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.     

磺化杂萘联苯聚醚酮酮醚酮质子交换膜材料的合成与表征

以1,4-二(3-磺酸钠-4-氟代苯甲酰基)苯(SBFBB)和4,4’-二氟二苯酮(DFK)为二卤单体,与杂萘联苯类双酚进行溶液亲核缩聚反应,通过调控SBFBB与DFK的比例,制备了一系列具有不同磺化度的高分子量磺化杂萘联苯聚醚酮酮醚酮(SPPEKKEKs)。采用红外光谱、核磁共振谱、示差扫描量热分析等对SPPEKKEKs的结构和性能进行了表征,随着磺化度增加,SPPEKKEKs的玻璃化转变温度增大。以氮甲基吡咯烷酮为溶剂制备质子交换膜,随着SPPEKKEKs的磺化度增加,质子交换膜的含水率和质子传导率增加,95℃时,质子交换膜的质子传导率均达到10-2S.cm-1,SPPEKKEKs质子交换膜具有较好的耐氧化性能。     

用于燃料电池质子交换膜材料的磺化聚芳醚酮砜的合成与性能研究

以叔丁基对苯二酚(TBHQ)为双酚单体,1,4-二(4′-氟苯甲酰基)苯,3,3′-二磺酸钠基-4,4′-二氧二苯砜(SDCDPS)为原料,采用亲核缩聚反应,通过调整磺化单体和非磺化单体的比例与叔丁基对苯二酚共聚,合成了一系列具有不同磺化度的聚芳醚酮砜.通过红外光谱(FTIR),TGA,DSC等分析方法对其结构及性能进行了表征.并用TEM对其内部形态进行了研究,建立了结构与性能之间的关系.通过对膜进行综合性能评价发现,磺化度为0.8的磺化聚芳醚酮砜膜的质子传导率在80℃时达到了0.061 S/cm接近了Nafion 117,而且其甲醇渗透系数为3.4×10-7cm2/s远低于Nafion 117,在质子交换膜燃料电池(PEMFC)和直接甲醇燃料(DMFC)电池中表现出了好的应用前景.     

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.     

新型磺化聚苯并咪唑的合成及性能

以对苯二酚及对氟苯甲腈为原料, 合成了1,4-二(4-羧基苯氧基)苯, 再经磺化反应合成了1,4-二(4-羧基苯氧基)苯-2-磺酸钠(BCPOBS-Na), 并以4,4'-二羧基二苯醚(DCDPE)作为非磺化二酸单体与3,3'-二氨基联苯胺反应合成了一系列磺化聚苯并咪唑(SPBI). 通过红外光谱、 核磁共振及热重分析等手段对聚合物的结构及性能进行了分析. 研究了聚合物的特性黏度、 溶解性、 成膜性及聚合物薄膜的力学性能.     

新型燃料电池质子交换膜──含叔丁基的磺化聚芳醚砜

以3,3'-二磺酸钠基-4,4'-二氯二苯砜(SDCDPS)、叔丁基对苯二酚(TBHQ)、二氟二苯酮(DFBP)为原料,利用亲核缩聚反应,通过调整磺化单体(SDCDPS)和非磺化单体(DFBP)的比例与叔丁基对苯二酚(TBHQ)共聚,合成了不同磺化度的聚芳醚砜.聚合物成膜后的研究结果表明,该膜具有良好的机械性能和电化学性能,可能在质子交换膜燃料电池中得到应用.     

含亚环己基荷电聚醚醚酮的合成表征与性能

以 3,3′ 二磺酸钠基 4,4′ 二氟二苯酮和 4,4′ 二氟二苯酮与 4,4′ 亚环己基双酚进行亲核共缩聚 ,合成了磺化度从 0 4～ 2 0的一系列含亚环己基的荷电聚醚醚酮 .聚合物除保持了荷电聚醚醚酮良好的热稳定性和机械性能外 ,还具有良好的耐水性 .聚合物的DSC和广角X射线衍射数据表明 :上述磺化度聚合物均呈无定型聚集态结构 .比较了聚合物与双酚A系列荷电聚醚醚酮的性能差异 ,讨论了聚合物的溶解特点     

新型萘酐型磺化聚酰亚胺质子交换膜的合成

以新型磺化二胺单体, 1,4-双(4-胺基-2-磺酸基苯氧基)苯(DS-TBDA)与非磺化单体1,4′-二胺基二苯醚（ODA）、 1,4,5,8-萘四酸二酐(NTDA)为原料, 采用高温聚合法, 制备了一系列具有不同磺化度的萘酐型磺化聚酰亚胺(S-PI)质子交换膜材料, 并研究了材料性能与结构的关系. 磺化度超过33%时, 质子传导率可达到与Nafion膜同一数量级的水平, 而甲醇透过率均在2.85×10-7 cm2/s以下, 比Nafion膜低1-2个数量级. 研究结果表明, 该膜有望在直接甲醇燃料电池(DMFC)中获得应用.     

