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）.     

Novel pyridine-based ether ester diamine and resulting thermally stable poly (ether ester amide)s

A novel pyridine-based ether ester diamine was prepared in three steps. Reaction of 1,5-dihydroxy naphthalene with 4-nitrobenzoyl chloride afforded 5-hydroxy-1-naphthyl-4-nitrobenzoate (HNNB). Reduction of nitro group resulted in preparation of an amino compound named 5-hydroxyl-1-naphthyl-4-aminobenzoate (HNAB). The diamine was synthesized by nucleophilic substitution reaction of 5-hydroxyl-1-naphthyl-4-aminobenzoate with 2,6-dichloropyridine in the presence of K₂CO₃. The obtained diamine was fully characterized and used to prepare novel thermally stable poly (ether ester amide)s via polycondensation reaction with different aromatic and aliphatic diacid chlorides. All the polymers were characterized and their physical and thermal properties were studied.     

New poly(ester amide ether amide)s from a novel flexible diamine and different diacid chlorides using TMSCl for in situ silylation

A novel flexible diamine with built-in ester, amide and ether groups named terephthalic acid bis(4-{2-[2-(2-amino ethoxy)ethoxy]ethyl carbamoyl}phenyl) ester (TABE), was synthesized via two steps. Nucleophilic reaction of 4-hydroxybenzoic acid with terephthaloyl chloride in the presence of NaOH yielded terephthaloyl bis (4-oxybenzoic) acid (TOBA). The diamine (TABE) was prepared via two direct and indirect methods. In the indirect method TOBA was converted to related diacid chloride and reacted with 1,8-diamino-3,6-dioxaoctane (DADO). Direct method was achieved through the reaction of TOBA with DADO via Yamazaki method. TOBA and TABE were fully characterized and TABE was used to prepare new poly(ester amide ether amide)s through polycondensation with different diacid chlorides in the presence of trimethylchlorosilane (TMSCl). The polymers were characterized using conventional methods and their physical properties including inherent viscosity, thermal behavior, thermal stability, crystallinity, and solubility were studied. The polymers showed good thermal stability and improved solubility.     

Synthesis of novel poly(aryl ether amide)s containing the phthalazinone moiety

Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[ 4-( 4-aminophenoxy) phenyl ]-(2H )-phtha-lazin-1-one and 1, 2-dihydro-2-( 4-aminophenyl )-4-[ 4-( 4-aminophenoxy) -3, 5-dimethylphenyl ] - (2H) -phthalazin-1-one were successfully synthesized using readily available heterocyclic bisphenol-like monomers through two steps in high yield. A series of novel poly( aryl ether amide)s containing the phthalazinone moiety with inherent viscosities of 1.16-1.67 dL/g were prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N, N-dimethyl-formamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide ( DMSO ), N-methyl-2-pyrrolidinone (NMP), and pyridine. The polymers had high glass transition temperatures (Tg) in the 291-329℃ range.     

Synthesis of photoreactive poly(ether ether ketone)s containing alkyl groups

Poly(ether ether ketone)s containing alkyl groups were prepared by nucleophilic substitution reaction of alkyl-substituted difluoro diaryl ethers with hydroquinone or by electrophilic substitution reaction of alkyl-substituted diaryl ether with 4,4′-oxydibenzoic acid in PPMA. Polycondensations proceeded smoothly and produced polymers having inherent viscosities up to 0.5-–1.6 dL/g. The polymers were quite soluble in strong acid, dipolar aprotic solvents, and chloroform at room temperature. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight loses of the polymers were observed in the range above 450°C in nitrogen atmosphere. The glass transition temperatures of the polymers ranged from 128 to 146°C. Furthermore, Polymer 3b functioned as a photosensitive resist of negative type for UV radiation. The resist had a sensitivity of 42 mJ/cm² and a contrast of 2.5, when it was postbaked at 100°C for 10 min, followed by development with THF/acetone at room temperature. © 1996 John Wiley & Sons, Inc.     

