含氰侧基联苯型聚芳醚醚酮酮的合成及表征

通过一种反应条件较为温和的反应新工艺,合成联苯二甲酰氯,即4,4’-二氯甲酰基联苯(BC IBP)。然后,在无水A lC l3及N-甲基吡咯烷酮(NMP)/1,2-二氯乙烷(DCE)复合溶剂的存在下,将2,6-二苯氧基苯甲腈(DPOBN)与BC IBP进行低温缩聚反应,合成了一类新型含氰侧基联苯型聚芳醚醚酮酮。用IR,DSC,TG,WAXD及元素分析等方法对其结构和性能进行了表征。结果表明,所合成的聚合物具有预期结构且为非晶态聚合物;其玻璃化转变温度(Tg)为211℃,在氮气气氛中及在空气气氛中的热分解5%的温度(Td)分别为523℃及498℃,说明其具有突出的耐高温性能;聚合物除了能在浓H2SO4,CF3COOH/CHC l3等强质子性溶剂当中溶解外,对其他的溶剂均不溶解,说明聚合物具有优异的耐化学腐蚀性能。     

聚芳醚砜酮纤维的热性能

采用DSC、TG测定了含联苯结构聚芳醚砜酮 (PPESK)纤维的热性能 ,结果表明 ,纤维的玻璃化温度随砜酮比的增大而提高 ,纤维的起始分解温度大于 463℃。当砜酮比为 15 / 85 ,5 0 / 5 0 ,75 / 2 5时 ,纤维的玻璃化温度分别为 2 5 7.62 ,2 78.64 ,2 79.71℃ ;热分解活化能分别为 15 0 .8,2 19.9,195 .5kJ/mol;热分解反应级数分别为 1,1.76,1级     

间位苯基取代聚芳醚砜醚酮酮的合成与性能研究

以4,4′-二苯氧基二苯砜(DPODPS)、对苯二甲酰氯(TPC)和间苯二甲酰氯(IPC)为单体,无水AlCl3/二氯乙烷(DCE)/N,N-甲基甲酰胺(DMF)为催化溶剂体系,通过低温溶液共缩聚反应,合成系列聚芳醚砜醚酮酮(PESEKKs),用IR、DSC、WAXD、TG等技术对聚合物进行了结构和性能的表征,研究结果表明,随着高分子主链中间位苯基结构单元的增加,对共聚玻璃化转变温度(Tg)和热分解温度(Td)影响不大,熔融温度(Tm)和结晶则逐渐降低,但仍保持良好的耐热性,溶解性等到很大改善。     

Synthesis and properties of poly(aryl ether ketone ketone)/poly(aryl ether ether ketone ketone) copolymers with pendant cyano groups

2,6‐Diphenoxybenzonitrile (DPOBN) was synthesized by reaction of phenol with 2,6‐difluorobenzonitrile in N‐methyl‐2‐pyrrolidone in the presence of KOH and K₂CO₃. Poly(aryl ether ketone ketone)/poly(aryl ether ether ketone ketone) copolymers with pendant cyano groups were prepared by the Friedel–Crafts electrophilic substitution reaction of terephthaloyl chloride with varying mole proportions of diphenyl ether and DPOBN using 1,2‐dichloroethane as solvent and N‐methyl‐2‐pyrrolidone as Lewis base in the presence of anhydrous AlCl₃. The resulting polymers were characterized by various analytical techniques, such as FT‐IR, differential scanning calorimeter, thermal gravimetric analysis, and wide‐angle X‐ray diffraction. The crystallinity and melting temperature of the polymers were found to decrease with increase in concentration of the DPOBN units in the polymer. Thermogravimetric studies showed that all the polymers were stable up to 514°C in N₂ atmosphere. The glass transition temperature was found to increase with increase in concentration of the DPOBN units in the polymer when the molar ratios of DPOBN to DPE ranged from 10/90 to 30/70. The copolymers containing 30–40 mol % of the DPOBN units exhibit excellent thermostability at (350 ± 10)°C and have good resistance to acidity, alkali, and organic solvents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3601–3606, 2007     

