Synthesis and properties of aromatic polyesters and brominated polyesters derived from α,α′-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene

The interfacial polycondensation technique was used for the preparation of polyarylates and brominated polyarylates. Polyarylates and brominated polyarylates were prepared by mixing a solution of diacid chloride such as terephthaloyl chloride, isophthaloyl chloride, or their mixture in dichloromethane with an aqueous alkaline solution of ,-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene or ,-bis(4-hydroxy-3,5-dibromophenyl)-1,4(or 1,3)-diisopropylbenzene using triethylbenzylammonium chloride as the phase transfer agent. Moderate to high molecular weight polyarylates with _inh up to 1.27 dL/g were obtained, and most of them could be cast into tough and flexible films depending on the polymer composition. In general, polymers containing more 1,3-isomer or isophthaloyl chloride moieties gave transparent and flexible films and had lower glass transition temperatures and higher solubility. Although these polymers have two isopropylidene linkages in their repeating units, they still exhibit moderately high thermal stability and show no obvious weight loss before 400 °C. The introduction of bromine on the polymer backbone caused a decrease of inherent viscosity, crystallinity, and thermal stability of the polyarylates, while causing an increase in glass transition temperature and a great enhancement of fire retardancy.     

Synthesis,characterization and photoluminescence properties of copper(II)–azido/thiocyanato complexes with thiazolylazo dye and1,2-bis(diphenylphosphino)ethane

A series of copper(II) complexes of the formula [Cu(L)(dppe)(N₃)₂] (1a–3a) and [Cu(L)(dppe)(NCS)₂] (1b–3b) (where L = 4-(2′-thiazolylazo)chlorobenzene (L₁); 4-(2′-thiazolylazo)bromobenzene (L₂) and 4-(2′-thiazolylazo)iodobenzene (L₃); dppe = cis-1,2-bis(diphenylphosphino)ethane) has been prepared and characterized on the basis of their elemental analysis, molar conductance, magnetic moment, IR, UV–vis and ¹H NMR spectral studies. The electrochemical behaviour of the complexes showed that the redox responses of copper(II) complexes shifted to more negative potential in order of decrease in electron withdrawing nature of the substituent on the azo ligands. All the complexes exhibit intraligand (π→π*) fluorescence in blue-green region with high quantum yield in DMF solution.     

An efficient,clean synthesis of 3,3′-(arylmethylene)bis(2-hydroxynaphthalene-1,4-dione) derivatives

A clean, simple and efficient method for the synthesis of 3,3′-(arylmethylene)bis(2-hydroxynaphthalene-1,4-dione) derivatives has been developed which uses the reaction of 2-hydroxynaphthalene-1,4-dione and aromatic aldehydes in the presence of a catalytic amount of LiCl in aqueous media. To the best of our knowledge, this is the first report on such a synthesis of 3,3′-(arylmethylene)bis(2-hydroxynaphthalene-1,4-dione).     

New optically active poly(amide-imide)s based on N,N′-(pyromellitoyl)-bis-L-amino acid and 1,3-bis(4-aminophenoxy) propane: Synthesis and characterization

Five new poly(amide-imide)s 8a–e were synthesized through the direct polycondensation reaction of five chiral N,N′-(pyromellitoyl)-bis-L -amino acids 3a–e with 1,3-bis(4-aminophenoxy) propane 7 in a medium consisting of N-methyl-2-pyrrolidone, triphenyl phosfite, calcium chloride, and pyridine. The polycondensation reaction produced a series of novel poly(amide-imide)s containing trimethylene moiety in the main chain in high yield with inherent viscosities between 0.34 and 0.65 dL/g. The resulted polymers were fully characterized by means of FTIR spectroscopy, elemental analyses, inherent viscosity, and solubility tests. Thermal properties of these polymers were investigated by using thermal gravimetric analysis (TGA) and differential thermal gravimetric (DTG). All of the polymers were soluble at room temperature in polar solvents such as N,N-dimethyl acetamide, N,N-dimethyl formamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. N,N′-(pyromellitoyl)-bis-L -amino acids 3a–e were prepared in quantitative yields by the condensation reaction of pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic acid 1,2,4,5-dianhydide) 1 with L -alanine 2a , L -valine 2b , L -leucine 2c , L -isoleucine 2d , and L -phenyl alanine 2e in acetic acid. Also 1,3-bis(4-aminophenoxy) propane 7 was synthesized by using a two-step reaction. At first 1,3-bis(4-nitrophenoxy) propane 6 was prepared from the reaction of 4-nitrophenol 4 with 1,3-dibromoprapane 5 in NaOH solution. Then, dinitro compound 6 was reduced by using Na₂S. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The synthesis and characterization of a mesomorphic brush type polycarbosilane: poly[1,1-bis(4′-biphenyl)silabutane]