高磺化度芳香聚醚醚酮的合成与表征

用3,3'-二磺酸钠基-4,4-二氟二苯酮合成了具有高磺化度的荷电聚醚醚酮.用红外吸收光谱及DSC对其进行了表征.研究了共聚物的组成、热稳定性、溶解性、成膜性及磺化度对共聚物性能的影响.     

Novel fluorinated polyimides derived from an unsymmetrical diamine containing trifluoromethyl and methyl pendant groups

Novel fluorinated polyimides were prepared from an unsymmetrical diamine, 3‐methyl‐4‐(4‐amino‐2‐trifluoromethylphenoxy)‐4'‐aminobenzophenone ( 3 ), with four aromatic dianhydrides via a one‐step high‐temperature polycondensation procedure. All the obtained polyimides were soluble in some polar solvents such as NMP, DMAc, and DMF. Flexible and tough films were prepared by casting from polymer solution. These polyimide films exhibited high optical transparency, good mechanical and thermal properties. Moreover, they possessed low dielectric constants and low‐moisture absorption. Due to their properties, these fluorinated polyimides could be considered as photoelectric and microelectronic materials. Copyright © 2010 John Wiley & Sons, Ltd.     

新型可溶性聚芳醚酮的合成与表征

聚芳醚酮是一类具有独特的耐热性、耐疲劳性、耐辐射性、化学稳定性、阻燃性和介电性等诸多优异性能的工程塑料 ,广泛应用于航天、军事、电子、信息、核能和精密仪器等领域[1,2 ] .具有不同性质并有不同应用特性的聚芳醚酮的研究已有报道 [3～ 8] .将甲基、苯基和叔丁基等不同取代基引入到聚芳醚酮中可提高溶解性 ,改善加工性能 ,其中引入一些功能型侧基也可实现聚芳醚酮的功能化 .我们合成了一种含甲苯取代基的新型聚芳醚酮 ,大侧基的引入含影响到玻璃化转变温度 ( Tg)、结晶性和介电性能 ,可改善溶解性、成膜性及加工流动性等诸多性能 .…     

高Tg含萘聚芳醚酮的合成与性能

利用Friedel-Craft和去醚化反应成功地制备了具有对称取代结构的含萘双酚单体1,5-二(3-甲基)苯羰基-2,6-二羟基萘, 并且通过高温亲核取代反应制得了两种高分子量的芳香族聚合物, 对这两种新型聚合物的热性能、溶解性能、机械性能及介电常数等进行了表征.     

新型含氟聚芳醚酮的合成与表征

聚芳醚酮具有很高的热稳定性和优良的电性能及机械性能 ,已经被广泛应用于宇航、电子及核能等高技术领域 [1] .氟元素的引入可以降低材料介电常数、折光指数和吸水率 ,提高热稳定性、溶解性和阻燃性 ,增加材料透明度 ,使这类聚合物在光电子、光学和微电子等应用领域的研究倍受关注 [2～ 4 ] .本文在合成含三氟甲基苯侧基的聚芳醚酮 [5] 的基础上 ,设计并合成了新型的含氟量更高的单体和聚合物 ,并对其性能进行了初步研究 .1　实验部分1 .1　试剂与仪器　 [3,5 -二 (三氟甲基 ) ]苯代对苯醌 (自制 ) ;锌粉 ,A.R.级 ,天津化学试剂一厂产品 ;…     

Radiation degradation of poly(arylene ether ketone)s

The resistance of five poly(arylene ether ketone)s with related chemical structures to degradation by ionizing radiation has been studied by ESR spectroscopy and yields of volatile products. All of the polymers showed high resistance to radiation with low yields of radicals after irradiation in vacuum at 77 K (when up to 84% of the radicals were identified as radical anions) and much lower yields at 300 K. The yields of volatile products were much less than reported for poly(arylene sulfone)s [1, 2]. Methyl substitution on a main-chain aromatic ring decreased the radiation resistance, but methane only comprised 10% of the volatile products from the methyl-substituted polymers. A polymer containing an isopropylidene group in the main chain and a substituent aromatic carbonyl showed significantly decreased radiation resistance. Extremely low radical yields were obtained after irradiation in air at 300 K, contrary to many polymers. XPS analysis showed an increase in C–O bonds on the surface after irradiation in air.     