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.     

磺化聚酰胺的合成及性能

以对苯二酚及对氟苯甲腈为原料, 合成了芳香二羧酸单体1,4-二(4-羧基苯氧基)苯(BCPOB-COOH), 再经磺化反应合成了磺化芳香二羧酸单体1,4-二(4-羧基苯氧基)苯-2-磺酸钠(BCPOBS-Na). 另外, 以芳香二胺单体4,4'-二氨基二苯醚(ODA)为原料, 合成了磺化芳香二胺单体4,4'-二氨基二苯醚-2,2'-二磺酸(ODADS). 以N-甲基-2-吡咯烷酮(NMP)为溶剂、 亚磷酸三苯酯(TPP)与吡啶(Py)为缩合剂, 氯化钙或氯化锂或二者的组合为催化剂, 通过Yamazaki-Higashi直接缩聚, 使芳香二羧酸和芳香二胺中的磺化单体与非磺化单体反应, 制得了两种磺化芳香聚酰胺(Sulfonated polyamide, SPA). 通过红外光谱、 核磁共振波谱及热重分析等手段对聚合物的结构及性能进行了表征与分析, 并研究了聚合物的特性黏度、 溶解性、 成膜性及聚合物薄膜的力学性能等. 结果表明, 通过Yamazaki-Higashi直接缩聚制备的2种磺化芳香聚酰胺在极性非质子性溶剂中具有优良的溶解性能、 较高的耐热性能及优异的力学性能.     

Synthesis of fluoro-containing sulfonated poly(phthalazinone ether ketone ketone)s and their properties as PEM in PEMFC and DMFC

A series of sulfonated poly(ether ketone ketone)s (SPPFEKKs) containing both of phthalazinone and hexafluoroisopropylidene moieties were synthesized by direct nucleophilic polycondensation reaction from 4-(4-hydroxyphenyl)-1(2H)-phthalazinone (DHPZ), 4,4-hexafluoroisopropylidene-diphenol (BPAF), 1,4-bi(4-fluorobenzoyl) benzene (DFKK) and 1,4-bi(3-sodium sulfonate-4-fluorobenzoyl) benzene (SDFKK). The obtained SPPFEKKs had high molecular weight with inherent viscosity ranged from 1.29 to 1.53 dL/g and their chemical structure was characterized by FT-IR and ¹H NMR. The ionic membranes of SPPFEKKs showed high proton conductivity, for instance, SPPFEKK-120 (DS = 1.20) demonstrated 1.0 × 10⁻¹ S/cm proton conductivity at 95 °C, which was very close to that of Nafion^®117. All the SPPFEKK membranes exhibited methanol permeability lower than 2.76 × 10⁻⁷ cm²/s, which was much lower than that of Nafion^®117 (2.38 × 10⁻⁶ cm²/s). These copolymers also showed excellent thermal stability and good solubility in aprotic polar organic solvents. The ionic membranes of SPPFEKK demonstrated tensile strength varied from 57 to 69 MPa depending on their DS.     

磺化侧苯基杂萘联苯聚醚酮酮的合成与性能

以4-(3-苯基-4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ-P)、 4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)和1,4-二(4'-氟苯甲酰基)苯(BFBB)为原料, 经溶液亲核取代缩聚反应, 通过调节DHPZ-P和DHPZ的比例, 合成了一系列侧苯基杂萘联苯聚醚酮酮(PPEKK-P), 然后以浓硫酸为磺化剂, 制备出一系列磺化侧苯基杂萘联苯聚醚酮酮(SPPEKK-P). 利用傅里叶变换红外光谱(FTIR)和氢核磁共振谱(¹H NMR)对聚合物结构进行表征, 结果表明, 磺酸基团引入到聚合物链的侧苯基上. 采用溶液浇铸法制备SPPEKK-P质子交换膜. SPPEKK-P膜的吸水率、 溶胀率和质子传导率均随离子交换容量(IEC)的增加而增加, 且具有较好的耐氧化性. IEC最高的SPPEKK-P-100膜的质子传导率在95℃能达到7.44×10^-2 S/cm, 且甲醇渗透系数为5.57×10^-8 cm²/s, 阻醇性能优于Nafion117膜.     

