Synthesis and properties of poly(arylene ether imide ketone)s

Poly(arylene ether ketone)s containing imide units were prepared by the aromatic nucleophilic displacement reaction of the potassium salts of bisphenols with bis(4-fluorobenzoyl)phthalimides in N-methyl-2-pyrrolidone at elevated temperature. The polymers having inherent viscosities of 0.34–0.77 dL/g were obtained in 2 h. The polymers exhibited glass transition temperatures ranging from 216 to 268°C and decomposition temperatures (5% weight loss under air atmosphere) ranging from 450–570°C mainly depending on the bisphenols used in the polymer synthesis. The isothermal TGA measurements (400°C under air or nitrogen atmosphere) revealed that the 4,4'-biphenol- and hydroquinone-based poly(arylene ether ketone imide)s belong to a superior class of heat resistant polymers. The mechanical properties of these polymers are also described. © 1994 John Wiley & Sons, Inc.     

Synthesis and properties of poly(arylene ether phenyl-s-triazine)s

A series of new poly(arylene ether phenyl-s-triazine)s was prepared by the nucleophilic aromatic substitution polymerization of the potassium salt of bisphenols with 2,4-bis (halophenyl)-6-phenyl-s-triazine in N-methyl-2-pyrrolidone at elevated temperature. The polymers with inherent viscosities exceeding 0.5 were obtained after polymerization for 1 h using 2,4-bis(fluorophenyl)-6-phenyl-s-triazine as a monomer. The glass transition temperatures of the resulting polymers ranged from 200 to 260°C depending on the bisphenol used in the polymer synthesis. The poly(arylene ether phenyl-s-triazine)s demonstrated excellent thermal stabilities in excess of 490°C (5% weight loss in air). The isothermal TGA measurements (400°C under air or nitrogen atmosphere) revealed that the 4,4'-biphenol- and hydroquinone-based poly(arylene ether phenyl-s-triazine)s belong to the most superior class of heat resistant polymers, such as polyimide Kapton?. The mechanical properties of these polymers are also described. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of new fluorescent poly(arylene ether)s

The poly(arylene ether)s were prepared by the nucleophillic aromatic substitution polymerization of phenolphthalin and its derivatives with activated aromatic difluorides. The polymers had glass transition temperatures ranging from 210 to 240°C. Though the monomers have no fluorescence, the resulting polymers fluoresced a light green color in solid and solution states. The maximum excitation and emission wavelengths are 420 nm and 470 nm, respectively. In the polymer solutions, the fluorescence intensity decreased gradually, but the intensity was recovered by heating the polymer at 220°C for a few minutes. The fluorescent polymer had a stable radical. A model compound having the same repeating unit of the polymer was also prepared. The fluorescence properties of this model were almost the same as those of the polymers. © 1994 John Wiley & Sons, Inc.     

Sulfone-Containing polymers as high barrier materials

Three types of sulfone-containing polymers, poly(carbonate-sulfone)s, poly(ester-sulfone)s, and poly(urethane-sulfone)s, were characterized as high barrier materials. They were made by condensing sulfone-containing diol, 1,3-bis(3-hydroxypropylsulfonyl)propane (Diol-333), or 1,4-bis(3-hydroxypropylsulfonyl)butane (Diol-343), with diphenyl carbonate, diphenyl esters, and diisocyanates, respectively. The incorporation of polar sulfone groups into polymer backbones increases the glass transition temperature of polymers in all cases; however, the increment is different with different functional linkages. The increments in polycarbonates and polyesters are higher than that in polyurethanes. This is because the interactions between carbonate or ester groups are much weaker than the interactions between sulfone groups, whereas the hydrogen bonding between urethane groups is comparable with the polar interaction between sulfone groups. The polymers were coated on 50-μm-thick Kapton films by solution casting and their permeabilities toward carbon dioxide were measured at 25°C using the ASTM D1434 volumetric method. The sulfone-containing polymers have carbon dioxide permeability coefficients at least 50 times smaller than the corresponding polymers without sulfone groups. The carbon dioxide barrier properties of sulfone-containing polymers are comparable with ethylene/vinyl alcohol copolymers (EVAL), which are commercial high barrier polymers. An isomer effect on polymer permeability was observed in the aromatic-aliphatic poly(ester-sulfone) series. The permeability coefficients of the aromatic-aliphatic poly(ester-sulfone)s decrease from terephthalate to isophthalate to phthalate, corresponding to the increase of chain flexibility above the T_g. These results support the hypothesis that high chain flexibility in the rubbery state and a glass transition temperature above room temperature are two key factors that promote low permeability. © 1994 John Wiley & Sons, Inc.     