Fluorenyl-containing sulfonated poly(aryl ether ether ketone ketone)s (SPFEEKK) for fuel cell applications

A series of fluorenyl-containing sulfonated poly(aryl ether ether ketone ketone)s (SPFEEKK) were synthesized via aromatic nucleophilic substitution polymerization. The sulfonation content (SC) was controlled by the feed ratios of sulfonated and nonsulfonated monomers. Flexible and strong membranes in the sulfonic acid form were obtained from cast membranes in the sodium salt forms by treatment with acid. The thermal properties, water uptake, swelling ratio, water state, oxidative stability, proton conductivity and methanol permeability were investigated. All the polymers had proton conductivities greater than 1 × 10⁻² S/cm at room temperature, and the conductivity values of m-SPFEEKK-80 and p-SPFEEKK-80 were up to 1.86 × 10⁻¹ and 1.78 × 10⁻¹ S/cm at 100 °C. This series of polymers also possessed good dimensional stability in water and low methanol crossover.     

新型可溶性含氟聚芳醚酮的合成、表征及性能

制备了新型可溶性含氟聚芳醚酮高性能材料, 使该材料结合了含氟聚合物与聚芳醚酮两种材料的优点, 既具有很好的热稳定性、溶解性和阻燃性, 又有较低的介电常数和吸湿性[5,9,10]. 对于提高聚芳醚酮类材料的性能, 拓展其使用范围和加工方法具有很大的开发前景和实用价值.     

Synthesis and properties of novel poly(aryl ether ketone)s containing both 2,6‐naphthylene moieties and amide linkages in the main chains

A new monomer, 2,6‐bis(4‐phenoxybenzoyl)naphthalene (BPOBON), was easily synthesized via simple synthetic procedures from readily available materials. A series of novel poly(aryl ether ketone)s containing both 2,6‐naphthylene moieties and amide linkages in the main chains were prepared by the Friedel‐Crafts acylation solution copolycondensation of isophthaloyl chloride with a mixture of BPOBON and N,N'‐bis(4‐phenoxybenzoyl)‐1,4‐phenylenediamine (BPBPPD), over a wide range of BPOBON/BPBPPD molar ratios, in the presence of anhydrous AlCl₃ and N‐methylpyrrolidone in 1,2‐dichloroethane. All the polymers are semicrystalline and had remarkably increased T_gs over the conventional PEEK and PEKK due to the incorporation of naphthalene and amide linkages in the main chains. The polymers with 50–70 mol% BPOBON had not only high T_gs of 179–186 °C, but also moderate T_ms of 321–328 °C, which are very suitable for the melt processing. These polymers had tensile strengths of 101.5–107.1 MPa, Young's moduli of 2.13–2.39 GPa, and elongations at break of 11.8–13.7% and exhibited excellent thermal stability and good resistance to organic solvents. Copyright © 2013 John Wiley & Sons, Ltd.     

一种新型磺化聚醚醚酮的合成、表征和性能

以特丁基对苯二酚、3,3′-二磺酸钠基-4,4′-二氟二苯酮和4,4′-二氟二苯酮为单体,制备了具有高磺化度的聚醚醚酮.该系列聚合物可溶,并具有良好的成膜性.对聚合物及其膜的一些性能进行了研究.     

聚醚醚酮链段连接方式与其性能关系的研究

利用亲核取代反应,通过缩聚法合成了一种新型聚芳醚酮50％交替共聚物PEDEK-PETMDEK,通过¹HNMR证明其具有预期的结构.通过考察50％无规共聚物、50％交替共聚物、均聚物PEDEK和PET-MDEK的溶解性和热性能,发现聚醚醚酮共聚物的链段连接方式对聚合物性能有很大影响.50％交替共聚物是一种无定形固体,易溶于通常的有机溶剂,而50％无规共聚物却是半结晶聚合物,除浓硫酸外几乎不溶于任何溶剂;50％交替共聚物具有比50％无规共聚物更高的玻璃化转变温度.     