Synthesis and properties of novel poly(phthalazinone ether ketone ketone)

A novel poly(phthalazinone ether ketone ketone) was prepared via the nucleophilic substitution polycondensation of bis-1,4-(4-chlorobenzoyl)benzene and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one. The synthesized polymer exhibited high glass-transition temperature, excellent thermooxidative properties, and fair rheological properties. The polymer was soluble in some polar solvents. Electronic friction and membrane properties are also discussed. The results indicate that the polymer falls in the class of high temperature resistance engineering plastics. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 823–826, 2001     

Rheological properties in blends of poly(aryl ether ether ketone) and liquid crystalline poly(aryl ether ketone)

Rheological properties of the blends of poly(aryl ether ether ketone) (PEEK) with liquid crystalline poly(aryl ether ketone) containing substituted 3‐trifluoromethylbenzene side group (F‐PAEK), prepared by solution precipitation, have been investigated by rheometer. Dynamic rheological behaviors of the blends under the oscillatory shear mode are strongly dependent on blend composition. For PEEK‐rich blends, the systems show flow curves similar to those of the pure PEEK, i.e., dynamic storage modulus G′ is larger than dynamic loss modulus G″, showing the feature of elastic fluid. For F‐PAEK‐rich systems, the rheological behavior of the blends has a resemblance to pure F‐PAEK, i.e., G″ is greater than G′, showing the characteristic of viscous fluid. When the PEEK content is in the range of 50–70%, the blends exhibit an unusual rheological behavior, which is the result of phase inversion between the two components. Moreover, as a whole, the complex viscosity values of the blends are between those of two pure polymers and decrease with increasing F‐PAEK content. However, at 50% weight fraction of PEEK, the viscosity‐composition curves exhibit a local maximum, which may be mainly attributed to the phase separation of two components at such a composition. The changes of G′ and G″ with composition show a trend similar to that of complex viscosity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4040–4044, 2006     

Synthesis and characterization of poly(ether sulfone) and poly(ether sulfone ketone) copolymers

Poly(ether sulfone) and poly(ether sulfone ketone) copolymers (I–V) were synthesized by the nucleophilic substitution reaction of 4,4′-dihydroxy diphenyl sulfone (DHDPS, A) with various mole proportions 4,4′-difluoro benzophenone (DFBP, B) and 4,4′-difluoro diphenyl sulfone (DFDPS, C) using sulfolane as solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by physicochemical and spectroscopic techniques. All polymers were found to be amorphous, and the glass transition temperature (T_g) was found to increase with the sulfonyl content of the polymers. ¹³C-nuclear magnetic resonance (NMR) spectral data was interpreted in terms of the compositional triads, BAB, BAC, CAC, ABA, and ABB, and indicate that transetherification occurs at high concentration of DFBP units in the polymer (IV). The good agreement between the observed and calculated feed ratios validates the triad analysis. Thermal decomposition studies reveal that the thermal stability of the polymers increases with increase in the carbonyl content in the polymer. Activation energies for thermal decomposition were found to be in the range of 160–203 kJ mol⁻¹ with the cleavage of ϕ SO₂ bond being the preponderant mode of decomposition and depended on the block length of the sulfonyl unit. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2113–2121, 1999     

Synthesis and characterization of novel soluble poly(ether ketone sulfone)s with pendant polychloro groups