Summary Poly[1,1-bis(4-biphenyl)silabutane] (II) has been prepared by the anionic ring opening polymerization of 1,1-bis(4-biphenyl)silacyclobutane. II shows mesomorphic behavior by DSC. The¹³C NMR T₁ relaxation times have been measured. These are found to be smaller than those of poly(1,1-dimethylsilabutane)by an order of magnitude. This may result from interaction of the highly rigid biphenyl side chain moieties. The thermal stability of II is higher than that for other 1,1-disubstituted polysilabutanes.     

Synthesis and characterization of a novel kind of thermotropic liquid crystalline poly(urea-ester)s based on bis(4′-hydroxyphenyl)-tolyene-2,4-diurea

A new diphenol monomer bis(4′-hydroxy-phenyl)-tolyene-2,4-diurea was synthesized by reaction of 2,4-toylene diisocyanate with p-aminophenol in N,N-dimethylformamide (DMF). The product was characterized by elemental analysis (EA), differential scanning calorimetry (DSC), and ¹H-NMR. And a novel kind of liquid crystalline poly(urea-ester)s were obtained by using this monomer. By using a polarizing microscope with hot stage (POM), wide-angle X-ray diffraction (WAXD) and small-angle X-ray diffraction (SAXD) the polymers were proven to be nematic liquid crystal. The result of DSC showed that the effect of the monomer composition on the melting point of poly(urea-ester)s was significant. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 577–583, 2001     

Nickel complex-mediated copolymerization of regioisomeric 5,5′-bis(chlorobenzoyl)-2,2′-dimethoxybiphenyls: synthesis of wholly aromatic copolyketones

Aromatic coupling copolymerization of 5,5^′-bis(4-chlorobenzoyl)-2,2^′-dimethoxybiphenyl (1) and 5,5^′-bis(3-chlorobenzoyl)-2,2^′-dimethoxybiphenyl (2) has successfully afforded higher-molecular-weight polyketones than either of the corresponding homopolymerizations. The wholly aromatic copolyketones thus obtained have highly amorphous nature with high glass transition temperatures (T_g).     

Advantageous mechanochemical synthesis of copper(Ⅰ)selenide semiconductor,characterization,and properties

Copper(I)selenide-nanocrystalline semiconductor was synthesized via one-step mechanochemical synthesis after 5 min milling in a planetary ball mill.The kinetics of synthesis was followed by X-ray powder diffraction analysis and specific surface area measurements of milled 2Cu/Se mixtures.The X-ray diffraction confirmed the orthorhombic crystal structure of Cu₂Se with the crystallite size～25 nm.The surface chemical structure was studied by X-ray photoelectron spectroscopy,whereby the binding energy of the Cu 2p and Se 3d signals corresponded to Cu⁺and Se^2?oxidation states.Transmission electron microscopy revealed agglomerated nanocrystals and confirmed their orthorhombic structure,as well.The optical properties were studied utilizing ultraviolet-visible spectroscopy and photoluminescence spectroscopy.The direct bandgap energy 3.7 eV indicated a blue-shift phenomenon due to the quantum size effect.This type of Cu₂Se synthesis can be easily adapted to production dimensions using an industrial vibratory mill.The advantages of mechanochemical synthesis represent the potential for inexpensive,environmentally-friendly,and waste-free manufacturing of Cu₂Se.     

