一种杂环磺化聚芳醚腈酮质子交换膜材料的合成及表征

用含二氮杂萘酮结构类双酚DHPZ,3,3′-二磺酸钠基-4,4′-二氟二苯酮,2,6-二氯苯腈以及4,4′-二氟二苯酮,通过缩合共聚合反应合成了一系列不同磺化度、高分子量的磺化聚芳醚腈酮.聚合物特性粘数为0·58~2·0dL/g.用红外光谱(FT-IR),核磁共振谱(1H-NMR)表征了聚合物结构.用差示扫描量热仪(DSC)和热重分析仪(TGA)研究了聚合物的耐热性能,研究表明其玻璃化温度(Tg)可达352℃,5%热失重温度大于500℃.以N-甲基吡咯烷酮为溶剂,溶液浇铸法制备了聚合物膜,并测定了膜的溶胀率以及质子交换能力.结果表明,与Nafion膜相比,磺化聚芳醚腈酮膜在相同的质子交换能力条件下,溶胀率显著降低.     

Preparation and characterization of branched and linear sulfonated poly(ether ketone sulfone) proton exchange membranes for fuel cell applications

Branched sulfonated poly(ether ketone sulfone)s (Br‐SPEKS) were prepared with bisphenol A, bis(4‐fluorophenyl)sulfone, 3,3′‐disodiumsulfonyl‐4,4′‐difluorobenzophenone, and THPE (1,1,1‐tris‐p‐hydroxyphenylethane), respectively, at 180 °C using potassium carbonate in NMP (N‐methylpyrrolidinone). THPE, as a branching agent, was used with 0.4 mol % of bisphenol A to synthesize branched copolymers. Copolymers containing 10–50 mol % disulfonated units were cast from dimethylsulfoxide solutions to form films. Linear sulfonated poly(ether ketone sulfone)s (SPEKS) were also synthesized without THPE. The films were converted from the salt to acid forms with dilute hydrochloric acid. A series of copolymers were studied by Fourier transform infrared, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion‐exchange capacity (IEC), a measure of proton conductivity, was evaluated. The synthesized Br‐SPEKS and SPEKS membranes exhibit conductivities (25 °C) from 1.04 × 10^?3 to 4.32 × 10^?3 S/cm, water swell from 20.18 to 62.35%, IEC from 0.24 to 0.83 mequiv/g, and methanol diffusion coefficients from 3.2 × 10^?7 to 4.7 × 10^?7 cm²/S at 25 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1792–1799, 2008     

Synthesis and Properties of Poly(Aryl Ether Ketone) Copolymers with Trifluoromethyl‐Substituted Benzene in the Side Chain

The new monomer (4‐(4′‐trifluoromethyl)phenoxyphenyl)hydroquinone (TFPOPH) was synthesized in a three‐step synthesis. A series of poly(aryl ether ketone) copolymers were prepared by the reaction of (4‐(4′‐Trifluoromethyl)phenoxyphenyl)hydroquinone and hydroquinone (HQ) with 4,4′‐difluorobenzophenone (DFB) in the presence of potassium carbonate in tretramethylene sulfone (TMS). Thermal analyses of the fluorinated copolymers showed that the glass transition temperature and 5.0% weight loss temperature are similar with that of PEEK, and the crystallinity decreased with increasing of TFPOPH. For the copolymer synthesized with the molar fraction of TFPOPH in the diphenol monomers (TFPOPH, HQ) being over 0.2, no cold crystallization temperature and melting temperature were detected, indicating that these copolymers are almost amorphous. The crystal structure of the copolymers with the molar fraction of TFPOPH being not higher than 0.2 is rhombic. The solubility in polar aprotic solvents of poly(aryl ether ketone)s copolymers increases and dielectric constant decreases step by step.     

