含磺酸钠基的杂萘联苯聚芳醚砜酮的合成与表征

对4,4'-二氯二苯砜进行磺化改性制得磺化二氯二苯砜,不同比例的4,4'-二氯二苯砜和磺化二氯二苯砜与含二氮杂萘酮结构的类双酚单体(DHPZ)及4,4'-二氟二苯酮共聚合制得不同磺化度的磺化聚醚砜酮.对磺化单体及聚合物进行了IR和¹HNMR表征,并研究了聚合物的溶解性和成膜性能.     

新型直接交联磺化聚芳醚砜燃料电池用质子交换膜的合成及性能

以4,4′-二氟二苯砜、4,4′-联苯二酚、3,3′-二磺化-4,4′-二氟二苯砜二钠盐和三羟基苯为原料, 经高温溶液缩聚反应, 制备了一系列不同磺化度的新型交联磺化聚芳醚砜(CSPAES). 利用1H NMR和FTIR对聚合物结构进行表征. 采用溶液浇铸法制备了聚合物膜. 对膜的离子交换容量、吸水率、尺寸变化、机械性能和质子导电率进行了分析. 结果表明, 通过交联处理的磺化聚芳醚砜的水溶胀性明显降低, 当IEC为2.43时, CSPAES膜M(6/4-5)在水中的质子导电率达到260.5 mS/cm, 约为相同条件下Nafion112的2倍.     

Synthesis,characterization, and blends of high temperature poly(arylether sulfone)s

The preparation of poly(4-oxy-1,4-phenylenesulfonyl-4,4′-biphenylene-4-sulfonylphenylene) (PBP) has been accomplished by the base mediated, polycondensation reaction between two biphenyl containing monomers. The bisphenol, 4,4′-bis[(4-hydroxyphenyl) sulfonyl]biphenyl (HSB), was reacted with 4,4′-bis[(4-chlorophenyl)sulfonyl]-biphenyl (CSB) in tetramethylene sulfone solvent. The highest mechanical properties and glass transition temperature was observed for polymer PBP with a reduced viscosity around 1.0 dL/g. Consequently, the current synthesis route provides polymer with higher properties than other historical preparative routes. Blends of PBP with a different poly(ether sulfone) were miscible based on the observance of a single glass transition temperature. The T_gs of the polymer blends exhibited an unusual positive deviation from the weighted linear averages of the components.     

含砜基和二氮杂萘酮结构的聚酰亚胺无规共聚物的合成与性能

芳香聚酰亚胺是重要的高性能工程塑料品种之一 ,但是大多数刚性棒状分子链的全芳聚酰亚胺不溶于普通的有机溶剂 ,而且直至其分解温度也不熔 ,这给聚酰亚胺的加工带来困难 ,因此 ,限制了它的使用[1 ] .提高聚酰亚胺的可加工性并能保持其优异的耐热性能是目前研究的热点 .为了提高聚酰亚胺的溶解性能 ,基于分子设计的基本原则[2 ] ,合成了一种鲜见报道的非对称的含二氮杂萘酮结构的新型二酐单体 ,其结构为 :ＯＯＯＯＮＮＯＯＯＯ　　本文以 4,4′ 二氨基二苯醚和 4,4′ 二氨基二苯砜为共缩聚型聚酰亚胺的二胺单体 ,与等当量的该二酐单体利用“…     

Effect of the SO2 group in the diamine fragment of polyimides on their structural, thermophysical, and mechanical properties

Experimental and theoretical investigations, including an all-atom computer simulation, are performed for block samples of thermoplastic polyimides, amorphous R-BAPS (based on R dianhydride 1,3-bis(3??,4-dicarboxyphenoxy)benzene and diamine BAPS 4,4??-bis(4??-aminophenoxy)biphenyl sulfone), and crystallizable R-BAPB (based on R dianhydride and diamine BAPB 4,4??-bis(4??-aminophenoxy)biphenyl), which differ in either the presence or absence of the sulfone group in the repeating unit of the polyimide macromolecule. The features of thermophysical, structural, and mechanical properties of R-BAPS and R-BAPB are related to the formation of associates from sulfur and oxygen atoms of the sulfone group that are stabilized by electrostatic interactions.     