聚芳醚腈共聚物的合成与性能

以二卤代苯甲腈，对苯二酚，间苯二酚为原料，制备了几种不同间苯二酚／对苯二酚比的聚芳醚腈树脂。采用流涎成膜法制备了它们的薄膜。对薄膜样品进行了红外光谱分析和热分析，测定了力学性能，在扫描电子显微镜上观察了薄膜拉伸断面。     

Self-Crosslinkable poly(arylene ether)s containing pendent phenylenetriazene groups

Self-crosslinkable poly(arylene ether)s 6 , and 8 , containing pendent triazene groups were prepared by nucleophilic substitution reaction of poly(arylene ether)s 5 , and 7 , respectively, with 1-[4-(4-hydroxyphenoxy)phenylene]triazenes, 4 , in the presence of potassium carbonate in N,N-dimethylacetamide. A series of triazenes 4 containing various substituents have been synthesized. Self-crosslinkable polymer 6e containing phenyl-substituted triazene pendants can be crosslinked at 215°C, which is about 40°C lower than the glass transition temperature of the virgin base polymer 5 . The degree of crosslinking can be tailored by varying the concentration of the pendent phenylenetriazene groups in the polymer. After curing, the flexible polymer films (ca. 10 μm thick) exhibit high gel contents, increased glass transition temperatures, improved resistance to organic solvents, and little change in dielectric constant and thermal stability. These self-crosslinkable poly(arylene ether)s are potential candidates for electronic applications. © 1994 John Wiley & Sons, Inc.     

Synthesis,characterization, and comparison of properties of new fluorinated poly(arylene ether)s containing phthalimidine moiety in the main chain

Four new poly(arylene ether)s have been prepared by the reaction of N‐phenyl‐3,3‐bis(4‐hydroxyphenyl)phthalimidine (PA) with four different perfluoroalkylated monomers namely 1,3‐bis(4′‐fluoro‐3′‐trifluoromethyl benzyl) benzene, 4,4′‐bis(4′‐fluoro‐3′‐trifluoromethyl benzyl) biphenyl, 2,6‐bis(4′‐fluoro‐3′‐trifluoromethyl benzyl) pyridine, and 2,5‐bis(4′‐fluoro‐3′‐trifluoromethyl benzyl) thiophene. The poly(arylene ether)s were characterized by different spectroscopic, thermal, mechanical, and electrical techniques. The poly(arylene ether) containing quadriphenyl unit in the main chain showed very high glass transition temperature of 291°C and outstanding thermal stability upto 556°C for 10% weight loss under a 4:1 nitrogen:oxygen mixture. The polymers were soluble in a wide range of organic solvents. Transparent thin films of these polymers exhibited tensile strengths upto 75 MPa and elongation at break upto 32%. The films of these polymers showed low water absorption of 0.26%. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

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.     

Linear and Hyperbranched Poly(arylene ether)s from a New Semifluorinated AB Monomer

A new trifluoromethyl-activated AB monomer has been successfully synthesized by Pd-initiated coupling of 4-bromo anisole with 4-fluoro-3-trifluoromethylphenylboronic acid followed by demethylation. The monomer leads to a semifluorinated poly(arylene ether) by nucleophilic displacement polymerization reaction. The AB monomer has been further copolymerized with a corresponding AB ₂ monomer to form the corresponding semifluorinated hyperbranched (hb) poly(arylene ether). The resulting linear and hb poly(arylene ether)s exhibited weight average molecular weight of 75700 and 144100 g/mol, respectively. The hb copolymer exhibited better solubility in different organic solvents compared to the linear poly(arylene ether). The polymers showed excellent thermal stability up to 522°C at 10% wt loss in air and glass transition temperatures as high as 187°C. The mechanical properties of the linear poly(arylene ether) film 1a exhibited tensile strength at break of 89 MPa, elongation at break of up to 3% and a Young’s modulus value of 2.66 GPa. The films of the polymers were hydrophobic in nature and showed water contact angle as high as 93.6°.     