Synthesis and characterization of poly(arylene ether)s containing 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one or 6‐(4‐hydroxyphenyl)pyridazine moieties

A series of novel soluble pyridazinone‐ or pyridazine‐containing poly(arylene ether)s were prepared by a polycondensation reaction. The pyridazinone monomer, 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one ( 1 ), was synthesized from the corresponding acetophenone and glyoxylic acid in a simple one‐pot reaction. The pyridazinone monomer was successfully copolymerized with bisphenol A (BPA) or 1,2‐dihydro‐4‐(4‐hydroxyphenyl)phthalazin‐1(2H)‐one (DHPZ) and bis(4‐fluorophenyl)sulfone to form high‐molecular‐weight polymers. The copolymers had inherent viscosities of 0.5–0.9 dL/g. The glass‐transition temperatures (T_g's) of the copolymers synthesized with BPA increased with increasing content of the pyridazinone monomer. The T_g's of the copolymers synthesized from DHPZ with different pyridazinone contents were similar to those of the two homopolymers. The homopolymers showed T_g's from 202 to 291 °C by differential scanning calorimetry. The 5% weight loss temperatures in nitrogen measured by thermogravimetric analysis were in the range of 411–500 °C. 4‐(6‐Chloropyridazin‐3‐yl)phenol ( 2 ) was synthesized from 1 via a simple one‐pot reaction. 2 was copolymerized with 4,4′‐isopropylidenediphenol and bis(4‐fluorophenyl)sulfone to form high‐T_g polymers. The copolymers with less than 80 mol % pyridazinone or chloropyridazine monomers were soluble in chlorinated solvents such as chloroform. The copolymers with higher pyridazinone contents and homopolymers were not soluble in chlorinated solvents but were still soluble in dipolar aprotic solvents such as N‐methylpyrrolidinone. The soluble polymers could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3328–3335, 2006     

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 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 d...     

Membranes from poly(aryl ether)‐based ionomers containing multiblock segments of randomly distributed nanoclusters of 18 sulfonic acid groups

Multiblock copolymers 1a (M_n = 31,500–47,400) of sulfonated poly(aryl ether)s were synthesized by polycondensation of 4,4′‐difluorobenzophenone (DFBP), bis(4‐hydroxyphenyl)sulfone (BHPS), and an hydroxy‐terminated sulfonated oligomer, which was synthesized from DFBP and 2,2′,3,3′,5,5′‐hexaphenyl‐4,4′‐dihydroxybiphenyl a . The copolymerization of trimeric monomer b with DFBP and BHPS gave a series of copolymers 1b (M_n = 26,200–45,900). The copolymers were then sulfonated with chlorosulfonic acid to give ionomers 3a with hydrophilic multiblock segments and ionomers 3b with segments containing clusters of 18 sulfonic acid groups. The proton exchange membranes cast from ionomers 3a and 3b were characterized with regard to thermal stability, water uptake, proton conductivity, and morphology. Transmission electron microscopy images of 3a‐1 and 3b‐1 revealed a phase separation similar to that of Nafion that may explain their higher proton conductivities compared with randomly sulfonated copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4762–4773, 2009     

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.     

Synthesis and characterization of poly(aryl ether imide)s containing electroactive perylene diimide and naphthalene diimide units

The synthesis and polymerization of two new electroactive bisphenols derived from 3,4,9,10‐perylenetetracarboxylic dianhydride and 1,4,5,8‐naphthalenetetracarboxylic dianhydride with 2‐(4‐aminophenyl)‐2‐(4‐hydroxyphenyl)propane, respectively, are described. Copolymerization using the two new bisphenols and 4,4′‐isopropylidenediphenol with bis(4‐fluorophenyl)sulfone and 4,4′‐difluorobenzophenone, afforded a series of soluble electrochromic poly(aryl ether imide)s with glass‐transition temperatures ranging from 160 to 315 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3467–3475, 2000     

Polyelectrolytes for Fuel Cells Made of Sulfonated Poly(phthalazinone ether ketone)s

Novel sulfonated poly(phthalazinone ether ketone)s were synthesized directly by aromatic nucleophilic polycondensation of 4‐(4‐hydroxyphenyl)phthalazinone with various ratios of 5,5′‐carbonylbis(2‐fluorobenzenesulfonate) to 4,4′‐difluorobenzophenone. The 10% weight loss temperature of the products is higher than 500°C. The resulting ionomers show low swelling (14.7, 16.7 and 17.8%), while the corresponding IEC are 1.58, 1.88 and 2.16 meq/g, respectively. The low swelling results from hydrogen bonding. The membranes show very good perspectives in polymer electrolyte membrane fuel cell applications.     