Synthesis and characterization of aromatic poly(ether ketone)s containing cyclotriphosphazene units

Bis(4-oxybenzoic acid) tetrakis(phenoxy) cyclotriphosphazene (IUPAC name: 4-[4-(carboxyphenoxy)-2,4,6,6-tetraphenoxy-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin-2-yl]oxy-benzoic acid) was synthesized and direct polycondensed with diphenylether or 1,4-diphenoxybenzene in Eaton's reagent at the temperature range of 80–120°C for 3 hours to give aromatic poly(ether ketone)s. Polycondensations at 120°C gave polymer of high molecular weight. Incorporation of cyclotriphosphazene groups in the aromatic poly(ether ketone) backbone greatly enhanced the solubility of these polymers in common organic polar solvents. Thermal stabilities by TGA for two polymer samples of polymer series ranged from 390 to 354°C in nitrogen at 10% weight loss and glass transition temperatures (T_g) ranged from 81.4 to 89.6°C by DSC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1227–1232, 1998     

含苯乙炔基的可交联聚芳醚酮交替共聚物的合成与热性能

以耐高温高性能树脂-聚芳醚酮作为研究对象, 从改善材料的加工工艺性及提高材料的使用温度出发, 对含有苯乙炔基的交替共聚物进行了系统研究. 实验结果表明, 该系列聚合物固化前具有较好的溶解性, 固化过程中显示出较好的热稳定性, 固化后具有较高的玻璃化转变温度和优异的热稳定性与热氧稳定性, 且降低聚合物的分子量没有对固化物的热性能产生明显影响, 在高性能复合材料基体树脂方面具有潜在的应用价值.     

High optical transparency and low dielectric constant of novel soluble polyimides containing fluorine and trifluoromethyl groups

A novel aromatic diamine containing fluorine and trifluoromethyl groups, α-bis(4-amino-3,5-difluorophenyl)-4-(trifluoromethyl)phenylmethane (1), was synthesized. Based on diamine 1 and four aromatic dianhydrides, a series of polyimides (PI) with high fluorine content were prepared via a one-step high-temperature polycondensation procedure. These obtained PIs were readily soluble in a variety of organic solvents, and they could afford flexible and strong films with low dielectric constants (2.57–2.84 at 1 MHz) and low moisture absorptions (0.23–0.45%). Thin films of these PIs exhibited high optical transparency and light color, with the cutoff wavelength at 311–354 nm and transmittance higher than 83% at 450 nm. Moreover, these PIs possessed eminent thermal stability and good mechanical properties.     

Relaxation behavior of aliphatic-aromatic poly(ether amide)s as revealed by dynamic mechanical and dielectric methods

The mechanical and dielectric relaxation of a set of aromatic-aliphatic polyamides containing ether linkages have been examined as a function of temperature (−140 to 190°C) and frequency (3 to 10⁶ Hz). The polymers differ in the orientation (meta and para) of the aromatic rings, in the length of the aliphatic chain, and in the number of ether linkages per repeating unit. Dynamic mechanical experiments showed three main relaxation peaks related to the glass transition temperature of the polymers (α relaxation), the subglass relaxations associated to the absorbed water molecules (β) and to the motion of the aliphatic moieties (γ). Dielectric experiments showed two subglass relaxation processes (β and γ) that correlates with the mechanical β and γ relaxations, and a conduction process (σ) above 50°C that masks the relaxation associated to the glass transition. A molecular interpretation is attempted to explain the position and intensity of the relaxation, studying the influence of the proportion of para- or meta- oriented phenylene rings, the presence of ether linkages and the length of the aliphatic chain. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 457–468, 1997