A novel monomer of tetrachloroterephthaloyl chloride (TCTPC) was prepared by the chlorination of terephthaloyl chloride catalyzed by ferric chloride at 175–180°C for 10 h and confirmed by FTIR, MS, and elemental analysis. Five new polychloro substituted poly(aryl ether ketone sulfone)s (PEKSs) with inherent viscosities of 0.68–0.75 dL/g have been prepared from 4,4′‐diphenoxydiphenylsulfone, 4,4′‐bis(2‐methylphenoxy) diphenylsulfone, 4,4′‐bis(3‐methylph‐enoxy)diphenylsulfone, 4,4′‐bis(2,6‐dimethylphenoxy)diphenylsulfone, and 4,4′‐bis(1‐naphthoxy)‐diphenylsulfone with TCTPC by electrophilic Friedel‐Crafts acylation in the presence of DMF with anhydrous AlCl₃ as a catalyst in 1,2‐dichloroethane, respectively. These polymers having weight–average molecular weight in the range of 76,600–83,900 are all amorphous and show high glass transition temperatures ranging from 213 to 250°C, the 5% weight loss temperature over 450°C, high char yields of 60–67% at 700°C in nitrogen and good solubility in CHCl₃ and polar solvents such as DMF, DMSO, and NMP at room temperature. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 85.1–90.8 MPa, Young's moduli of 2.52–3.24 GPa, and elongations at break of 21.2–27.2%. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of poly(aryl ether sulfone ether ketone ketone) (PESEKK)

4,4′‐bis(Phenoxy)diphenyl sulfone (DPODPS) was synthesized by reaction of phenol with bis(4‐chlorophenyl) sulfone in tetramethylene sulfone in the presence of NaOH. Two poly(aryl ether sulfone ether ketone ketone)s (PESKKs) with high molecular weight were prepared by low temperature solution polycondensation of DPODPS and terephthaloyl chloride (TPC) or isophthaloyl chloride (IPC), respectively, in 1,2‐dichloroethane and in the presence of aluminum chloride (AlCl₃) and N‐methylpyrrolidone (NMP). The resulting polymers were characterized by various analytical techniques, such as FT‐IR, ¹H‐NMR, DSC, TG, and WAXD. The results show that the T_g and T_d of PESEKKs are much higher, but its T_m is lower than those of PEKK. The other results indicate that PESEKKs exhibit excellent thermostabilities at 300 ± 10°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 489–493, 2005     

聚芳醚酮/含甲基侧基聚芳醚砜醚酮酮的合成与表征

以2，2’-二甲基-4,4'-二苯氧基二苯砜(o-CH3-DPODPS)、二苯醚(DPE)和对苯二甲酰氯(TPC)为单体，在无水A1C13、1，2-二氯乙烷和N，N-二甲基甲酰胺存在下，通过低温溶液缩聚反应。合成了一系列新型含甲基侧基的聚芳醚酮／聚芳醚砜无规共聚物。用FT-IR，WAXD，DSC和TG等方法对聚合物进行了表征。结果表明，随着2,2'-二甲基-4，4'-二苯氧基二苯砜含量的增加，共聚物的玻璃化转变温度逐渐提高，熔融温度则逐渐下降。     

Preliminary investigation of poly(ether sulfone)/poly(aryl ether ketone) containing 1,4‐naphthalene blends

The blends of poly(ether sulfone) and poly(aryl ether ketone) containing 1,4‐naphthalene were prepared by melt mixing in a Brabender‐like apparatus. The specimens for measurements were made by compression molding under pressure and then were water‐quenched at room temperature. The tensile strength, tensile modulus, elongation at break, thermal analysis, and scanning electron microscopy were each measured. The dependence of tensile strength, tensile modulus, and elongation at break on blend systems was obtained. The effects of composition and miscibility on the mechanical properties are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 472–476, 2006     

Synthesis and characterization of novel poly(aryl ether ketone ketone)s containing the o‐dibenzobene moiety

The synthesis of a novel chloro monomer containing the 1,2‐dibenzoylbenzene moiety was described. The chloro monomer was reacted with 4‐(4‐hydroxyphenyl)‐1(2H)‐phthalazinone compound in the presence of excess anhydrous potassium carbonate in an aprotic solvent (Sulfolane), and high molecular weight amorphous poly(aryl ether ketone ketone) was synthesized. The polymers with high glass transition temperature were soluble in solvents such as chloroform and nitrobenzene at room temperature and easily cast into flexible, colorless, and transparent films. The 5% weight loss of the polymers was >400 °C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1487–1492, 2001     

