STUDIES ON BIPYRIDINIUM SALTS AND THEIR POLYMERS Ⅰ. SYNTHESIS OF 4, 4''-(1, 4-PHENYLENE-)BIS-[N-ALKYL (ARYL)-2, 6-DIPHENYL-] PYRIDINIUM SALTS AND THEIR POLYMERS FROM CORRESPONDING BIPYRYLIUM SALT*

The reaction of pyrylium salt with primary amine has been utilized to synthesize 4,4'-bipyri-dinium salts and pyridinium polymers. Seven new 4,4'-(1,4-phenylene-) bis-[N-alkyl(aryl)-2,6-diphenyl-] pyridinium perchlorates 4 and five corresponding bipyridinium polymers 5 were preparedwith good yields from 4,4'-(1,4-phenylene-) bis-(2,6-diphenyl-) pyrylium perchlorate 3. Preliminarytests have been made for their redox behavior and catalytic activity.     

Synthesis and Properties of Aromatic Poly(Ether Sulfone)s and Poly(Etherketone)s Containing Naphthalene or Quinoline Units,and Methyl-Substituted Biphenyl-4,4′-Diols

Abstract

A series of poly(ether sulfone)s and poly(ether ketone)s were synthesized from combinations of 1,5- and 2,6-bis(4-fluorosulfonyl)naphthalene, 2,6-bis(4-fluorobenzoyl)naphthalene, and 2,6-bis(4-fluorobenzoyl)quinoline with 3,3′,5,5′-tetramethylbiphenyl-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol. The polycondensations proceeded quantitatively in diphenylsulfone in the presence of anhydrous potassium carbonate to afford polymers with inherent viscosities between 0.40 and 1.28 dL/g measured in N-methyl-2-pyrrolidone or concentrated sulfuric acid. The tetramethyl- and hexamethyl-substituted aromatic polyethers exhibited good thermal stability, did not decompose below 330°C in both air and nitrogen atmospheres, and had higher glass transition temperatures than the corresponding unsubstituted polymers. The methylsubstituted poly(ether sulfone)s and poly(ether ketone)s showed good solubility in such common organic solvents as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, tetrahydrofuran, chloroform, and 1,4-dioxane.     

Polymerization by oxidative coupling. II. Co-redistribution of poly(2,6-diphenyl-1,4-phenylene ether) with phenols

Poly(2,6-diphenyl-1,4-phenylene ether) reacts with phenols in the presence of an initiator to form a mixture of low molecular weight hydroxyarylene ethers. Although the reaction is similar to the equilibration of poly(2,6-dimethyl-1,4-phenylene ether) with phenols, higher reaction temperatures and larger initiator concentrations are required. Compounds as 3,3′,5,5′-tetraphenyl-4,4′-diphenoquinone, tert-butyl perbenzoate, and benzoyl peroxide are active initiators. The structure of the polymer affects the extent to which the polymer equilibrates.     

一种杂环磺化聚芳醚腈酮质子交换膜材料的合成及表征

用含二氮杂萘酮结构类双酚DHPZ,3,3′-二磺酸钠基-4,4′-二氟二苯酮,2,6-二氯苯腈以及4,4′-二氟二苯酮,通过缩合共聚合反应合成了一系列不同磺化度、高分子量的磺化聚芳醚腈酮.聚合物特性粘数为0·58~2·0dL/g.用红外光谱(FT-IR),核磁共振谱(1H-NMR)表征了聚合物结构.用差示扫描量热仪(DSC)和热重分析仪(TGA)研究了聚合物的耐热性能,研究表明其玻璃化温度(Tg)可达352℃,5%热失重温度大于500℃.以N-甲基吡咯烷酮为溶剂,溶液浇铸法制备了聚合物膜,并测定了膜的溶胀率以及质子交换能力.结果表明,与Nafion膜相比,磺化聚芳醚腈酮膜在相同的质子交换能力条件下,溶胀率显著降低.     

苯并二噁唑系列聚合物的合成及表征

以4,6-二氨基-1,3-苯二酚盐酸盐为原料,分别和对苯二甲酸、1,4-萘二甲酸、2,6-萘二甲酸、2,5-噻吩二甲酸、4,4-′(1,2-二苯基乙烯)二甲酸在多聚磷酸介质中反应,合成单环的聚(1,4-亚苯基)苯并二噁唑(PBO)、稠环的聚(1,4-亚萘基)苯并二噁唑(1,4-PNBO)和聚(2,6-亚萘基)苯并二噁唑(2,6-PNBO)、杂环的聚(2,5-亚噻吩基)苯并二噁唑(PTBO)及含有两个苯环的聚-4,4′-亚(1,2-二苯乙烯基)苯并二噁唑(4,4′-PDPEBO).采用傅立叶红外光谱、热重分析、元素分析、特性黏数分析对系列聚合物进行了表征.研究结果表明PBO、1,4-PNBO、4,4-′PDPEBO、2,6-PNBO和PTBO 5种聚合物的耐热性能依次降低,特性黏数依次为25.40、16.76、20.63、15.38和14.63 dL/g.     