Synthesis of poly(ether-ketone-amide)s by palladium-catalyzed polycondensation of aromatic dibromides containing ether ketone structure,aromatic diamines,and carbon monoxide

Aromatic poly(ether-ketone-amide)s were prepared by the palladium-catalyzed polycondensation of aromatic dibromides containing ether ketone units, aromatic diamines, and carbon monoxide. Polymerizations were carried out in N,N-dimethylacetamide (DMAc) in the presence of palladium catalyst, triphenylphosphine, and 1,8-diazabicyclo [5,4,0]-7-undecene (DBU), and resulted in poly(ether-ketone-amide)s with inherent viscosities up to 0.82 dL/g under mild conditions. The polymers were quite soluble in strong acid, dipolar aprotic solvents, and pyridine. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight losses of the polymers were observed in the range above 400°C in nitrogen atmosphere. The glass transition temperatures of the polymers were about 200°C, which are higher than those of poly(ether-ketone) analogues. These polymers also showed good tensile strength and tensile modulus. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(arylene ether)s derived from 4,4′‐bishydroxybiphenyl and 4,4′‐bishydroxyterphenyl

A series of poly(arylene ether)s were successfully prepared by aromatic, nucleophilic substitution reactions with various perfluoroalkyl‐activated bisfluoromonomers with 4,4′‐bishydroxybiphenyl and 4,4′‐bishydroxyterphenyl. 4,4′‐Bishydroxyterphenyl was synthesized through the Grignard coupling reaction of magnesium salt of 4‐bromoanisole with dibromobenzene followed by demethylation with pyridine–hydrochloride. The products obtained by the displacement of fluorine atoms exhibited good inherent viscosity, up to 0.77 dL/g, and number‐average molecular weights up to 69,300. These poly(arylene ether)s showed very good thermal stability, up to 548 °C for 5% weight loss according to thermogravimetric analysis under synthetic air, and high glass‐transition temperatures, up to 259 °C according to differential scanning calorimetry, depending on the exact repeat unit structure. These polymers were soluble in a wide range of organic solvents, such as N‐methylpyrrolidone, dimethylformamide, tetrahydrofuran, toluene, and CHCl₃, and were insoluble in dimethyl sulfoxide and acetone. Thin films of these poly(arylene ether)s showed good transparency and exhibited tensile strengths up to 132 MPa, moduli up to 3.34 GPa, and elongations at break up to 84%, depending on their exact repeating unit structures. These values are comparable to those of high‐performance thermoplastic materials such as poly(ether ether ketone) (PEEK) and Ultem poly(ether imide) (PEI). These poly(arylene ether)s exhibited low dielectric constants. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 55–69, 2002     

Synthesis of poly (ether-sulfone-amide)s by palladium-catalyzed polycondensation of aromatic dibromides containing ether sulfone structure,aromatic diamines,and carbon monoxide

A general method for the preparation of aromatic poly (ether-sulfone-amide)s has been developed. Polymerization is based on the palladium-catalyzed polycondensation of aromatic dibromides containing ether sulfone structural units, aromatic diamines, and carbon monoxide. Reactions were carried out in N, N-dimethylacetamide (DMAc) in the presence of palladium catalyst, triphenylphosphine, and 1,8-diazabicyclo [5,4,0]–7–undecene (DBU), and gave a series of poly (ether-sulfone-amide)s with inherent viscosities up to 0.86 dL/g under mild conditions. The polymers were quite soluble in strong acids, dipolar aprotic solvents, and pyridine. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight losses of the polymers were observed in the range above 470°C in air. The glass transition temperatures of the polymers were around 230°C, which are higher than those of poly (ether-sulfone) analogues. These polymers also showed the good tensile strengths and tensile modulus. © 1994 John Wiley & Sons, Inc.     