Synthesis and Thermal Crosslinking Behavior of Poly（aryl ether ketone）s Containing 1,4-Naphthalene Moieties

A new monomer, 1,4-bis(4-fluorobenzoyl) naphthalene (compound 2) was synthesized via a two-step reaction. 1,4-Naphthalenedicarboxylic acid chloride (compound 1) was prepared by using the acyl chlorization reaction of 1,4-naphthalenedicarboxylic acid with thionyl chloride. The Friedel-Crafts acylation of compound 1 with fluorobenzene afforded compound 2 in a 80% yield. The polycondensation of compound 2 with various bisphenols in tetramethylene sulfone(TMS) in the presence of excess potassium carbonate as a condensation reagent was carried out at 210℃ to quantitatively afford the corresponding poly(aryl ether ketone)s (compounds 3-8) containing 1,4-naphthalene moieties. Thermal analyses showed that the polymers have Tg values ranging from 496 to 500 K and are thermally stable in air with initial mass loss above 500℃. These novel polymers exhibited an excellent solubility in organic solvents including NMP, DMAc, and chloroform, etc. In addition, the glass transition temperatures of these polymers increased and the polymers became insoluble in chloroform after treated at 260℃, indicating the occurrence of a thermal crosslinking reaction.     

Synthesis of a new sulfonated monomer for poly(aryl ether)s

A new sulfonated monomer suitable for polyarylether synthesis was made. 1,1'‐(p‐Phenylenedioxy)bis[4‐(4‐fluorobenzoyl)]benzene was prepared from phosphorus pentoxide/methanesulfonic acid (PPMA), 1,4‐diphenoxybenzene, and p‐fluorobenzoic acid in good yield. This compound was selectively monosulfonated on the most activated ring with fuming sulfuric acid and isolated as the sodium salt. Poly(aryl ethers) made from this monomer may find use as proton exchange membranes. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:553–556, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20137     

含氟聚醚醚酮酮的制备及其性能

以邻氟对苯二酚和4,4′-二氟三苯二甲酮为原料通过亲核缩聚反应,合成含氟聚醚醚酮酮(FPEEKK)材料。 用FTIR、1H NMR和WAXD进行了结构表征,用DSC、TGA测试了热性能,并研究了聚合物的溶解性、吸水性、介电性能及光学性能。 结果表明,含氟聚醚醚酮酮具有较好的热性能（N2气气氛中,5%热分解温度为505 ℃）;能溶于氯仿、四氢呋喃和N,N-二甲基甲酰胺等有机溶剂;具有较低的吸水率(0.24%)和介电常数（ε=3.0）;在近红外区1300和1550 nm处吸收非常弱。     

Synthesis of poly(arylene ether ketone)s bearing skeletal crown ether units for cation exchange membranes

Poly(arylene ether ketone)s (PAEKs) are the most commonly known high‐performance materials used for ion exchange and fuel cell membranes. Described here is the design of novel sulfonated PAEKs (SPAEKs) and nonsulfonated PAEKs containing crown ether units in the main chain, which can be used in sensing applications and ion‐selective membranes. To this end, 4,4′(5′)‐di(hydroxybenzo)‐18‐crown‐6 was synthesized and used as monomer in a step growth polymerization to form crown ether‐containing PAEKs and SPAEKs. The successful synthesis of PAEKs containing 18‐crown‐6 and sulfonate groups was confirmed by gel permeation chromatography, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy. Membranes are fabricated from the sulfonated polymers. Potassium ion transport properties of the SPAEK and crown ether‐containing SPAEK membranes are assessed by diffusion dialysis. Potassium ion diffusion in the crown ether‐containing SPAEK membranes is almost four times lower than K⁺ diffusion in the native polymer membranes, without crown ether. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2786–2793     

Synthesis and properties of highly branched sulfonated poly(arylene ether)s as proton exchange membranes

A series of branched sulfonated poly(arylene ether)s were successfully synthesized using 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene (B₃) as branching agent. The synthesized branched copolymers were soluble in polar organic solvents, such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc) and dimethylsulfoxide (DMSO), and could be cast to form tough and smooth films. The effect of degree of branching (DB) on the proton conductivity, swelling ratio and oxidative stability of the membranes was investigated. With increasing DB value, the proton conductivity and oxidative stability of the membranes increased. A maximum oxidative stability of the branched membrane with 4% of DB value was determined to be 3.4 times larger than that of the linear membrane. In addition, as the DB value increased, the swelling ratio of the membranes decreased from 13.51% to 9.09% at 80 °C. The results indicated that increasing DB value might be an effective way to improve the properties of proton exchange membranes.     

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