含氮杂环聚芳醚酮三元共聚物的性能

聚芳醚酮是一种新型热塑性耐高温高分子材料,具有优异的力学性能、电性能、抗辐射性能等,特别适合作高性能复合材料的基质及超级工程塑料,关于聚芳醚酮已有多篇文章报道,而基于C-N偶合反应合成的聚芳醚酮报道甚少^[1],我们曾报道含氮杂环聚醚酮酮PPEKK的合成^[2].本文以1,4-二(4-氯代苯甲酰基)苯,4,4′-二氟二苯酮及4-(4-羟基苯基)-2,3-二氮杂 萘-1-酮为原料,合成了主链中含有C—N键的新型含氮杂环聚芳醚酮三元共聚物 (PPEKEKK),对共聚物的结构和性能进行了表征.     

高性能聚芳醚酮的合成与性能(Ⅰ)——对苯二酚、联苯二酚、4,4′,-二氟二苯酮三元共聚体系

聚醚醚酮(PEEK)具有突出的耐高温水解和耐辐照性能以及良好的断裂韧性,现已在核能、宇航等高技术领域得到应用。研制新型聚芳醚酮是目前十分活跃的课题。本文采用亲核取代路线,以对苯二酚、联苯二酚、4,4′-二氟二苯酮为单体合成了一系列含亚联苯结构的新型聚芳醚酮,并对基基本性能进行了测定。     

含二氮杂萘酮结构聚芳醚腈酮酮的合成及表征

以5种含杂萘联苯结构的单体与2,6-二氯苯腈、1,4-二(4-氟代苯甲酰基)苯为原料进行亲核缩聚反应,制备了一系列含有杂萘联苯结构的新型聚芳醚腈酮酮树脂.其特性粘度在0.51~1.15 dL.g-1之间.采用FT-IR,示差扫描量热仪(DSC),热重分析仪(TGA)对聚合物的结构和性能进行了表征,结果表明,聚芳醚腈酮酮的玻璃化转变温度(Tg)在252~294℃之间,10%热失重温度(Td)在457℃以上,具有优异的耐热性能.聚芳醚腈酮酮均可溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、和氯仿等极性非质子型有机溶剂中,聚合物均可溶解于NMP后浇铸得到透明的、韧性好的薄膜.     

氟取代聚芳醚酮低温合成及其结构研究

通过傅克酰基化反应合成4,4'-二(4-氟苯甲酰基)二苯醚、4,4'-二(五氟苯甲酰基)二苯醚、4,4'-二(4-氟苯甲酰基)二苯硫醚以及4,4'-二(五氟苯甲酰基)二苯醚4种长链双卤单体,并进一步制备了含二氮杂萘酮聚芳醚酮聚合物.通过多氟取代双卤单体在含二氮杂萘酮聚芳醚酮聚合物主链中引入氟原子.多氟取代双卤单体具有多...     

含4-苯基二氮杂萘酮结构共聚芳酯的合成及性能

以4-[4-(4羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮(DHPZ-DA)、4,4'-二羧基二苯醚(DAPE)和2,2'-二(4-羟基苯基)丙烷(PBA)为原料,采用溶液缩聚法,合成了一系列聚芳酯,其数均分子量在1.2×104～1.7×104之间.通过FTIR和1H-NMR对聚芳酯结构进行了表征.该系列...     

新型含环氧端基聚芳醚酮的合成及表征

以 4,4′ 二氟二苯酮和 4 (4 羟基苯基 ) 2 ,3 二氮杂萘 1 酮经亲核取代逐步聚合制得含二氮杂萘酮结构的聚芳醚酮低聚物 ,再与环氧氯丙烷反应制得了所需分子量的含环氧端基的聚芳醚酮 (E PPEK) .用FT IR和1H NMR表征了分子链结构 ,并测定了聚合物的玻璃化转变温度Tg 和溶解性 .     