Synthesis and characterization of 4,4’–(dimethylsilylene) bis( phenyl chloroformate) and 4,4’–(dimethylgermylene)bis(phenyl chloroformate) and their use in the synthesis of poly(urethanes)

Summary The synthesis of 4,4–(dimethylsilylene)bis(phenyl chloroformate) and 4,4–(dimethylgermylene)bis(phenyl chloroformate) is described according to the same route for the synthesis of bisphenol–A bischloroformate. These compounds were characterized using elemental analysis, FT–IR and NMR spectroscopy. Poly(urethanes) derived from these bischlororformates containing silicon or germane in the main chain, were obtained in benzene solution by reaction with 4,4–methylenedianiline in the presence of pyridine. Poly(urethanes) were characterised by spectroscopic methods and the thermal properties (Tg and thermal stability) were compared with the homologue poly(urethane) obtained from bisphenol–A chloroformate.     

Synthesis and properties of polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane

A new kind of polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane was prepared by the anionic polymerization with a “seed solution” as initiator. The synthesis of monomers N,N′-bis(hydroxydiphenylsilyl)tetraphenylcyclodisilazane (BHPTPC), N,N′-bis(chlorodiphenylsilyl)tetraphenylcyclodisilazane (BCPTPC), and 1,3-dichloro-1,1,3,3-tetraphenyldisilazane (DCTPS) are all reported in this study. The synthesized polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane was characterized by ¹H–NMR, ²⁹Si–NMR, gel permeation chromatography (GPC), and intrinsic viscosity. The thermal stability of the polysiloxane was studied by isothermal gravimetric analysis (IGA). The results demonstrated that the synthesized polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane had excellent thermal stability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 929–933, 2001     

Low-dielectric-constant aromatic homopolyimide and copolyimide derived from pyromellitic dianhydride, 4,4′-oxydianiline, 2,2-bis[4-(4-aminephenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene,or 1,3-bis(4-aminophenoxy)benzene

Low-dielectric-constant aromatics, homopolyimide and copolyimide, were introduced. Homopolyimides were prepared by pyromellitic dianhydride (PMDA) as an anhydride monomer and 4,4′-oxydianiline (ODA), 2,2-bis[4-(4-aminephenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, or 1,3-bis(4-aminophenoxy)benzene as an amine monomer. The copolyimides were prepared with PMDA as an anhydride monomer, ODA as an amine monomer with the addition of 2,2-bis[4-(4-aminephenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, or 1,3-bis(4-aminophenoxy)benzene as another amine monomer. The polyimides were well characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, thermomechanical analysis, dielectric measurements, and tensile testing. The homopolyimide and copolyimides showed lower dielectric constants than the homopolyimide formed by ODA and PMDA. The results also indicate that the interchain distance, the quantities of phenyl ether, and the position of the substitute are factors that not only affected the thermal performance of polyimide by improving the molecular flexibility but also reduced the dielectric constant of polyimide by increasing the free volume of the molecular chain and decreasing the polarization points per unit volume. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47405.     

Entry to alkynylplatinum(IV) chemistry using hypervalent iodine(III) reagents,and the synthesis of triphenyl{4,4′-bis(tert-butyl)-2,2′-bipyridine}iodoplatinum(IV)

The reaction of phenyl(alkynyl)iodine(III) triflates with diorganoplatinum(II) complexes provides a general route for the synthesis of a new class of alkynylplatinum(IV) complexes containing Pt^IVR₂(CCR²) groups, e.g., the 4,4^′-bis(tert-butyl)-2,2^′-bipyridine complexes PtIR₂(CCSiMe₃)(Bu^t₂bpy) (R=Me, Ph); IPh₂(OTf) reacts with PtPh₂(Bu^t₂bpy) to form the first archetypal triarylplatinum(IV) complex PtIPh₃(Bu^t₂bpy).     