Synthesis and characterization of poly(phthalazinone biphenyl ether sulfone ketone)s from 4,4′-dichlorobenzophenone

A series of poly(aryl ether sulfone ketone)s containing phthalazinone and biphenyl moieties were synthesized by aromatic nucleophilic displacement polycondensation of 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one (DHPZ), 4,4′-dichlorobenzophenone (DCB), 4,4′-dichlorodiphenyl sulfone (DCS) and 4,4′-biphenol (BP) in different molar ratios. The obtained copolymers were characterized by different instrumental techniques (FTIR, TGA, DSC, WAXD, etc.). The inherent viscosities of these polymers were in the range of 0.43–0.56 dL g⁻¹. They were amorphous and had good solubility in polar aprotic organic solvents. The copolymers exhibited high glass transition temperatures (T _gs) between 225°C and 256°C and excellent thermal stability up to 517–526°C (thermal decomposition temperatures for 5% weight loss, T _{d, 5%}) in nitrogen. The tensile strength and elongation at break of the polymers ranged from 63 MPa to 71 MPa and from 18% to 21%, respectively. The processability of the material was effectively improved by the introduction of biphenyl group into polymer backbone.     

Co‐poly(aryl ether sulfone)s containing phthalimidine moiety in the main chain

Several new co‐poly(arylene ether sulfone)s have been prepared by the reaction of 4,4′‐fluorodiphenyl sulfone (FDS) with different bisphenols namely 4,4′‐isopropylidenediphenol (BPA), 4,4′‐hexafluoroisopropylidenediphenol (6F‐BPA), and N‐phenyl‐3,3‐bis(4‐hydroxyphenyl)phthalimidine(PA). The homo‐poly(arylene ether sulfone)s are named as 1a, 2a, and 3a. The copolymers namely 2b, 2c, 2d and 3b, 3c, 3d have been prepared, respectively, on reaction of FDS with BPA or 6F‐BPA using different molar ratios of PA such as 25, 50, and 75. The poly(aryl ether sulfone)s 1a containing PA unit in the main chain showed a very high glass transition temperature of 280°C and an outstanding thermal stability up to 510°C for 5% weight loss under synthetic air. Depending on the mole% of PA, the glass transition temperatures of the copolymers can be varied. The polymers were soluble in a wide range of organic solvents. Transparent thin films of these polymers exhibited tensile strengths upto 84 MPa and Young's modulus up to 3.16 GPa. The films of these polymers showed low water absorption of 0.24%. Copyright © 2009 John Wiley & Sons, Ltd.     

用于燃料电池的磺化聚芳醚砜质子交换膜材料的直接合成与性能研究

将磺化二氯二苯砜(SDCDPS)、二氯二苯砜(DCDPS)与4,4′-联苯酚(BP)通过亲核缩聚反应得到一系列具有不同磺化度的磺化聚芳醚砜(SPAES)共聚物.通过FT-IR,TGA和DSC等分析方法对其结构及性能进行表征.并用透射电镜对其内部形态进行分析,建立了结构与性能之间的关系.研究了不同磺化度对膜性能的影响.结果表明,聚合物中磺酸基团的增多导致了磺化聚芳醚砜膜的吸水率、离子交换容量、质子传导率和甲醇渗透系数的增加.通过对膜的综合性能评价发现,磺化度为0.8的磺化聚芳醚砜膜在80℃时的质子传导率为0.116S/cm,100℃时的质子传导率为0.126S/cm,均高于Nafion117膜(0.114S/cm和0.117S/cm),且甲醇渗透系数为8.4×10-7cm2/s,远远低于Nafion117膜(2.1×10-6cm2/s).     