侧链含萘可交联聚芳醚酮的合成及性能

以4,4'-二羟基苯基正戊酸和4,4'-二氟二苯酮为原料, 二甲基亚砜(DMSO)为溶剂, 采用亲核取代反应合成侧基含羧基的聚芳醚酮均聚物, 进一步与1-萘酚和2-萘酚接枝制备新型含萘可交联聚芳醚酮. 用核磁共振(NMR)、红外光谱(FTIR)、示差扫描量热(DSC)和热重分析(TGA)表征其结构和性能, 含萘聚芳醚酮在常用有机溶剂如N,N-二甲基乙酰胺(DMAc)、DMSO, 四氢呋喃(THF)中有良好的溶解性, 并具有很好的成膜性. DSC测试结果显示, 在170℃热处理2 h的交联聚合物的玻璃化转变温度(T_g)提高40℃. TGA数据显示接枝后的聚合物的5%热失重温度提高40~50℃, 证明其发生交联反应. 结果表明, 新型含萘可交联聚芳醚酮具有热固性树脂的耐溶剂和耐高温特性, 进一步拓宽了聚芳醚酮的应用前景.     

反应型共聚醚酮酮及其关环产物的合成与表征

自从 8 0年代初英国ＩＣＩ公司[1] 将以 4,4′ 二氟二苯酮和氢醌为单体经溶液亲核取代反应合成的聚醚醚酮 (ＰＥＥＫ)投放市场以来 ,聚芳醚酮作为一类新型耐热高分子材料备受瞩目 .由于这类材料具有优异的绝缘性、良好的机械性能、自熄性以及高的耐辐射性等 ,在微电子和航天航空等高科技领域中广泛应用 .为了克服已工业化品种因为高的结晶性带来的难溶解、难溶融、难加工的缺点 ,90年代人们将目光投向合成无定形、可溶解的新型聚芳醚酮 ,比较成功的方法有[2～ 7] :( 1 )在分子主链中引入柔性基团 ;( 2 )采用不对称单体以减小聚合物的结晶性 …     

二甲基取代杂环联苯聚芳醚的合成与性能

由自制的二甲基取代类双酚4-(3,5-二甲基-4-羟基苯基)-2,3-二氮杂萘-1-酮(DM-HPPZ)单体和4,4'-二氟二苯酮、4,4'-二氯二苯砜进行亲核缩聚反应,制备了一类新型的二甲基取代聚芳醚酮、聚芳醚砜及其共聚物聚芳醚砜酮树脂材料.在适宜的聚合条件下,获得了高分子量的聚合物,其特性粘度为0.44～0.75DL·g^-1.利用DSC和TGA研究了聚合物的耐热性能,结果表明,新型聚芳醚玻璃化温度高(568～595K),耐热稳定性好(5%热失重温度大于416℃);拉伸强度为45.4～85.0MPa,力学性能优良.新型聚芳醚在氯仿、DMAc等极性有机溶剂中可溶解并浇铸得到透明、韧性高的薄膜.共聚物结合了聚醚酮好的力学性能和聚醚砜高的耐热性的特点,因此综合性能更佳.     

甲基取代的聚芳醚酮酮酰亚胺树脂的合成与性能

N,N′-(4,4′-二苯甲烷)-二偏苯三甲酰亚胺酰氯(DIDC-M)与4,4′-二(2-甲基-苯氧基)三苯二酮(o-Me-DPOTPDK) 进行低温溶液共缩聚,制备了甲基侧基取代的聚芳醚酮酮酰亚胺(o-Me-PEKKI)聚合物.用FT-IR,1H-NMR,DSC,TG 和WAXD对聚合物的结构和性能进行了表征.研究表明:聚合物为非晶态结构;具有较高的玻璃化转变温度(Tg:241 ℃)和较好的耐热性能(Td:487 ℃);能溶解于间甲酚、NMP、氯仿、四氯乙烷等有机溶剂中.     

