resistant property. No detectable endothermic inflection for glass transitions is observed in the DSC traces of all polymers up to 450 °C, and the polymers exhibit excellent thermal stability with decomposition temperatures for 5% mass-loss ranging from 493-540 °C. All these attracting properties make the s-triazine-containing ring-chain polymers good candidates as matrixes for high performance polymeric materials.     

Synthesis and thermal properties of conjugated poly[(silylene)diacetylene silazanes]

A series of novel conjugated polymers, poly[(silylene)diacetylene silazanes] having different substituents on silicon were prepared by ammonolysis of the corresponding α,ω-dichlorodiorganosilylenediacetylene oligomers. The polymers had the number-average molecular weight between 700 and 2800, and the polydispersity index between 1.07 and 1.43. The polymers showed good solubility in common organic solvents. The structures of the poly[(silylene)diacetylene silazanes] were characterized by Fourier transform infrared, ¹H, ¹³C, ²⁹Si NMR, elemental analyses, and gel permeation chromatography. The thermal properties were measured with thermogravimetric analysis and differential scanning calorimetry. The resulting polymers had good thermal stability, and the DSC showed lower glass-transition temperature (T_g). They had good processability due to non-crystallization. Treatment of these polymers at appropriate temperature led to thermal polymerization of the acetylene unit to form a new cross-linking network system. These polymers have the potential to be used as precursors for Si/C/N-based ceramics.     

Polymeric organosilicon system VIII. Synthesis of poly[(disilanylene)diethynylene] with highly conducting properties

The reaction of bis(trimethylsilyl)butadiyne with 2 equiv. of methyllithium, followed by 1,2-dichloro-1,2-dimethyldiphenyl- or 1,2-dichloro-1,2-diethyldimethyldisilane gives poly[(1,2-dimethyldiphenyldisilanylene)diethynylene] (II) or poly[(1,2- diethyldimethyldisilanylene)diethynylene] (III), respectively. Films of II and III become conducting when treated with SbF₅ vapor.     

Synthesis and structure of 1,10-phenanthroline bis{[2-(2-pyrrole)-methylimino]4-methylphenolato}nickel(II)

Summary Electrochemical oxidation of nickel in an acetonitrile solution containing 2-pyrrole-[N-(2-hydroxy-4-methyl-phenyl)methylimine] (H₂L) and 1,10-phenanthroline (phen) yielded Ni(HL)₂·phen, whose crystal structure was determined by XRD. The nickel atom has a distorted octahedral geometry, and is coordinated to the phenolic oxygen and imino nitrogen atoms of two Schiff base ligands. The i.r. and u.v.-vis. spectra of the complex are discussed and related to the structure.     

Electrochemical synthesis and characterization of poly(pyrrole-co-tetrahydrofuran) conducting copolymer

The direct electrochemical copolymerization of pyrrole and tetrahydrofuran in various monomer ratios was carried out by potentiostatic methods in nitromethane solution. The copolymer has been characterized using FT-IR, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetrical analysis (TGA), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and elemental analysis. The results showed that the electrochemical oxidation of pyrrole and tetrahydrofuran comonomers generated true copolymers rather than blends of the two homopolymers. The copolymer showed a better flexibility than pure polypyrrole. The electrical conductivity of the copolymers increases with the amount of polypyrrole in the copolymer between the value of 1.69 S/cm and 0.71 S/cm.     

Gas transport properties of soluble poly(phenylene sulfone imide)s

Gas transport of helium, hydrogen, carbon dioxide, oxygen, argon, nitrogen, and methane in three soluble poly(phenylene sulfone imide)s based on 2,2-bis(3,4-decarboxyphenyl) hexafluoropropane dianhydride (6FDA) has been investigated. The effects of increasing length of well-defined oligo(phenylene sulfone) units on the gas permeabilities and diffusivities were determined and correlated with chain packing of the polymers. Activation energies of diffusion and permeation were calculated from temperature-dependent time-lag measurements. The influences of the central group in the diamine moiety of 6FDA-based polyimides on physical and gas transport properties are discussed. The incorporation of a long oligo(phenylene sulfone) segment in the polymer backbone decreases gas permeability and permselectivity simultaneously. The decreases in permeability coefficients can be mainly related to decreases in diffusion coefficients. Changing the central group of diamine moiety from  S to  SO₂ leads to a 45–50% decrease in CO₂ and O₂ permeabilities without appreciable increase in the selectivities. This is considered to be due to the formation of charge transfer complexes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1855–1868, 1997     

Ferrocene clicked poly(3,4-ethylenedioxythiophene) conducting polymer: Characterization, electrochemical and electrochromic properties

The “click” chemistry, Cu(I)-catalyzed azide–alkyne cycloaddition reaction, was applied to covalently functionalize the poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer film with an excellent electron transfer mediator (ferrocene). Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and Raman spectroscopy were used to characterize the ferrocene-grafted PEDOT conducting polymer film, and it was proved that the grafting procedure via click reaction had a high efficiency. The ferrocene groups covalently grafted in the polymer films turned out to own a relatively fast electron transfer rate and show multi-color states via adjusting applied potential.     

Synthesis of hydrogen-terminated aliphatic bis(ethynyl ketone)s and aliphatic poly(enamine-ketone)s and poly(enonesulfide)s

Hydrogen-terminated aliphatic bis(ethynyl ketone)s (H-ABEKs): 1,9-decadiyne-3,8-dione ( 3a ) and 1,13-tetradecadiyne-3,12-dione ( 3b ) were prepared by the Friedel-Crafts reaction of bis(trimethylsilyl) acetylene (BTMSA) with adipoyl chloride and sebacoyl chloride, followed by desilylation with an aqueous buffer solution. Aliphatic poly(enamine-ketone)s (APEKs) and aliphatic poly(enonesulfide)s (APESs) were prepared in nearly quantitative yield by the nucleophilic addition polymerization of 3a,b with various diamines and dithiols in N,N-dimethylformamide (DMF) and m-cresol at room temperature during 14-22 h. Aromatic diamines and dithiols gave polymers that were soluble only in m-cresol. Primary diamines gave exclusively APEKs with the cis (Z) configuration. Dithiols gave APESs which contained more cis (Z) than trans (E) configurations. The inherent viscosities (η_inh) of the APEKs ranged from 0.05 to 0.73 dL/g. The APESs gave η_inh ranging from 0.36 to 2.21 dL/g.