Preparation of silicon containing polymers. II.. Effect of structure on the thermal stability of organosilicon aramids

Two silicon-containing acid dichlorides, bis(4-chlorocarbonylphenyl)dimethylsilane and bis(4-chlorocarbonylphenyl)diphenylsilane, were synthesized and reacted with 1,3-phenylene diamine, 1,4-phenylene diamine, 4,4′-diaminodiphenyl, 4,4′-diaminodiphenyl methane 4,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl sulfone in the preparation of 12 structurally different high molecular weight aromatic polyamides. A low-temperature interfacial polycondensation technique was used. Most of the polyamides formed tough, transparent, flexible films and were characterized by solubility, solution viscosity, infrared spectroscopy (IR), and glass transition temperature (T_g). The thermal behavior of these aramids was studied by dynamic thermogravimetry. The effect of diamine and acid dichloride structure on the aramids properties is also discussed.     

Synthesis and studies of homopolyamides based on 2,4-bis(6-chlorocarbonyl-2-naphthyloxy)-6-(4-methyl-1-piperazinyl)-s-triazine

Abstract  

Ten homopolyamides have been synthesized by polycondensation of the monomer 2,4-bis(6-chlorocarbonyl-2-naphthyloxy)-6-(4-methyl-1-piperazinyl)-s-triazine and different diamines such as 4,4′-biphenyldiamine, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfonamide, 2,4-diaminotoluene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and ethylenediamine. All polyamides were characterized by solubility, density, viscosity measurements, IR, NMR spectroscopy, and thermogravimetric analysis. The products were found to possess high thermal stability.     

Arylidene Copolyether Sulfones. I. Synthesis and Characterization of Some New Copolyether Sulfones Containing Dibenzylidene Cyclopentanone Moieties

Abstract

New copolyether sulfones containing 2,5-bis(4-oxo-benzylidene)-cyclopentanone moieties were prepared in the conventional literature manner by condensing the dipotassium salts of 2,5-bis(4-hydroxyphenzyl- idene)cyclopentanone (I) and 2, 2-bis(4-hydroxyphenyl)propane (Bisphenol A, III) with 4,4′-dichlorodiphenyl sulfone (II), or by condensing the dipotassium salts of I with chlorine-terminated Bisphenol A-4,4′-di-chlorodiphenylsulfone copolymers (V). The resulting copolyether sulfones were confirmed by IR, viscometry, DSC measurements, thermooptical (TOA), and thermogravimetric analysis (TGA).     

Addition polyimides. III. Thermal behavior of bismaleimides

This article describes the synthesis of N,N′-bis(3,3′-maleimidophenyl) sulfone (S) and its Michael addition products with (4,4′-diaminodiphenyl) methane (S-M), 4,4′-diaminodiphenyl ether (S-E), (3,3′-diaminodiphenyl) sulfone (S-DDS_m), (4,4′-diaminodiphenyl) sulfone (S-DDS_p), (3,3′,3″-tris aminophenyl) phosphine oxide (S-TAP), and 9,9-bis(p-aminophenyl) fluorene (S-B). Curing behavior of these bisimides was investigated by differential scanning calorimetry. Activation energy of curing reaction was determined by using isothermal and multiple heating rate method. Thermal stability of bisimides was evaluated by thermogravimetric analysis. Better char yields were obtained in S-TAP resins.     

三元共聚脲序列分布及二胺反应活性比的研究

以己二胺(HDA)、间苯二胺(MPD)、4,4'-二氨基二苯醚、4,4'-二氨基二苯甲烷、4,4'-二氨基二苯砜及2,4-甲苯二异氰酸酯为原料,合成了一系列三元共聚脲,以三元共聚序列结构分析的理论为基础,建立了一套普适性较强的利用核磁氢谱分析和计算机分峰处理,研究三元共聚脲在不同反应条件下的序列结构方法,计算了无规度B值和链段序列长度L_na与L_nb.定量关联了不同反应条件下二胺单体间的反应活性比.结果表明,二胺单体间的反应活性比随反应条件的变化而变化     