Influence of the bisphenol structure on the direct synthesis of sulfonated poly(arylene ether) copolymers. I

New sulfonated poly(arylene ether sulfone) copolymers with high molecular weights were successfully synthesized with controlled degrees of disulfonation of up to 70 mol % via the direct copolymerization of sulfonated aromatic dihalides, aromatic dihalides, and one of four structurally distinct bisphenols. The disodium salts of the 3,3′‐disulfonated‐4,4′‐dichlorodiphenyl sulfone and 3,3′‐disulfonated‐4,4′‐difluorodiphenyl sulfone comonomers were synthesized via the sulfonation of 4,4′‐dichlorodiphenyl sulfone or 4,4′‐difluorodiphenyl sulfone with 30% fuming sulfuric acid at 110 °C. Four bisphenols (4,4′‐bisphenol A, 4,4′‐bisphenol AF, 4,4′‐biphenol, and hydroquinone) were investigated for the syntheses of novel copolymers with controlled degrees of sulfonation. The composition and incorporation of the sulfonated repeat unit into the copolymers were confirmed by ¹H NMR and Fourier transform infrared spectroscopy. Solubility tests on the sulfonated copolymers confirmed that no crosslinking and probably no branching occurred during the copolymerizations. Tough, ductile films were solvent‐cast that exhibited increased water absorption with increasing degrees of sulfonation. These copolymers are promising candidates for high temperature proton‐exchange membranes in fuel cells, which will be reported separately in part II of this series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2264–2276, 2003     

Selectively sulfonated poly(aryl ether sulfone)‐b‐polybutadiene for proton exchange membrane

A series of selectively sulfonated poly(arylene ether sulfone)‐b‐polybutadiene copolymers (SPAES‐b‐PB) were prepared based on carboxyl terminated polybutadiene (CTPB) and sulfonated poly(arylene ether sulfone) (SPAES) that was directly prepared by polycondensation of 4,4′‐isopropylidenediphenol with different molar ratios of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenyl sulfone (SDCDPS) to 4,4′‐dichlorodiphenylsulfone (DCDPS), and subsequent selective postsulfonation of flexible PB block was carried out. Epoxidized modification of membranes was conducted by an in situ‐generated peracid method. The content of sulfonic acid groups attaching to aromatic rings in SPAES was determined by ¹H NMR and was in good aggrement with the controlled ratios. The effect of sulfonated rigid blocks on the postsulfonation of PB blocks was studied by Fourier transform infrared spectroscopy. The glass transition temperature (T_g) and the temperature of the melting peak (T) of membranes in acid form were studied by differential scanning calorimetry. Fenton's reagent test revealed that the selectively sulfonated SPAES‐b‐PB membranes had good stability to oxidation. The microstructure of rod‐like rigid SPAES blocks and interpenetrating network of ions were observed by transmission electron microscopy. Complex impedance measurement showed that an epoxidized membrane with SPAES‐40 exhibited the highest proton conductivity (1.08 × 10^?1 S/cm, 90 °C), which was due to the formation of obvious ionic networks. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 665–672, 2006     

Synthesis and characterization of sulfonated poly(phthalazinone ether ketone) for proton exchange membrane materials

As a novel class of proton exchange membrane materials for use in fuel cells, sulfonated poly(phthalazinone ether ketone)s (SPPEKs) were prepared by the modification of poly(phthalazinone ether ketone). Sulfonation reactions were conducted at room temperature with mixtures of 95–98% concentrated sulfuric acid and 27–33% fuming sulfuric acid with different acid ratios, and SPPEK was obtained with a degree of sulfonation (DS) in the desired range of 0.6–1.2. The presence of sulfonic acid groups in SPPEK was confirmed by Fourier transform infrared analysis, and the DS and structures were characterized by NMR. The introduction of sulfonic groups into the polymer chains increased the glass‐transition temperature above the decomposition temperature and also led to an overall decrease in the decomposition temperature. Membrane films were cast from SPPEK solutions in N,N‐dimethylacetamide. Water uptakes and swelling ratios of SPPEK membrane films increased with DS, and SPPEKs with DS > 1.23 were water‐soluble at 80 °C. Proton conductivity increased with DS and temperature up to 95 °C, reaching 10^?2S/cm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 497–507, 2003     