Synthesis and Characterization of Novel Poly(Arylene Ether)s from 4,4′‐Thiodiphenol

Four novel perfluoroalkylated poly(arylene ether)s have been synthesized successfully using four perfluoroalkyl‐activated bisfluoro monomers. These polymers are synthesized through nucleophilic displacement of the fluorine atoms on the benzene ring with 4,4′‐thiodiphenol and are named as 1a, 1b, 1c and 1d, respectively. The polymers obtained by displacement of the fluorine atoms exhibit weight‐average molar masses up to 3.9×10⁴ g · mol^?1 in Gel permeation chromatography. These poly(arylene ether)s showed very high thermal stability up to 548°C for 10% weight loss in TGA under nitrogen and high glass transition temperature (T_g) up to 178°C in DSC depending on the repeat unit structures. The glass transition temperatures taken as peak in tan δ in DMA measurements are in good agreement with the DSC T_g values. All the polymers synthesized are soluble in a wide range of organic solvent such as CHCl₃, CHCl₂, THF, NMP, DMF and toluene. Transparent thin films of these polymers cast from THF exhibited tensile strengths up to 72 MPa, modulus up to 1.69 GPa with low elongation at break depending on their exact repeating unit structures. Rheological properties showed ease of processability of these polymers with no change in melt viscosity with temperature.     

Synthesis of thermally crosslinkable fluorine‐containing poly(arylene ether ketone)s—II. Propargyl ether terminated poly(arylene ether ketone)s

Novel thermally crosslinkable fluorine‐containing poly(arylene ether ketone)s comprised of 2,3,5, 6‐tetrafluoro‐1,4‐phenylene moiety were synthesized by the termination of polymer chain ends with propargyl ether groups in order to improve solvent resistance. Crosslinking reaction occurred over 250°C through the formation of both chromen ring and polyene structure. This structure change brought about not only the outstanding solvent resistance but also the increase in glass transition temperature (T_g). The cured films also exhibited excellent thermal stability, transparency and hydrophobicity derived from fluorine atoms. Copyright © 2004 John Wiley & Sons, Ltd.     

New poly(arylene ether)s with pendant phosphonic acid groups

Soluble brominated poly(arylene ether)s containing mono‐ or dibromotetraphenylphenylene ether and octafluorobiphenylene units were synthesized. The polymers were high molecular weight (weight‐average molecular weight = 115,100–191,300; number‐average molecular weight = 32,300–34,000) and had high glass‐transition temperatures (>279 °C) and decomposition temperatures (>472 °C). The brominated polymers were phosphonated with diethylphosphite by a palladium‐catalyzed reaction. Quantitative phosphonation was possible when 50 mol % of a catalyst based on bromine was used. The diethylphosphonated polymers were dealkylated by a reaction with bromotrimethylsilane in carbon tetrachloride followed by hydrolysis with hydrochloric acid. The polymers with pendant phosphonic acid groups were soluble in polar solvents such as dimethyl sulfoxide and gave flexible and tough films via casting from solution. The polymers were hygroscopic and swelled in water. They did not decompose at temperatures of up to 260 °C under a nitrogen atmosphere. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3770–3779, 2001     

Synthesis and characterization of new semifluorinated linear and hyperbranched poly(arylene ether phosphine oxide)s through B2 + A2 and AB2 approaches

A new phosphorus containing trifluoromethyl-activated bisfluoro B₂ monomer has been synthesized successfully by coupling reaction of 4-methoxyphenylphosphonic dichloride and the Grignard salt of 5-bromo-2-fluorobenzotrifluoride. This monomer was converted to linear poly(arylene ether phosphine oxide)s by nucleophilic displacement of the fluorine atom on the benzene ring with several diphenols. The B₂ monomer was further demethylated to form an AB₂ monomer which on self condensation yielded hyperbranched poly(arylene ether phosphine oxide) with identical phosphorous containing moiety. The products obtained exhibit weight-average molecular weights as high as 600,000 g mol⁻¹ in SEC. These linear and hyperbranched poly(arylene ether phosphine oxide)s showed thermal stability as high as 516 °C for 10% weight loss in TGA in nitrogen and showed glass transition temperatures up to 253 °C in DSC. All the polymers were soluble in a wide range of organic solvents, e.g., CHCl₃, THF, NMP and DMF, however, the hb sample showed a significant lower solution viscosity compared to linear samples of similar molar mass. Transparent thin films of linear poly(arylene ether phosphine oxide)s casted from dichloromethane exhibited tensile strengths up to 50 MPa, a modulus of elasticity up to 0.95 GPa and elongation at break up to 36% depending on their exact repeating unit structures. No free standing films could be prepared from the hb analogue due to the missing entanglements, but stable thin polymer films on silicon wafers with high hydrophobicity were formed which showed water contact angles as high as 91°.     