Synthesis and characterization of thermally stable poly(ether-azomethine)s derived from 1,1-bis[4-(4-benzaldehyde oxy)-3-methyl phenyl] cyclopentane

A new dialdehyde 1,1-bis[4-(4-benzaldehyde oxy)-3-methyl phenyl] cyclopentane (BBMPC) was synthesized starting from cyclopentanone and O-cresol to give 1,1-bis(4-hydroxy-3-methyl phenyl)cyclopentane (BHMPC); followed by reaction with 4-fluorobenzaldehyde in N, N-dimethyl formamide (DMF), containing anhydrous potassium carbonate. New series of poly(ether-azomethine)s were synthesized from (BBMPC) with different diamines such as 4,4′- diamino diphenyl ether (ODA); 4,4′-diaminodiphenyl methane (MDA); 4-aminophenyl sulfone (SDA); p-phenylene diamines (p-PDA), etc. in N, N’- dimethyl acetamide (DMAc) with 5 wt% LiCl by the solution polycondensation method. Inherent viscosities of these polymers were in the range 0.20 to 0.38 dL/g indicating formation of moderate molecular weights. These polymers exhibited good solubility in various polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), DMAc, DMF, etc. However some polymers showed partial solubility in DMF and DMAc. X-Ray diffraction pattern of polymers showed amorphous nature. Thermal stability was assessed by 10% weight loss temperature and the degradation temperature of the resultant polymers falls in the ranges from 444-501°C in nitrogen. The glass transition temperature was in the range of 155-205°C. The structure-property correlation among these polyazomethines were studied; in view of their potential applications as high performance polymers.     

Sulfone-linked paracyclophanes via macrocyclic aromatic thioethers: synthetic and structural investigations

Reaction of 4,4'-sulfonylbis(benzenethiol) with 4,4'-dichlorodiphenylsulfone under pseudo-high-dilution conditions leads to macrocyclic thioethersulfones [-S-Ar-SO2-Ar-]n (Ar = 1,4-phenylene). These include a highly strained [1+1] cyclodimer (n = 2), a cyclotrimer resulting from thioetherexchange reactions, and a [2+2] cyclotetramer which can adopt two entirely different conformations in the crystalline state, one having molecular D2d ("tennis-ball-seam") symmetry. The same type of reaction is successful using 4,4'-thiobis(benzenethiol) instead of 4,4'-sulfonylbis(benzenethiol) and affords macrocycles with a higher ratio of thioether to sulfone linkages. Exhaustive oxidation of macrocyclic thioethersulfones with hydrogen peroxide affords a series of sulfone-linked paracyclophanes, [-Ar-SO2-]4, [-Ar-SO2-]6, [-Ar-SO2-]8 and [-Ar-SO2-]12. Single crystal X-ray analysis reveals [Ar-SO2-]4 to be a near-perfect square box, whilst the cyclic hexamer [-Ar-SO2-]6 adopts a much more irregular conformation. and [-Ar-SO2-]8 displays a "double-box" structure clearly related to that of [Ar-SO2-]4.     

Polyquinoxalines. III

Six thermally stable polyquinoxalines have been prepared by the reactions of combinations of three tetraamines, 3,3′,4,4′-tetraaminodiphenyl sulfone (II), and 3,3′,4,4′-tetraaminodiphenyl ether (V), with two bisglyoxals, 4,4′-diglyoxalyldiphenyl sulfide dihydrate (III) and 4,4′-diglyoxalyldiphenyl sulfone dihydrate (IV). The polymers were prepared from polymerization in two stages. The first stage, a solution polymerization, produces an initially low or moderate molecular weight material, which is advanced to a high molecular weight (η_inh > 1.0) by heating at 375°C. under reduced pressure. All the polyquinoxalines have excellent thermal stability both in nitrogen and in air and improved solubility.     