2-(1′-alkoxyvinyl) thiazolidines: synthesis and study of ring-chain tautomerism

2-Alkoxypropenals react with 2-aminoethanethiol to yield mixtures of tautomeric 2-(1-alkoxyvinyl)thiazolidines and imino thiols. The ring-chain tautomeric equilibria, studied by ¹H NMR spectroscopy, were strongly dependent on the solvent polarity, ratio of reagents, and pH of the medium.     

Synthesis,characterization and properties of polyimides from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride and imidazole-blocked 2,5-bis[(n-alkyloxy)methyl]-1,4-benzenediisocyanates

Summary By the solution condensation of 3,3,4,4-benzophenonetetracarboxylic dianhydride (BTDA) with imidazole-blocked 2,5-bis[(n-alkyloxy)methyl]-1,4-benzenediisocyanates (C_m-BDIs) a series of aromatic polyimides (C_m-BP-PIs) having flexible (n-alkyoxy)methyl (-CH₂O-n-C_mH_2m+1, m=4, 6, 8) side chains were prepared and characterized by IR- and ¹H-NMR spectroscopy and their properties were measured and discussed in respect to the effects of side chains. Inherent viscosities of the polymers were in the 0.23–0.34 dL/g range. All the polymers were highly soluble in N,N-dimethylpropyleneura(DMPU) and C₆- and C₈-BP-PIs even in CHCl₃ at room temperature. UV-VIS spectra showed that the -electrons are delocalized along the main chain. TGA studies showed a two-step pyrolysis behavior and in DSC Tg's of C₄-, C₆- and C₈-BP-PIs were determined to be 184, 135 and 127 °C, respectively. Wide-angle X-ray diffractometry for as-polymerized samples revealed a quite low crystallinity with only loosely developed layered structure.     

A convenient method for synthesis of bis-2,2′-(1,3,4-thiadiazole) and bis-3,3′-(1,2,4-triazole) derivatives

Reactions of the bis-hydrazonoyl chloride 1 with ketene N,S-acetal 2 and the active methine thioanilides 4 and 6 provide a new convenient site-selective synthetic strategy to functionalized bis-3,3′-(1,2,4-triazoles) 3 and bis-2,2′-(1,2,4-thiadiazoles) 5 and 7.     

Synthesis and properties of poly(ester imide) copolymers from 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis(trifluoromethyl)benzidine,and 4-aminophenyl-4′-aminobenzoate

A series of poly(ester imide) (PEsI) copolymers were synthesized using 3,3′,4,4′-biphenyltetracarboxylic dianhydride (4,4′-BPDA), 2,2′-bis(trifluoromethyl)benzidine (TFMB), and 4-aminophenyl-4′-aminobenzoate (APAB) as the monomers. Wide-angle x-ray diffraction results revealed that the average interchain distances of these polymers ranged from 4.6 to 5.7 Å, increasing with the increase of TFMB contents. PEsI-0.3 and PEsI-0.4 exhibited a glass transition temperature (T_g) of 445 and 455°C, respectively, while no distinctive T_g was observed for the PEsI copolymers when the APAB content was >50 mol%. The coefficients of thermal expansion (CTE) of these PEsI copolymers ranged from 3.8 to 24.2 ppm K⁻¹, increasing with the increase of TFMB contents. The PEsI copolymers exhibited a modulus of 5.7–7.8 GPa, a tensile strength of 282–332 MPa, and an elongation-at-break of 10.2%–23.3%. Furthermore, these copolymers exhibited a dielectric constant of 2.53–2.76, and a low dissipation factor (D_f) of 0.0026–0.0032 at 10 GHz in dry state. Because of their excellent combined properties, these PEsI copolymers are promising candidates as dielectric substrate materials for the applications in next generation flexible printed circuit boards operating at high frequencies.     