Entangled coordination polymers with mixed N- and O-donor organic linkers: a case of module-matching priority

A series of four coordination polymers showing entangled architectures based on cobalt and mixed N-donor/O-donor ligands, namely [Co(4,4'-BPIPA)(TP)]·2DMF (1), [Co(4,4'-BPIPA)(2,6-NDC)(DMF)]·DMF (2), [Co(4,4'-BPIPA)(2,6-NDC)]·2DMF (3) and [Co(4,4'-BPIPA)(4,4'-BPDC)]·2DMF (4) (4,4'-BPIPA = N,N'-bis-4-pyridinyl-isophthalamide, TP = terephthalic acid, 2,6-NDC = 2,6-naphthalenedicarboxylic acid, 4,4'-BPDC = 4,4'-biphenyldicarboxylic acid), have been synthesized under solvothermal conditions. Complex 1, containing 4,4'-BPIPA and relatively short dicarboxylate ligands (TP), exhibits two-dimensional (2D) two-fold interpenetration of double wavy 4(4)-sql nets. Complex 2 displays interesting 2D→3D parallel polycatenation of undulated 2D 4(4)-sql layers built by 4,4'-BPIPA and moderate dicarboxylate ligands (2,6-NDC). Complexes 3 and 4, although constructed of dicarboxylate ligands with different lengths (moderate 2,6-NDC and long 4,4'-BPDC), possess similar 3-fold interpenetration of identical self-catenated single nets with 6(5)·8-mok topologies. It has been found that the length of the dicarboxylate ligands plays a key role of module-matching in the self-assemblies of complexes 1-4. Moreover, the effect of the conformations of 4,4'-BPIPA, which can be controlled by tuning reaction temperatures, is also discussed.     

Blends of an epoxy thermosetting polymer with aromatic liquid-crystalline polyesters

A series of aromatic liquid-crystalline polyesters with different composition have been synthesized to adjust transition temperatures and molecular weight. Miscibility of polyesters with bisphenol-A-diglycidyl ether (DEGBA), 4,4′-methylene-bis(3-chloro-2,6-dimethylaniline) (MCDEA) and the influence on transition temperatures has been studied. Miscibility of binary and ternary mixtures was found over the whole range of composition depending on the temperature. Thermoset formation by curing of LC-polyester / DEGBA / MCDEA mixtures containing different amounts of polyester resulted in reaction-induced phase separation with polyester content from 30 to 50 wt.%. Cloud point techniques, scanning electron microscopy (SEM) and dynamic mechanical thermal analysis (DMTA) have been applied.     

Polyesters from 2,6-dihydroxy-9,10-dihydro-9,10-ethanoanthracene and 2,6-dihydroxyanthracene

High molecular weight, film-forming, amorphous polyesters have been prepared from 2,6-dilydroxy-9,10-dihydro-9,10-ethanoanthracene with adipic, sebacic, dodecanoic, isophthalic, 4,4′-oxybibenzoic, 2,6-naphthoic, 4,4′-bibenzoic, and terephthalic acid. Thermal elimination of ethylene from these polymers has yielded the corresponding polyesters from 2,6-dihydroxyanthracene which were of high molecular weight, film forming, and crystalline.     

Polyamides from 2,6,(7)-diamino-9,10-dihydro-9,10-ethanoanthracene and 2,6,(7)-diaminoanthracene

High-molecular-weight, film-forming, amorphous polyamides have been prepared from 2,6(7)-diamino-9,10-dihydro-9,10-ethanoantracene with adipic, sebacic, dodecanoic, isophthalic, 4,4′-oxybibenzoic, 2,6-naphthoic, 4,4′-bibenzoic, and terephthalic acid. Thermal elimination of ethylene from these polymers has yielded the corresponding polyamides from 2,6(7)-diaminoanthracene which were of high molecular weight, film forming, and crystalline.     

