Aromatic polyethers,polysulfones, and polyketones as laminating resins. VI. Polymers from 2,5-dicyanoterephthalic acid

Aromatic poly(keto ether sulfones) containing various amounts of pendant cyano groups were synthesized from 1,4-bis(p-phenoxybenzoyl)-2,5-dicyanobenzene, 1,3-bis(p-phenoxybenzenesulfonyl)benzene, and isophthaloyl chloride by a Friedel-Crafts type polymerization. These polymers softened at 160–190°C and had inherent viscosities of 0.44–0.61 in hexamethylphosphoric triamide. Crosslinkings were made by heating the polymers alone or in the presence of zinc chloride at 360–370°C to give black resinous materials that were insoluble in hexamethylphosphoric triamide in which the original polymers dissolved quite readily.     

Synthesis of New Substituted 2,3-Dihydro-1,4-dioxin-2-ones and 1,4-Dioxan-2-ones

3-Alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones reacted with acetyl chloride in the presence of zinc(II) chloride to give 5-acetyl-3-alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones. Oxidation of the latter with hydrogen peroxide in formic acid, followed by treatment with magnesium bromide, afforded 3-alkyl-6-methyl-1,4-dioxane-2,5-diones. Chlorination of 6-hydroxymethyl-1,4-dioxan-2-ones with thionyl chloride and subsequent dehydrochlorination led to formation of 6-methylene-1,4-dioxan-2-ones.     

Fluorescence quenching and laser photolysis of dipyrrolylbenzenes in the presence of chloromethanes

Fluorescence quenching of 1,4-bis(1H-pyrrol-1-yl)benzene, 1-(1H-pyrrol-2-yl)-1-(1-vinyl-1H-pyrrol-1-yl)benzene, and 1,4-bis(1-vinyl-1H-pyrrol-2-yl)benzene with chloromethanes (methylene chloride, chloroform, and carbon tetrachloride) in solvents with different polarities follows electron-transfer mechanism. The occurrence of an electron-transfer step is confirmed by formation of short-lived pyrrolylbenzene radical cations. An exception is quenching of fluorescence of 1,4-bis(1-vinyl-1H-pyrrol-2-yl)benzene in n-hexane in the presence of CCl₄ and CHCl₃ and in pure CCl₄. In this case, neutral 1,4-bis(1-vinyl-1H-pyrrol-2-yl)benzene^·-Cl radical is formed via recombination of 1,4-bis(1-vinyl-1H-pyrrol-2-yl)benzene radical cation and chloride anion. A relation was found between the nature of the short-lived species detected by laser photolysis and stable product obtained by stationary photolysis.     

Novel synthesis of electroconducting polymers from simple monomers with transition metal complex catalysts

Electroconductive polyaromatics or polyarylenes have been successfully prepared by the oxidative polymerization of the corresponding simple monomers over the transition metal complex catalyst. For example, poly(1,4-phenylene) was prepared from benzene by using oxygen as an oxidant and a copper(I) chloride-aluminum chloride double complex as the catalyst. The same catalytic system was applied to the preparation of poly(2,5-pyrrolylene) and poly(2,5-thienylene) from pyrrole and 2,2′-bithiophen, respectively. The electrochemical oxidative polymerization was also carried out for the preparation of the poly(1,4-phenylene) and poly(1,4-naphthylene) films in the presence of copper(I) chloride and aluminum chloride.     

Synthesis of New Substituted 2,3-Dihydro-1,4-dioxin-2-ones and 1,4-Dioxan-2-ones

3-Alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones reacted with acetyl chloride in the presence of zinc(II) chloride to give the corresponding 3-alkyl-5-acetyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones. Oxidation of the latter with hydrogen peroxide in formic acid, followed by treatment with magnesium bromide, afforded 3-alkyl-6-methyl-1,4-dioxane-2,5-diones. Successive chlorination and dechlorination of 6-hydroxymethyl-1,4-dioxan-2-ones yielded 6-methylene-1,4-dioxan-2-ones.     

Active polycondensation with hexamethylenediamine of sebacates having 1,4-pyrone nuclei

Sebacates from alcohols having a 1,4-pyrone nucleus were synthesized, and their reactivities toward diamine were investigated. The polycondensation reactions of di(6-hydroxymethyl-1,4-pyron-3-yl) sebacate or di(2-methyl-1,4-pyron-3-yl) sebacate with hexamethylenediamine took place easily even at room temperature to form a high molecular weight nylon 610 in a quantitative yield. The reactivities of these active diesters with diamine were much higher than that of the corresponding diphenyl ester and were almost comparable to those of acid chlorides. It was also found that inorganic salts such as lithium chloride, zinc chloride, or calcium chloride had a strong influence on the molecular weight of the resulting polyamide. The reactivity enhancement of the active diesters toward aminolysis could be attributed mainly to the acidic character of the leaving group.     