Synthesis and properties of aromatic poly (ether sulfone)s and poly (ether ketone)s based on methyl-substituted biphenyl-4,4′-diols

Novel methyl-substituted aromatic poly (ether sulfone)s and poly (ether ketone)s were synthesized from combinations of 3,3′,5,5′-tetramethylbipheny-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol, and 4,4′-dichlorodiphenyl sulfone and 4,4′-difluorobenzo-phenone by nucleophilic aromatic substitution polycondensation. The polycondensations proceeded quantitatively in a N-methyl-2-pyrrolidone-toluene solvent system in the presence of anhydrous potassium carbonate to afford the polymers with inherent viscosities between 0.86 and 1.55 dL/g. The methyl-substituted poly (ether sulfone)s and poly (ether ketone)s showed good solubility in common organic solvents such as chloroform, tetrahydrofuran, pyridine, m-cresol, and N,N-dimethylacetamide. The tetramethyl- and hexamethyl-substituted aromatic polyethers had higher glass transition temperatures than the corresponding unsubstituted polymers, and did not decompose below 350°C in both air and nitrogen atmospheres. The films of the methyl-substituted poly (ether ketone)s became insoluble in chloroform by the irradiation of ultraviolet light, indicating the occurrence of photochemical crosslinking reactions. © 1994 John Wiley & Sons, Inc.     

含二氮杂荼酮结构新型聚芳醚系列高性能聚合物的合成与性能

从分子结构设计出发 ,以价廉易得的苯酚、苯酐为原料 ,经温和的工艺合成了结构全新的 4 ( 4′ 羟基苯基 ) 2 ,3 二氮杂萘 1 酮 (DHPZ) ,对其合成反应路线、合成反应动力学、反应机理进行了深入研究 .在大量实验研究基础上 ,结合分子立体结构的计算机模拟 ,确认其具有非共平面扭曲结构特征 ,其N—H键和O—H键具有类似的反应活性 ,是一种类似双酚的新单体 .以DHPZ与多种市售双卤单体如二氟二苯酮 (DFK)、二氯二苯砜 (DCS)、二氯二苯双酮 (DCKK)、二氯二苯腈 (DCBN)等经溶液亲核取代逐步聚合反应制得一系列含二氮杂萘酮结构的新型高性能聚醚砜 (PPES)、聚醚酮 (PPEK)、聚醚砜酮 (PPESK)、聚醚酮酮 (PPEKK)、聚醚砜酮酮(PPESKK)、聚醚腈酮 (PPENK)、聚醚腈砜 (PPENS)、聚醚腈砜酮 (PPENSK)等 ,对其结构进行了谱学表征 ,对其性能进行了全面测试 ,研究了其结构与性能关系 .谱学数据证明皆为无定型高聚物 .其玻璃化温度Tg 在 2 5 0～370℃之间 ,可以通过取代基团结构或主链上砜 酮基团比例进行调控 .在大量实验研究基础上 ,创造性提出“引入全芳环非共平面扭曲分子链结构赋予高聚物既耐高温又可溶解的优异综合性能”的分子结构设计理论 .在此分子设计理论指导下 ,设计并合成了含联苯二氮杂萘酮结构的新型二     

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.     

含蒽醌结构聚芳醚砜的合成及表征

以4,4'-二氟二苯砜,4,4'-联苯二酚及1,5-二氯蒽醌为原料,采用亲核缩聚方法将具有良好热稳定性的蒽醌生色团分子以共价键方式引入到聚芳醚砜体系中,制备出了蒽醌含量分别为10%、20%及30%的热分解温度在500℃以上的新型耐高温有机高分子染料.该系列聚合物具有较高的分子量和良好的溶解性.利用红外光谱(FTIR)、核磁共振(1H-NMR)等表征方法确定了聚合物的结构;利用紫外-可见光谱测试(UV-Vis)初步研究了聚合物的光谱学特性;利用差示扫描量热测试(DSC)和热失重分析测试(TGA)研究了聚合物的热性能.     

SYNTHESIS AND CHARACTERIZATION OF PHTHALAZINONE POLY(ARYL ETHER SULFONE KETONE)WITH CARBONYL GROUP*

A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfoneketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)-1(2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin insulfolane in the presence of K_2CO_3 to produce high molecular weight polymers which can be dissolved in some polarsolvents such as chloroform and nitrobenzene at room temperature and can be easily can into flexible, yellowish andtransparent films. PPESK is an amorphous polymer having a decomposition temperature above 400℃, which indicates that ithas high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agentindicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (ΔE) ofthe cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively.Therefore, the cross-linking reaction is approximately a first order reaction.     