Synthesis of novel poly(phthalazinone ether sulfone ketone)s and improvement of their melt flow properties

A series of novel poly(phthalazinone ether sulfone ketone)s was synthesized from bis(4-fluorophenyl) ketone, bis(4-chlorophenyl)sulfone, and 4-(4-hydroxybenzyl)-2,3-phthalazin-1-one through nucleophilic substitution polycondensation. The synthesized polymers exhibited surprisingly high glass transition temperatures and had excellent thermooxidative properties. The melt viscosities of these synthesized polymers are generally too high to be processed by common processing methods because of their very high glass transition temperatures and amorphous microstructure. An attempt was made to reduce their melt viscosities by solution blending the synthesized polymer with two kinds of oligomers: low molecular weight poly(phthalazinone ether sulfone ketone) and commercial poly(ether sulfone). The results proved that the addition of the oligomers to the polymers led to a marked decrease in melt viscosities. Furthermore, no obvious changes were observed in the thermal and mechanical properties of these blends after oligomer additions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1425–1432, 1997     

Synthesis and properties of poly(aryl ether sulfone)s containing the phthalazinone moiety

Three series of poly(aryl ether sulfone)s (PAESs) containing the phthalazinone moiety in the polymer backbone were synthesized by solution polycondensation of bis(4-chlorophenyl) sulfone with three commercial bisphenols and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one. Bisphenol-A, hydroquinone, and bis(4-hydroxyphenyl) sulfone, or bisphenol-S, were selected as the commercial bisphenols for copolymerization. The synthesized polymers exhibited very high glass transition temperatures and excellent thermooxidative properties. They also showed superior mechanical properties and fair rheological properties. The introduction of relatively flexible moieties, such as benzene rings, onto the poly(phthalazinone ether sulfone) (PPES) chain led to a decrease in glass transition temperature with respect to the phthalazinone homopolymer. However, the processability of PPES was improved dramatically by the addition of these commercial bisphenols. The properties of synthesized PAESs can be tailored by changing the molar ratios of bisphenols to phthalazinone monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:137–143, 1998     

Synthesis and characterization of novel soluble cardo poly(arylene ether ketone)s containing xanthene structures

9,9‐Bis(4‐hydroxyphenyl)xanthene (BHPX), a bisphenol monomer, was synthesized in 82% yield from xanthenone in a one‐pot, two‐step synthetic procedure. Four novel aromatic poly(ether ketone)s (PEKs) based on BHPX were prepared via a nucleophilic aromatic substitution polycondensation with four difluorinated aromatic ketones. The polycondensation proceeded in tetramethylene sulfone in the presence of anhydrous potassium carbonate and afforded the new cardo PEKs in nearly quantitative yields with inherent viscosities of 0.77–0.85 dL/g. High molecular weight PEKs having number‐average molecular weights (M_n's) in the range of 38,900–40,600 g/mol with the polydispersity index ranged from 1.97 to 2.06 are all amorphous and show high glass transition temperatures ranging from 210°C to 254°C, excellent thermal stability, and the temperatures at the 5% weight loss are over 538°C with char yields above 60% at 700°C in nitrogen. These new PEKs are all soluble in polar aprotic solvents such as N‐methyl‐2‐pyrrolidone and N, N′‐dimethylacetamide and could also be dissolved in chloroform and tetrahydrofuran. All the polymers formed transparent, strong, and flexible films with tensile strengths of 78–84 MPa, Young's moduli of 2.54–3.10 GPa, and elongations at break of 14–18 %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of sulfonated poly(phthalazinone ether sulfone ketone) for ultrafiltration and nanofiltration membranes