Synthesis of Poly(phthalazinone ether ketone) Containing Sodium Sulfonate Groups via Direct Polymerization

Poly (aryl ether ketone)s are a category of high performance engineering plastics which have outstanding thermal, physical and mechanical properties. Poly(aryl ether ketone) with sulfonic groups have received extensive attention for their potential usage as high performance gas dehumidification and ion exchange membrane materials1,2,3. Poly (phthalazinone ether ketone)4, one of poly(aryl ether ketone), shows excellent comprehensive properties and outstanding thermal stability, whose glass tra…     

Locally sulfonated poly(ether sulfone)s with highly sulfonated units as proton exchange membrane

Novel locally sulfonated poly(ether sulfone)s with highly sulfonated units were successfully synthesized for fuel cell applications. Poly(ether sulfone)s were prepared by the nucleophilic substitution of bis(4‐fluorophenyl) sulfone with 1,2,4,5‐tetrakis([1,1′‐biphenyl]‐2‐oxy)‐3,6‐bis(4‐hydroxyphenoxy)benzene and bis(4‐hydroxyphenyl) sulfide, followed by oxidation using m‐chloroperoxybenzoic acid. The desired highly sulfonated units were easily introduced by postsulfonation and each one had ten sulfonic acid groups. The sulfonated polymers gave tough, flexible, and transparent membranes by solvent casting. The high contrast in polarity between highly sulfonated units and hydrophobic poly(ether sulfone) units enabled the formation of defined phase‐separated structures and well‐connected proton paths. The sulfonated polymers exhibited excellent proton conductivity over a wide range of relative humidities. The proton conductivity of the sulfonated polymer with an ion exchange capacity value of 2.38 mequiv/g was comparable to that of Nafion 117 even at 30% relative humidity. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3444–3453, 2009     

Sulfonated naphthalene dianhydride based polyimide copolymers for proton‐exchange‐membrane fuel cells. I. Monomer and copolymer synthesis

A novel sulfonated diamine, 3,3′‐disulfonic acid‐bis[4‐(3‐aminophenoxy)phenyl]sulfone (SA‐DADPS), was prepared from m‐aminophenol and disodium‐3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone. The conditions necessary to synthesize and purify SA‐DADPS in high yields were investigated in some detail. This disulfonated aromatic diamine, containing ether and sulfone linkages, was used to prepare N‐methyl‐2‐pyrrolidinone‐soluble, six‐membered ring polyimide copolymers containing pendent sulfonic acid groups by a catalyzed one‐step high‐temperature polycondensation in m‐cresol. These materials showed much improved hydrolytic stability with respect to phthalimides. High‐molecular‐weight film‐forming statistical copolymers with controlled degrees of disulfonation were prepared through variations in the stoichiometric ratio of disulfonated diamine (SA‐DADPS) in its soluble triethylamine salt form to several unsulfonated diamines. Three unsulfonated diamines, bis[4‐(3‐aminophenoxy)phenyl] sulfone, 4,4′‐oxydianiline, and 1,3‐phenylenediamine, were used to prepare the copolymers. The characterization of the copolymers by ¹H NMR, Fourier transform infrared, ion‐exchange capacity, and thermogravimetric analysis demonstrated that SA‐DADPS was quantitatively incorporated into the copolymers. Solution‐cast films of the sulfonated copolymers were prepared and afforded tough, ductile membranes with high glass‐transition temperatures. Methods were developed to acidify the triethylammonium salt membranes into their disulfonic acid form, this being necessary for proton conduction in a fuel cell. The synthesis and characterization of these materials are described in this article. Future articles will describe the performance of these copolymers as proton‐exchange membranes in hydrogen/air and direct methanol fuel cells. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 862–874, 2004     

Synthesis of highly sulfonated poly(arylene ether sulfone) random (statistical) copolymers via direct polymerization