Molecular "compasses" and "gyroscopes". I. Expedient synthesis and solid state dynamics of an open rotor with a bis(triarylmethyl) frame

We describe our efforts toward the preparation of materials built with molecules possessing topologies analogous to those of macroscopic compasses and gyroscopes. Samples of 1,4-bis(3,3,3-triphenylpropynyl)benzene (3) were prepared by a simple two-step procedure from triphenylmethyl chloride (1) and 1,4-diiodobenzene. The structure of compound 3 is such that the central phenylene can play the role of a gyroscope wheel while the two tritylpropynyl groups can act as an axle and shielding framework. Crystals of a benzene clathrate were characterized by single crystal X-ray diffraction and variable-temperature solid state NMR while their thermal stability was determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The rotational dynamics of the phenylene group in the benzene clathrate and in desolvated samples were characterized in terms of a two-fold flipping process. Solid state rotational barriers of ca. 12.8 and 14.6 kcal/mol were estimated for the benzene clathrate and desolvated samples, respectively.     

Solvothermal synthesis,thermal and adsorption properties of metal-organic frameworks Zn and CoZn(DPB)

Journal of Thermal Analysis and Calorimetry - New mononuclear and hetero-binuclear MOFs derived from the reaction of 1,4-bis[(3,5-dimethyl)pyrazole-4-yl]benzene (H2DPB) with zinc nitrate or mixture...     

Effect of central spacer chain structure on cationic cyclopolymerization tendency of divinyl ethers

To clarify the effects of the central spacer chain structure of divinyl ethers on their cationic cyclopolymerization tendencies, 1,4‐bis[(2‐vinyloxy)ethoxy]benzene ( 1 ), 1,4‐bis[(2‐vinyloxy)ethoxy]butane ( 2 ), 1,6‐bis[(2‐vinyloxy)ethoxy]hexane ( 3 ), 1,8‐bis[(2‐vinyloxy)ethoxy]octane ( 4 ), and 1,4‐bis[(4‐vinyloxy)butoxy]butane ( 5 ) were polymerized with the hydrogen chloride/zinc chloride (HCl/ZnCl₂) initiating system in methylene chloride (CH₂Cl₂) at 0 °C at low initial monomer concentration ([M]₀ = 0.15 M). The polymerizations of divinyl ethers 2 and 3 gave soluble polymers quantitatively. In contrast, the polymerizations of divinyl ethers 1 , 4 , and 5 underwent gel formation at high monomer conversion. The content of the unreacted vinyl groups of the obtained soluble polymers was measured by ¹H NMR spectroscopy. Judging from the relatively low vinyl contents of the polymers produced even in the early stage of the polymerization (monomer conversion < ～20%), the cyclopolymerization occurred to some extent for 2 , 3 , and 4 . On the contrary, the polymers produced from 1 and 5 exhibited the relatively high vinyl content, indicating that the cyclopolymerization tendencies of 1 and 5 were lower than those of 2 , 3 , and 4 . These results are discussed in terms of the structural variety of the spacer chains: (1) the presence of benzene ring ( 1 vs 2 ), (2) their length ( 2 vs 3 and 4 ), and (3) the position of ether oxygen ( 4 vs 5 ). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4002–4012, 2002     

SYNTHESES OF BRANCHED POLY(ETHER KETONE)S WITH PENDANT FUNCTIONAL GROUPS BASED ON 1,1,1-TRIS(4-HYDROXYPHENYL)ETHANE

ABSTRACT

1,1,1-Tris(4-hydroxyphenyl)ethane, THPE, was silylated with chlorotrimethylsilane and the silylated THPE was polycondensed with 1,4-bis(4-fluorobenzoyl)benzene, BFBB, in dry N-methylpyrrolidone. The resulting poly(ether ketone) had a moderate molecular weight and contained a significant fraction of cyclic oligomers and polymers. The pendant trimethylsiloxy group allowed an in situ alkylation with chloropropionitrile, allylbromide, 3,4-dichlorobenzyl chloride, 4-nitrobenzyl bromide, 1,3-propane sultone and 1,4-butane sultone. The latter alkylating agents yielded poly(ether ketone)s having pendant sulfonic acid groups. Further functional groups were introduced by acylation of the pendant free OH-group (resulting from the hydrolysis of the Me₃SiO group) with acetic anhydride, methacrylic anhydride, cinnamoyl chloride and undecenoyl chloride.     

Adsorption properties of the MOF-5 metal-organic framework in relation to water and benzene

Adsorption properties of synthesized metal-organic frameworks based on 1,4-dicarboxylate ligands and zinc ions were studied. It was shown that the adsorption properties of these metal-organic frameworks in relation to water and benzene are much higher than those for the known adsorbents: KT-1 and KT-2 coals, USY and ZSM-5 zeolites, and pentasil.     