Sequence analysis of poly (ether sulfone) copolymers by 13C NMR

Random and block copolymers of poly (ether sulfone) (PES) and poly (ether ether sulfone) (PEES) were synthesized by the nucleophilic polycondensation of 4,4′‐dichlorodiphenyl sulfone (DCDPS) with 4,4′‐dihydroxydiphenyl sulfone (DHDPS) and hydroquinone (HQ). Chemical structures of these copolymers were characterized by ¹³C NMR. The monomer molar fraction, sequential distribution, and degree of randomness of the copolymers were determined through analyses of the resonances of quaternary carbons in the DCDPS unit. Experimental results show that the molar fractions of the comonomer determined by ¹³C NMR analyses are close to the charged values in the synthetic step. Moreover, these copolymers, which were prepared by different polymerization methods, revealed different number‐average sequential length and degree of randomness. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1624–1630, 2005     

Synthesis and Characterization of Polyesterimides Containing Ether Linkages

Abstract

Three novel dicarboxylic acids, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl sulfone, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl methane, and bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl ether, were synthesized, and several polyesterimides were prepared from diacid chlorides and bisphenols by solution polycondensation. The polymers were obtained in 65–88% yield and had inherent viscosities in the 0.18 to 0.64 dL/g range. The polymers were characterized by IR, elemental analysis, x-ray, TGA, DSC, and solubility tests. All the polymers were readily soluble in polar aprotic solvents and had a 10% weight loss temperature above 375°C in nitrogen.     

Direct copolymerization of sulfonated poly(phthalazinone arylene ether)s for proton‐exchange‐membrane materials

Sulfonated poly(phthalazinone ether ketone) (SPPEK) copolymers and sulfonated poly(phthalazinone ether sulfone) (SPPES) copolymers containing pendant sodium sulfonate groups were prepared by direct copolymerization. The reaction of disodium 3,3′‐disulfonate‐4,4′‐difluorobenzophenone (SDFB‐Na), 4,4′‐difluorobenzophenone (DFB), and 4‐(4‐hydroxyphenyl)‐1(2H)‐phthalazinone (DHPZ) at 170 °C in N‐methyl‐2‐pyrrolidione containing anhydrous potassium carbonate gave SPPEKs. SPPESs were similarly obtained with 3,3′‐disulfonate‐4,4′‐difluorophenyl sulfone, 4‐fluorophenyl sulfone (DFS), and DHPZ as monomers. The sulfonic acid groups, being on deactivated positions of the polymer backbone, were expected to be hydrolytically more stable than postsulfonated polymers. Fourier transform infrared and ¹H NMR were used to characterize the structures and degrees of sulfonation of the sulfonated polymers. Membrane films of SPPEKs with SDFB‐Na/DFB molar feed ratios of up to 60/40 and SPPESs with sulfonated 4‐fluorophenyl sulfone/DFS molar feed ratios of up to 50/50 were cast from N,N‐dimethylacetamide polymer solutions. Membrane films in acid form were then obtained by the treatment of the sodium‐form membrane films in 2 N sulfuric acid at room temperature. An increase in the number of sulfonate groups in the copolymers resulted in an increased glass‐transition temperature and enhanced membrane hydrophilicity. The sodium‐form copolymers were thermally more stable than their acid forms. The proton conductivities of the acid‐form copolymers with sulfonated monomer/unsulfonated monomer molar feed ratios of 0.5 and 0.6 were higher than 10^?2 S/cm and increased with temperature; they were less temperature‐dependent than those of the postsulfonated products. SPPESH‐50 showed higher conductivity than the corresponding postsulfonated poly(phthalazinone ether sulfone). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2731–2742, 2003     

4,4’-二氯二苯酮合成二氮杂萘联苯酮结构聚醚砜酮的研究

以4-(4-羟基苯基)*2,3-二氮杂萘-1-酮(DHPZ)、4,4’-二氯二苯砜(DCS)和4,4’-二氯二苯酮(DCK)为原料,采用分步加料的方法,合成了系列高分子量的聚芳醚砜酮共聚物(PPESKs),其特性黏度在0.40 ～0.61dL/g之间,解决了由于DCK活性低不适合用于聚芳醚合成的问题.采用FTIR、示差...