Novel biphenol‐based wholly aromatic poly (arylene ether sulfones) containing pendant sulfonate groups were prepared by direct aromatic nucleophilic substitution polycondensation of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenyl sulfone (SDCDPS), 4,4′‐dichlorodiphenylsulfone (DCDPS) and biphenol. Copolymerization proceeded quantitatively to high molecular weight in N‐methyl‐2‐pyrrolidinone at 190°C in the presence of anhydrous potassium carbonate. Tough membranes were successfully cast from the control and the copolymers, which had a SDCDPS/DCDPS mole ratio of either 40:60 or 60:40 using N,N‐dimethylactamide; the 100% SDCDPS homopolymer was water soluble. Short‐term aging (30 min) indicates that the desired acid form membranes are stable to 220°C in air and conductivity values at 25°C of 0.110 (40%) and 0.170 S/cm (60%) were measured, which are comparable to or higher than the state‐of‐the art fluorinated copolymer Nafion 1135 control. The new copolymers, which contain ion conductivity sites on deactivated rings, are candidates as new polymeric electrolyte materials for proton exchange membrane (PEM) fuel cells. Further research comparing their membrane behavior to post‐sulfonated systems is in progress.     

Synthesis and characterization of poly(arylene ether sulfone) copolymers with sulfonimide side groups for a proton‐exchange membrane

A sulfonimide‐containing comonomer derived from 4,4′‐dichlorodiphenylsulfone was synthesized and copolymerized with 4,4′‐dichlorodiphenylsulfone and 4,4′‐biphenol to prepare sulfonimide‐containing poly(arylene ether sulfone) random copolymers (BPSIs). These copolymers showed slightly higher water uptake than disulfonated poly(arylene ether sulfone) copolymer (BPSH) controls, but their proton‐conductivity values were very comparable to those of the BPSH series with similar ion contents. The proton conductivity increased with the temperature for both systems. For samples with 30 mol % ionic groups, BPSI showed less temperature dependence in proton conductivity and slightly higher methanol permeability in comparison with BPSH. The thermal characterization of the sulfonimide copolymers showed that both the acid and salt forms were stable up to 250 °C under a nitrogen atmosphere. The results suggested that the presumed enhanced stability of the sulfonimide systems did not translate into higher protonic conductivity in liquid water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6007–6014, 2006     

Synthesis and optical properties of poly(aryl ether ketone)s incorporating porphyrins in the backbones

A series of novel soluble poly(aryl ether ketone)s (PAEKs) based on 5,10‐bis(4‐hydroxyphenyl)?15,20‐diphenylporphyrin (cis‐DHTPP), 4,4′‐(hexafluoroisopropylidene) diphenol (6FBPA) and 4,4′‐difluorobenzophenone (DFB) were synthesized and characterized by FT‐IR, ¹H‐NMR, UV–vis and fluorescence spectroscopies. The intrinsic photophysical properties of porphyrins were preserved because of the absence of photoinduced electron transfer in the polymer chains. Investigation of the copolymers thermal properties indicated that these polymers had high glass transition temperatures and excellent thermal stabilities. The results of Z‐scan and optical limiting measurements manifested that incorporation of the porphyrin chromophore into the main chain engendered the novel PAEKs with superior nonlinear optical properties and optical limiting function, which could be effectively tuned by varying the molar ratio of porphyrin monomers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1282–1290     

Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N–C coupling reaction

High‐molecular‐weight poly(phthalazinone)s with very high glass‐transition temperatures (T_g's) were synthesized via a novel N–C coupling reaction. New bisphthalazinone monomers ( 7a–e ) were synthesized from 2‐(4‐chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34–0.91 dL/g, were prepared by the reaction of the bis(phthalazinone) monomers with an activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The poly(phthalazinone)s exhibited T_g's greater than 230 °C. polymer 8b synthesized from diphenyl biphenol and bis(4‐flurophenyl) sulfone demonstrated the highest T_g of 297 °C. Thermal stabilities of the poly(phthalazinone)s were determined by thermogravimetric analysis. All the poly(phthalazinone)s showed a similar pattern of decomposition with no weight loss below 450 °C in nitrogen. The temperatures of 5% weight loss were observed to be about 500 °C. The poly(phthalazinone)s containing 4,4′‐isopropylidenediphenol and 4,4′‐(hexafluoroisopropylidene) diphenol and diphenyl ether linkage were soluble in chlorinated solvents such as chloroform. Other poly‐(phthalazinone)s were soluble in dipolar aprotic solvents such as N,N′‐dimethylacetamide. The soluble poly(phthalazinone)s can be cast as flexible films from solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2481–2490, 2003