Low dielectric thermoset. II. Synthesis and properties of novel 2,6‐dimethyl phenol–dipentene epoxy

A 2,6‐dimethyl phenol–dipentene adduct was synthesized from dipentene (DP) and 2,6‐dimethyl phenol, and then a 2,6‐dimethyl phenol–DP epoxy was synthesized from the reaction of the resultant 2,6‐dimethyl phenol–DP adduct and epichlorohydrin. The proposed structures were confirmed by Fourier transform infrared, elemental analysis, mass spectra, NMR spectra, and epoxy equivalent weight titration. The synthesized 2,6‐dimethyl phenol–DP adduct was cured with 4,4‐diamino diphenyl methane, phenol novolac, 4,4‐diamino diphenyl sulfone, and 4,4‐diamino diphenyl ether. The thermal properties of the cured epoxy resins were studied with differential scanning calorimetry, dynamic mechanical analysis, dielectric analysis, and thermogravimetric analysis. These data were compared with those for the bisphenol A epoxy system. The cured 2,6‐dimethyl phenol–DP epoxy exhibited a lower dielectric constant (ca. 3.1), a lower dissipation factor (ca. 0.065), a lower modulus, lower thermal stability (5% degradation temperature = 366–424 °C), and lower moisture absorption (1.21–2.18%) than the bisphenol A system but a higher glass‐transition temperature (ca. 173–222 °C) than that of bisphenol A system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4084–4097, 2002     

Synthesis,Characterization and Comparison of Properties of Novel Fluorinated Polyimides Derived from Bisphenol–A‐di(phthaleic anhydride)

Four new poly(etherimide)s have been synthesized by reaction with commercially available bisphenol‐A‐(diphthaleic anhydride) (BPADA) with four different kinds of diamines, namely 4,4′‐bis(p‐aminophenoxy‐3,3″‐trifluoromethyl) terphenyl,4,4′‐bis(3″‐trifluoromethyl‐p‐aminobiphenyl ether)biphenyl,2,6‐bis(3′‐trifluoromethyl‐p‐aminobiphenyl ether)pyridine, 2,5‐bis(3′‐trifluoromethyl‐p‐aminobiphenylether)thiopene. The poly(etherimide)s are named as 1a, 1b, 1c and 1d, respectively. The synthesized polyimides show good solubility in various organic solvents. The polyimide films had low water absorption of 0.19–0.30% and low dielectric constant of 2.79–3.1 at 1 MHz. These polyimides showed very high thermal stability with decomposition temperature (5% wt loss) up to 522°C in nitrogen. Transparent thin films of these polyimides exhibited tensile strength up to 97 MPa, a modulus of elasticity up to 1.56 GPa and elongation at break up to 20%.     

双邻位甲基侧基聚芳醚酮醚酮酮/聚芳醚醚酮酮的合成与表征

聚芳醚醚酮酮(PEEKK)是继聚芳醚醚酮(PEEK)之后,由德国Hoechst公司开发出来的又一种全芳香结构热塑性耐高温特种工程塑料,由于PEEKK分子链规整性好,熔融温度高,加工成型非常困难,且具有极好的耐溶剂性,只能在浓硫酸等少数溶剂中可以溶解,使其应用受到了一定的限制,人们常常在主链上引入不同的大的基团(如萘环、二氮杂萘酮)、     

双水杨醛亚胺双核镍(Ⅱ)配合物降冰片烯加成聚合的研究

降冰片烯加成均聚产物具有好的热稳定性好和光学透明性,表现了优异的各向同性电性能,对金属具有很好的粘连附着性,可用于微电子器件的封装材料和液晶显示屏的保护涂层等领域,亦可作为耐高温工程材料使用,因而其制备和材料性能的研究备受学术界和企业界的青睐．降冰片烯加成聚合与传统的烯烃聚合具有许多相似     

Polyethers from 5,5′-methylene-bis (8-hydroxyquinoline)

Polyethers have been prepared by condensing the disodium salt of 5,5′-methylene-bis(8-hydroxyquinoline) (MBQ) with p-xylylene dichloride and dibromide, 4,4′-dichloromethyldiphenyl ether, 4,4′-dichloroacetyldiphenyl, 4,4′-dichloroacetyldiphenyl ether and methylene and ethylene dichlorides. All the polycondensations except those with the two aliphatic dihalides could be effected in dioxane and in DMF. The polycondensation of the disodium salt of MBQ with the two aliphatic dihalides could be effected in the absence of solvent in a sealed tube using Ullman catalysts. All the polyethers are insoluble in common organic solvents. I.R. spectra of the polyethers have been measured in KBr. The thermal and electrical properties of these polyethers have been studied.     