Phenothiazine cruciforms: synthesis and metallochromic properties

We report the synthesis and characterization of five novel phenothiazine-containing cruciforms (5-9). The targets were prepared by a NaH-promoted Horner reaction of tetraethyl(2,5-diiodo-1,4-phenylene)bis(methylene)diphosphonate with 10-hexyl-10H-phenothiazine-3-carbaldehyde. The formed intermediary 3,3'-(1E,1'E)-2,2'-(2,5-diiodo-1,4-phenylene)bis(ethene-2,1-diyl)bis(10-hexyl-10H-phenothiazine) was reacted with several different aromatic alkynes (1-tert-butyl-4-ethynylbenzene, N,N-dibutyl-4-ethynylaniline, 1-ethynyl-3-(trifluoromethyl)benzene, and 1-ethynyl-3,5-bis(trifluoromethyl)benzene) to give the corresponding cruciform fluororphores (XF). The XFs were fully characterized by NMR and IR spectroscopy and then exposed to trifluoroacetic acid as well as to several metal triflates. The XFs show dramatic shifts in emission and to a lesser extent in absorption when exposed to magnesium triflate or zinc triflate. In the case of magnesium triflate, a blue shift in emission was observed; in contrast, addition of zinc triflate results in either quenching or a red-shifted emission. Due to the electronic situation, these XFs display spatially separated frontier molecular orbitals, allowing the HOMO or the LUMO of the XFs to be addressed independently by addition of zinc or magnesium ions. Phenothiazine XFs may have potential in array-type sensory applications for metal cations.     

Synthese und Charakterisierung von Dimesitylzink

Synthesis and characterization of dimesityl zinc Dimesityl magnesium reacts with zinc chloride in THF solution forming dimesityl zinc. This compound is free of solvent and monomer in benzene. 2,2′-Bipyridine and tetramethylethylenediamine yield weak complexes. Thermal behaviour and spectroscopic properties of these compounds and some reactions of ZnMes₂ are described.     

New zinc phosphates decorated by imidazole-containing ligands

Four new zinc phosphates [Zn(HPO4)(C6H9N3O2)] (1), [Zn(HPO4)(C4H6N2)].H2O (2), [Zn2(HPO4)2(C14H14N4)].2H2O (3), and [Zn(HPO4)(C14H14N4)] (4) were synthesized in the presence of d-histidine, 1-methylimidazole, 1,4-bis(imidazol-1-ylmethyl)benzene (L1), and 1,2-bis(imidazol-1-ylmethyl)benzene (L2), respectively, and their structures were determined by X-ray crystallography. The inorganic framework of compounds 1, 2, and 3 is composed of vertex-shared ZnO3N and HPO4 tetrahedra that form four rings, which, in turn, are linked to generate a one-dimensional ladder structure. In 1 and 2 the organic groups (monoimidazole ligand) are located at each side of the ladders, while in 3 the bisimidazole ligand, 1,4-bis(imidazol-1-ylmethyl)benzene, links the ladders together to form a novel 2D structure. Compound 1 is the first zinc phosphate framework to be templated by an N-bonded chiral amino acid. In 4 the zero-dimensional four rings are joined together by the linear bridging ligand, 1,2-bis(imidazol-1-ylmethyl)benzene, to generate a one-dimensional framework with a new face-to-face structural motif. The 3D structure of compound 4 is stabilized by hydrogen-bonding, pi-pi interactions, and C-H...pi interactions. The approach of incorporating multifunctional ligands into zinc phosphate frameworks and linking the inorganic zinc phosphates subunits by an organic ligand provides opportunities for the design of new inorganic-organic open frameworks.     

含羧酸酯侧基的聚芳醚酮酮醚酮酮的合成与表征

以含羧基侧基的聚芳醚酮酮醚酮酮(PEKKEKK-A)树脂为原料,二氯亚砜(SOCl2)、二氯乙烷(DCE)、吡啶为催化溶剂体系,合成带甲酰氯侧基的聚芳醚酮酮醚酮酮(PEKKEKK-C)树脂.PEKKEKK-C与甲醇、乙醇、丁醇、辛醇、苯酚等发生酯化反应,得到5种含羧酸酯侧基的聚芳醚酮酮醚酮酮(PEKKEKK-E)s.用红外光谱(FTIR)、氢核磁谱(1H-NMR)、广角X射线衍射(WAXD)、热失重(TGA)、示差扫描量热(DSC)等技术对其结构与性能进行了分析表征.结果表明,聚合物为非晶聚集态;玻璃化转变温度(Tg)在175.7～236.8℃之间,较PEKK有较大幅度提高;出现两次热失重平台,分别在335～365℃,460～505℃之间,第一次失重可能由于酯分解所致,第二次失重可能是分子主链开始分解;树脂能溶解于DMAc、NMP、二氯甲烷等普通有机溶剂中,溶剂挥发后成膜性良好,可制成透明薄膜;断裂伸长率在6.34%～15.43%之间,拉伸强度在74.68～85.35MPa之间。     