Dynamic mechanical and thermal characteristics of homopolymers and copolymers containing arylene ether ketone units with carboxylic side groups and their salts

Properties of a poly(arylene ether ketone) with carboxyl side groups, copolymers containing units of this homopolymer, and their salts with different degrees of neutralization by alkali metals were studied by the methods of dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry. By varying the nature of a metal atom and the degree of neutralization of carboxylic groups of a homopolymer and their content in copolymers, one may change the properties of polymers, including their ability to form ion pairs and, hence, their glass transition temperatures. For polymer salts at the 100% neutralization of carboxylic groups, the storage modulus and the glass transition temperature are shown to increase with decreasing the radius of the metal ion. The thermal stability of poly(arylene ether ketone) with carboxylic side groups and copolymers with different contents of such groups may be controlled by varying the nature and content of the introduced metal.     

Synthesis and proton conductivities of phosphonic acid containing poly‐(arylene ether)s

A novel phosphonic acid containing bisphenol was successfully synthesized from phenolphthalein and m‐aminophenylphosphonic acid. A series of homo‐ and copoly‐(arylene ether)s containing phosphonic acid groups were prepared by solution nucleophilic polycondensation. These phosphonic acid containing polymers can readily be dissolved in common organic solvents, such as dimethyl sulfoxide, N‐methyl‐2‐pyrrolidinone, and N‐cyclohexylpyrrolidinone, and can be cast into tough and smooth films. The presence of phosphonic acid pendants in the poly‐(arylene ether)s was confirmed by NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and conductivity measurements. This is the first report on the attachment of phenylphosphonic acid groups as side chains to aromatic polyethers. These poly‐(arylene ether)s had very high glass‐transition temperatures ranging from 254 to >315 °C and high molecular weights. The conductivities of the synthesized polymers were analyzed by the Cole–Cole method, and they ranged from 10^?5 to 10^?6 Scm^?1. The synthesized polymers also exhibited good solution processability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3218–3226, 2001     

Poly(arylene ether)s and poly(arylene thioether)s containing the 1,2-dihydro-4-phenyl(2H)- phthalazinone moiety

A series of new high molecular weight poly(arylene ether)s containing the 1,2-dihydro-4-phenyl(2H)phthalazinone moiety have been synthesized. The inherent viscosities of these polymers are in the range of 0.33–0.64 dL/g. They are amorphous and readily soluble in chloroform, DMF, and DMAc. The glass transition temperatures of the polymers range from 241 to 320°C and the 5% weight loss temperatures in nitrogen atmosphere range from 473 to 517°C. The hydroxy group in the monomer 1,2-dihydro-4-(4-hydroxyphenyl)(2H)phthalazin-1-one has been selectively transformed into the N,N′-dimethylthiocarbamate group, which was then rearranged to give the S-(N,N′-dimethylcarbamate) group via the Newman–Kwart rearrangement reaction. A series of poly(arylene thioether)s containing the 1,2-dihydro-4-phenyl(2H)phthalazinone moiety have also been synthesized via two types of reactions, a N C coupling reaction and a one-pot reaction between the S-(N,N′-dimethylcarbamate) and activated dihalo compounds, in diphenyl sulfone in the presence of a cesium carbonate and calcium carbonate mixture. These poly(arylene thioether)s also have high glass transition temperatures (ranging from 217–303°C) and high thermal stabilities. Compared with their poly(ether) analogs, the poly(arylene thioether)s have glass transition temperatures several degrees lower, which is attributed to the more flexible C S C bonds. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 455–460, 1998