Microwave-assisted, Ir-catalyzed aromatic C–H borylation

One-step conversions of 1,3-disubstituted benzenes to aryl boronates and 2,6-disubstituted pyridines to heteroaryl boronates are described. Microwave heating was used for all reactions. [(COD)Ir(μ-OMe)]₂ and 4,4′-di-tert-butyl-2,2′-bipyridine were used as catalysts, in methyl tert-butyl ether. Acceleration of the rate of reaction was remarkable compared with that of same reaction under conventional heating conditions.     

SYNTHESIS AND CRYSTALLIZATION BEHAVIOR OF POLY(ETHER ETHER KETONE ETHER KETONE)(PEEKEK)*

In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) arereported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along thenucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallizationbehavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallizationfrom a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride(solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could beinduced by the above methods, and no polymorphism was found. The diflierences in the crystallization of PEEKEK inducedby the above methods are seen in their degree of crystallinity.     

Influence of the structure of the diol on the properties of aromatic polyesterimides

A series of aromatic polyesterimides with ester bonds in the side-chains has been obtained by the partial esterification of a polyamic acid prepared from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether with the following aromatic diols: 4,4′-di(2-hydroxyethoxy)-1,1′-binaphthyl, 2,2′-di(2-hydroxyethoxy)-1,1′-binaphthyl.di(2-hydroxyethoxy-1 -naphthyl)methane,2,2-di[4-(2-hydroxyethoxy)phenyl] propane.Influence of the structure of the diol on the thermal, mechanical and dielectric properties of resultant polymer foils has been studied. Properties of these foils have been compared with those obtained for the polypyromellitimide film of the 4,4′-diaminodiphenyl ether.     

含亚环己基荷电聚醚醚酮的合成表征与性能

以 3,3′ 二磺酸钠基 4,4′ 二氟二苯酮和 4,4′ 二氟二苯酮与 4,4′ 亚环己基双酚进行亲核共缩聚 ,合成了磺化度从 0 4～ 2 0的一系列含亚环己基的荷电聚醚醚酮 .聚合物除保持了荷电聚醚醚酮良好的热稳定性和机械性能外 ,还具有良好的耐水性 .聚合物的DSC和广角X射线衍射数据表明 :上述磺化度聚合物均呈无定型聚集态结构 .比较了聚合物与双酚A系列荷电聚醚醚酮的性能差异 ,讨论了聚合物的溶解特点     

Determination of tocopherols,tocopherolquinones and tocopherolhydroquinones by gas chromatography-mass spectrometry and preseparation with lipophilic gel chromatography

A method has been developed for the simultaneous determination of a range of aromatic amines using cation-exchange chromatography performed on a standard ion chromatography column using d.c. amperometric detection. The analytes separated were 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA), aniline, o-toluidine, benzidine, p-chloroaniline, 4,4'-diaminodiphenyl (4,4'-DDP), m-nitroaniline and 1-naphthylamine. A Dionex CS12 column was used with gradient elution from an initial eluent of 5% CH3CN+35 mM H2SO4 to 27% CH3CN+35 mM H2SO4 (at 35 min). Detection limits in the range 2.6-22.6 microg/l were observed for all analytes except m-nitroaniline, for which the detection limit was 201 microg/l. Linear calibrations and good precision were observed and the method was applied to the determination of benzidine, p-chloroaniline and 1-naphthylamine in wastewater samples. Further, the separation was also used (after some modification of the eluent conditions) for the determination of 2,4- and 2,6-toluene diisocyanate (2,4- and 2,6-TDI) and 4,4'-methylenediphenyl diisocyanate (4,4'-MDI) after their hydrolysis to 2,4-TDA, 2,6-TDA and 4,4'-DDP. Detection limits for 2,6- and 2,4-TDI and 4,4'-MDI were 3.8, 8.2, and 11.2 microg/l, respectively. The method was applied to the determination of diisocyanates in air.     

Coordination polymers containing rotaxane linkers

A class of coordination polymers in which the linking ligands are mechanically interlocked rotaxane molecules is reviewed. To date, four different, axle - wheel templating motifs have been used to create the [2]pseudorotaxane linkers for these unique solid-state materials; (1) protonated diaminoalkane axles with cucurbit[6]uril wheels, (2) 1,2-bis(4,4'-bipyridinio)ethane axles with dibenzo[24]crown-8 wheels, (3) 2,6-naphthalene dicarboxylate axles with tetra-imidazolium macrocycle wheels and (4) a Cu(i) complex of a 1,10-phenanthroline containing dicarboxylate axle with a 1,10-phenanthroline containing crown ether wheel. The synthesis and solid state structure of each coordination polymer is described. The future directions of this area of research and some designs for the next generation of these compounds are discussed.