Hydrogen‐bonded thermotropic liquid‐crystalline polyester–amides from bis(hydroxy alkamido)aranes: Synthesis and properties

Hydrogen‐bonded aromatic–aliphatic polyester–amides (PEAs) were prepared by solution/melt polycondensation of aromatic–aliphatic amidodiols 1,4‐bis(4‐hydroxybutyramide)benzene (BHBB), 1,4‐bis(5‐hydroxy pentamide)benzene, 1,4‐bis(6‐hydroxyhexamide)benzene, 1,4‐bis(4‐hydroxybutyramidexylene), 1,4‐bis(5‐hydroxypentamidexylene, 1,4‐bis(4‐hydroxybutyramide)benzene, and 1,4‐bis(6‐hydroxyhexamidexylene) with terephthaloyl chloride/dimethyl terephthalate. Aromatic–aliphatic amido diols were prepared by the aminolysis of γ‐butyrolactone, δ‐valerolactone, and ?‐caprolactone with aromatic diamines such as paraphenylene diamine and paraxylene diamine. The monomers and polymers were characterized by chemical analysis (hydroxyl value and elemental analysis), Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR. The thermal‐ and phase‐transition behaviors of the polymers were investigated by differential scanning calorimetry in combination with hot‐stage optical microscopy. Crystallinity of polymers was examined with wide‐angle X‐ray diffraction. The polymers exhibited liquid crystallinity with layered structures formed by self‐organization of the hetero intermolecular hydrogen‐bonded networks indicating smectic phases except for PEAs prepared from BHBB. The hydrogen atom of the phenyl‐substituent group forces the neighboring carbonyl groups out of plane of the rings preventing formation of layered structures in the case of BHBB. The PEAs retained intermolecular hydrogen bonding even in the mesomorphic state, and variations in the hydrogen‐bonded lamellae/micelles might be responsible for the variations from one smectic to another texture. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 335–346, 2003     

Discovery and crystal structure of a novel chlorocarbon host: perchlorofluorene-9-spirocyclohexa-2′,5′-diene

Chlorination of triphenylene (1a) employing a mixture of aluminium trichloride and sulphur monochloride in sulphuryl chloride leads to rearrangement with formation of the title chlorocarbon (2), a new host, as main product. X-ray crystal structure analyses of the unsolvated spirocycle (2) as well as of its inclusion compounds with guests benzene and cyclohexa-1,4-diene are described.     

Synthesis of ditopic ligands containing bis(1<Emphasis Type="Italic">H</Emphasis>-pyrazol-1-yl)-methane fragments

New approaches have been proposed for the synthesis of compounds containing two bis(1H-pyrazol-1-yl)methane fragments. Nucleophilic replacement of the halogen atoms in appropriate tetrabromo derivatives by pyrazoles in the superbasic system KOH-DMSO gave ditopic chelating ligands: 1,1,2,2-tetrakis(1H-pyrazol-1-yl)ethane, 1,4-bis[bis(1H-pyrazol-1-yl)methyl]benzene, and 1,4-bis[bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl]benzene. 1,4-Bis[bis(1H-pyrazol-1-yl)methyl]benzene was also synthesized by reaction of 1H-pyrazole with terephthalaldehyde in the presence of thionyl chloride. 1,1,2,2-Tetrakis(1H-pyrazol-1-yl)ethane was converted into the corresponding tetraiodo and tetranitro derivatives.     

Study of the effect of stabilizer on the degradation of poly(vinyl chloride) by pyrolysis–gas chromatography

The effect of stabilizer on the thermal degradation of poly(vinyl chloride) was studied by means of pyrolysis–gas chromatography. The stabilizers used in this study were dibutyltin dilaurate, dibutyltin bis(n-dodecyl mercaptide), barium stearate, and zinc stearate. PVC containing these stabilizers was degraded in a stream of nitrogen at temperatures ranging from 350 to 570°C. It was found that observed drastic reduction of benzene yield from the PVC containing zinc stearate had a close correlation with the formation of crosslinking structures.     

Synthesis of a symmetrical dithiirane

The reaction of p-xylene with epichlorohydrin in the presence of aluminum chloride gave 1,4-dimethyl-2,5-bis(1-chloro-2-hydroxypropyl)benzene, which serves as the starting compound for the synthesis of the corresponding symmetrical dithiirane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1319–1321, October, 1985.