Modification of poly(phthalazinone ether sulfone ketone) (PPESK) by sulfonation with concentrated or fuming sulfuric acid as sulfonation agents was carried out to prepare membrane materials with increased hydrophilicity and potentially increased fouling resistance. Sulfonated PPESK (SPPESK) copolymers, with a degree of sulfonation ranging from 10–300%, were prepared and characterized. Factors affecting the sulfonation reaction were studied, and reaction conditions for the preparation of SPPESK with different degrees of sulfonation were determined. Compared with the properties of PPESK, the hydrophilicity of SPPESK was increased, as shown by a reduced contact angle with water. The glass transition temperature was increased from 278°C (PPESK) to a maximum of 323°C for the highly sulfonated derivative, due to the strong polarity of  SO₃H and hydrogen bonding. Ultrafiltration membranes prepared with PPESK and SPPESK were compared. For a SPPESK asymmetric membrane, the PEG12000 rejection was 98% and the water flux was 876 kg · m⁻² · h⁻¹. SPPESK/PPESK composite nanofiltration membranes were also prepared and were shown to have short‐term operational stability up to 120°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1685–1692, 2001     

新型含偶氮结构聚芳醚砜醚酮酮的合成与表征

在无水AlCl3及N-甲基吡咯烷酮(NMP)/1,2-二氯乙烷(DCE)复合溶剂的存在下,将含砜基芳二醚类单体与含偶氮苯结构芳二甲酰氯进行低温付-克缩聚反应,合成了一类新型含偶氮结构聚芳醚砜醚酮酮树脂。用IR、TG、WAXD及元素分析等技术进行了结构表征和性能测试。结果表明:所合成的聚合物树脂具有预期结构且为非晶态聚合物;在N2气氛中质量损失5%的温度(Td)分别为445～463℃;聚合物除了能在浓硫酸、CF3COOH/CHCl3等强极性质子型溶剂中溶解外,还能溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等强极性非质子型溶剂中,也能在普通溶剂,如氯仿(CHCl3)、1,2-二氯乙烷(DCE)、四氢呋喃(THF)等中溶解。     

耐高温含氟聚芳醚酮和聚芳醚砜的合成与性能研究

通过三步反应合成新的含氟双酚单体3,4-二氟苯基对苯二酚,由该含氟双酚单体、4-氟苯基对苯二酚、邻苯基对苯二酚分别与4,4′-二氟二苯酮、4,4′-二氯二苯砜经亲核缩聚反应,制备了一系列新型聚芳醚酮和聚芳醚砜。采用 FT-IR、DSC、TGA及XRD手段等对聚合物的结构和性能进行了表征和研究,结果表明：合成的聚芳醚酮和聚芳醚砜具有优异的耐热性能,玻璃化转变温度分别在150~159 ℃和177~196 ℃之间,氮气中5 %热失重温度分别在527 ℃和507 ℃以上。合成的聚芳醚酮和聚芳醚砜具有良好的溶解性,室温下能溶解在N-甲基吡咯烷酮、二甲基乙酰胺、氯仿等有机溶剂中。     

含氯侧基聚芳醚酮醚酮酮的合成与表征

以α-萘酚为原料，通过和4，4′-二氟二苯酮在N，N-二甲基乙酰胺（DMAC）及K2CO3中的缩合反应制备了一种含萘环的新型芳醚单体4，4′-二（α-萘氧基）二苯酮（DNBP），将其分别与2，5-二氯对苯二甲酰氯（DCTPC）。对苯二甲酰氯（TPC）等芳二酰氯通过在NMP/AlCl3/ClCH2CH2Cl复合溶剂/催化剂体系中的低温溶液进行亲电共缩聚反应，合成了一系列在分子主链芳环上引入侧基氯原子的同时，又在主链中引入刚性萘环结构的新型聚芳醚酮醚酮酮无规共聚物。     

聚醚砜/磺化聚醚醚酮共混膜的制备和性能

采用流延法制备了聚醚砜(PES)含量不同的PES/磺化聚醚醚酮(SPEEK)共混膜。PES与SPEEK具有良好的相容性。所制备PES/SPEEK共混膜的含水率、溶胀度和甲醇透过系数均随PES含量的增加而降低。虽然共混膜的质子传导性能有所降低.但阻醇性能和溶胀性能提高,这说明PES/SPEEK共混膜是一种很好的直接甲醇燃料电池用固体高分子电解质膜材料。