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.     

Synthesis,curing and properties of poly(phthalazione ether sulfone ketone) copolymers crosslinked by click chemistry

Functionalized poly(phthalazinone ether sulfone ketone) was synthesized by successive chloromethylation and azidation, followed by curing reaction with the propargyl end-groups of various molecular weight crosslinking agents in the presence of Cu(Ⅰ) catalyst via the azide-alkyne click reaction. The influences of the chain length of crosslinking agents on the poly(phthalazinone ether sulfone ketone) system were studied. FTIR and DSC tests demonstrated certain crosslinking by azide-alkyne reaction with the formation of triazole ring. DSC results showed that curing temperature shifted to lower temperatures considerably in the presence of Cu(Ⅰ) catalyst. TGA showed cured polymers were of much higher thermal stability, including higher thermal decomposition temperatures and higher char-yielding properties. After being cured, the polymers became insoluble in organic solvents and the gel fraction of the cured polymers exceeded 71%. Wide-angle X-ray diffraction results indicated there was a short distance order in the poly(ether sulfone)(PES) main chain except for the azido methyl poly(phthalazinone ether sulfone ketone) and 4,4'-bis(2-propynyloxy) biphenyl( AMPPESK-BP) system.     

Synthesis and characterization of novel poly（aryl ether sulfone ketone）s containing phthalazinone and biphenyl moieties

A novel series of poly（aryl ether sulfone ketone）s （PPESKs） containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were between 38,330 and 67,900. The glass transition temperatures （Tg） and 5% decomposition temperatures were ranged in 253-269 ℃ and 488-500 ℃, respectively, The structures of these copolymers were confirmed by FT-IR and ^1H NMR. Moreover, all the resultant copolymers were amorphous determined by wide angle X-ray diffraction （WAXD）.     

Side-Chain Sulfonated Poly(arylene ether)s for Fuel Cell Applications

Summary: Poly(arylene ether sulfone)s of high molecular weight and narrow molecular weight distribution were obtained by melt polycondensation of 4,4′-difluorodiphenyl- sulfone and trimethylsilylethers of 4,4′-dihydroxydiphenylsulfone and phenylhydroquinone using CsF as catalyst. Although a block-like structure of the polymers could be expected from the course of reaction, only a single T_g ranging from 190 °C to 230 °C could be detected by DSC and which depended on the copolymer composition. Contrary to the sulfonation of similar poly(ether ether ketone)s the poly(arylene ether sulfone)s here reported were sulfonated both in the side chain and the main chain. Nonetheless the sulfonated poly(arylene ether sulfone)s showed high hydrolytic stability in water at 130 °C.     

含甲基磺化杂萘联苯聚醚砜酮质子交换膜材料的合成与性能

以4-(3,5-二甲基-4-羟基苯基)2,3-二氮杂萘-1-酮,3,3′-二磺酸钠-4,4′-二氟苯甲酮和4,4′-二氯二苯砜为原料,利用亲核缩聚反应,通过改变磺化单体的含量,制备出一系列不同磺化度的杂萘联苯聚醚砜酮(SPPESK-DM).采用FTIR、1H-NMR表征了聚合物的结构,热失重分析仪研究了聚合物的耐热稳定性,以N-甲基-2-吡咯烷酮为溶剂采用溶液浇铸法成膜研究该系列聚合物膜的性能.结果表明,SPPESK-DM磺酸基的热分解温度在260℃以上,主链分解温度在410℃以上;膜的吸水率、溶胀率、离子交换容量和质子传导率均随着磺化度的增大而增大,磺化度为1.0的SPPESK-DM50的质子传导率达到1.08×10-2S/cm(85℃),且甲醇渗透系数为2.06×10-7cm2/s,低于Nafion117膜的甲醇渗透系数(2×10-6cm2/s).此系列膜的耐氧化性比较优异,可望用于质子交换膜燃料电池中.