Synthesis and characterization of poly(11-(4′-cyano-trans-4-stilbenyloxy)undecanyl vinyl ether)

Summary Polymers based on 11-(4-cyano-trans-4-stilbenyloxy)undecanyl vinyl ether have been synthesized by living cationic polymerization, photo-initiated cationic polymerization using onium salts and thermal initiated cationic polymerization using onium salts. The polymers have been characterized by size exclusion chromatography, nuclear magnetic resonance spectroscopy, differential scanning calorimetry and polarized light microscopy. Living cationic polymerization resulted in a polymer of low molecular mass M_n3 600, with a uniformity index (D) of 1.2 displaying a focal conic texture indicative of smectic A (s_A) phase with preserved cyanogroup and trans-configuration. Photo-initiation using 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and diphenyliodonium hexafluorophosphate resulted in an insoluble polymer exhibiting only vague liquid crystalline textures. Initiation with phenothiazine and phenacyltetramethylenesulfonium hexafluoroantimonate also yielded a partly insoluble polymer with a disturbed s_A phase. It is suggested that the monomer and polymer are sensitive towards radicals leading to cross-linking and branching. The thermal initiation on systems with -methylbenzyltetramethylenesulfonium hexafluorophosphate and p-methoxybenzyltetramethylenesulfonium hexafluorophosphate resulted in completely soluble mesomorphic polymers of M_n13 000, D=1.7 and M_n26 000, D=2.8 respectively, in both cases with a preserved cyanogroup and a transconfiguration. Polarized light microscopy revealed a distinct focal conic structure indicative of s_A in both cases.     

Dietary comparison of conjugated linolenic acid (9 cis, 11 trans, 13 trans) and α-tocopherol effects on blood lipids and lipid peroxidation in alloxan-induced diabetes mellitus in rats

The present study investigated the dietary effect of conjugated linolenic acid (CLnA) on lipid profiles and lipid peroxidations in alloxan-induced diabetes mellitus in rats. Diabetic rats were fed with 20% sunflower oil (diabetic control), sunflower oil supplemented with 0.5% CLnA, sunflower oil supplemented with 0.15% α-tocopherol, and sunflower oil containing 0.25% CLnA+0.15% α-tocopherol. The results demonstrated that 0.5% CLnA, 0.15% α-tocopherol, and 0.25% CLnA+0.15% α-tocopherol each on supplementation significantly lowered total cholesterol and non-HDL-cholesterol in comparison with the diabetic control group. The TAG level was significantly lowered in both the 0.15% α-tocopherol and 0.25% CLnA+0.15% α-tocopherol groups. LDL lipid peroxidation and erythrocyte membrane lipid peroxidation were reduced significantly in each of the experimental groups vs. the control group. The CLnA+α-tocopherol diet induced a greater reduction in membrane lipid and liver lipid peroxidation than the α-tocopherol diet alone. In conclusion, dietary CLnA exerts antioxidant activity as evidenced by reduced lipid peroxidation in chemically induced diabetes mellitus.     

Synthesis,characterization and crystal structure of (cis-P,P′-diphenyl-1,4-diphospha-cyclohexane)molybdenum(0)tetracarbonyl

The preparation of the novel (cis-P,P′-diphenyl-1,4-diphospha-cyclohexane)molybdenum(0)tetracarbonyl complex is described. The spectral data and X-ray structure of the title complex are reported. The results of the crystallographic work show a distorted octahedral complex around the metal center, the first of its kind reported for the P,P′-diphenyl-1,4-diphospha-cyclohexane ligand.     

Synthesis,characterization and crystal structure of one Mn(II) complex with 4,4′-bisimidazolylbiphenyl and 4,4′-sulfonyldibenzoic acid

One new title compound [Mn₃(BIBP)(sdb)(NO₂⁻)₂(H₂O)₂]_n·2DMF (1) (BIBP = 4,4′-bisimidazolylbiphenyl, sdb = 4,4′-sulfonyldibenzoic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction. Magnetic susceptibility measurements indicate that compound 1 exhibits antiferromagnetic coupling interaction.