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.     

用于燃料电池的磺化聚芳醚砜质子交换膜材料的直接合成与性能研究

将磺化二氯二苯砜(SDCDPS)、二氯二苯砜(DCDPS)与4,4′-联苯酚(BP)通过亲核缩聚反应得到一系列具有不同磺化度的磺化聚芳醚砜(SPAES)共聚物.通过FT-IR,TGA和DSC等分析方法对其结构及性能进行表征.并用透射电镜对其内部形态进行分析,建立了结构与性能之间的关系.研究了不同磺化度对膜性能的影响.结果表明,聚合物中磺酸基团的增多导致了磺化聚芳醚砜膜的吸水率、离子交换容量、质子传导率和甲醇渗透系数的增加.通过对膜的综合性能评价发现,磺化度为0.8的磺化聚芳醚砜膜在80℃时的质子传导率为0.116S/cm,100℃时的质子传导率为0.126S/cm,均高于Nafion117膜(0.114S/cm和0.117S/cm),且甲醇渗透系数为8.4×10-7cm2/s,远远低于Nafion117膜(2.1×10-6cm2/s).     

以亲核取代反应制备质子交换膜用磺化聚酰亚胺

本文先通过缩合反应合成羟端基的二酰亚胺单体, 然后利用亲核缩聚反应, 与4,4′-二氯二苯砜及3,3′-二磺酸钠基-4,4′-二氯二苯砜共聚, 制备聚合物. 该合成路线反应周期短, 对温度和溶剂等条件要求不高, 简便易得.     

一类侧链型磺化聚芳醚砜质子交换膜的合成及表征

以4,4'-二氟二苯砜和N-溴代丁二酰亚胺为起始原料,经两步有机反应设计并合成了一种新型活性二氟砜单体:3,3'-双(苯氧基苯基)-4,4'-二氟二苯砜,并由该单体与4,4'-二氟二苯砜、4,4'-二羟基二苯甲酮经亲核缩聚合成了侧链型聚芳醚砜聚合物(PAES-xx).通过较温和的后磺化反应,制得了一系列磺化聚芳醚砜质子交换膜(SPAES-xx).对所制侧链型聚芳醚砜质子交换膜的结构和性能分别进行了表征分析.结果表明,该类质子交换膜具有适中的吸水率和较好的尺寸稳定性,80℃时最高质子传导率达0.16 S/cm.此外,该类质子交换膜还具有良好的热稳定性和机械性能,起始分解温度约为250℃;膜的拉伸强度为29.5~42.0MPa,拉伸模量为0.62~1.23 GPa,断裂伸长率在9.0%~31.9%.磺化膜优良的综合性能主要归因于侧链磺化结构的引入和相分离结构的形成.     

硫醚型芳香族二胺单体的合成及应用

以对氨基硫酸及４，４＇－二氯基二苯砜为原料合成了含硫醚键芳香族二胺单体：，用它制备的聚酰亚胺显示了良好的耐热性能。     

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.     

几种缩聚耐热聚合物单体纯度的差示扫描量热(DSC)测定

利用差示扫描量热法测定了缩聚单体的纯度。对于一种新型聚芳醚砜的单体4,4′—二氯二苯砜的纯度在99.0和99.9mol%时,所得缩聚物的比浓粘度分别可达0.36和0.62。提出了适用于缩聚单体纯度DSC测定法的试验程序。采用封闭坩埚,该法可用于升温时有少量升华(或挥发)的单体的纯度测定。     

磺酸基在侧链萘环上的磺化聚芳醚质子交换膜的制备与性能研究

以β-萘甲醛和2,6-二甲基苯酚为原料,合成出一种新型双酚单体.以此双酚单体和二氟单体(4,4'-二氟二苯甲酮或4,4'-二氟二苯砜)为基础,通过亲核取代反应,制备出两种高分子量聚芳醚.用氯磺酸对聚合物进行磺化,得到了2种磺酸基在侧链萘环上的磺化聚芳醚.该磺化聚芳醚能溶于N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等常见的有机溶剂,通过溶液浇注的方法制备出光滑、柔韧的膜.用红外光谱(FTIR),核磁共振谱(1H-NMR)表征了聚合物结构.用示差扫描量热仪(DSC),热重分析仪(TGA)研究了聚合物的耐热性能.结果表明,这些侧链磺化的质子交换膜具有高的电导率(4.2×10-2S/cm)、高的机械强度、低的溶胀率和较好的氧化稳定性.     

加速溶剂萃取-高效液相色谱法测定高分子食品接触材料中二苯砜和4,4’-二氯二苯砜

以丙酮作为提取溶剂,采用加速溶剂萃取方式提取,C18色谱柱分离,建立了高分子材料类食品接触材料中二苯砜和4,4’-二氯二苯砜的液相色谱测定方法。食品接触材料中二苯砜和4,4’-二氯二苯砜的检测限均为100 mg/kg,在聚醚砜、聚醚醚酮及聚醚酮醚酮酮3种基质中进行3水平的添加回收实验,回收率范围在81.1%~106.9%之间,相对标准偏差小于5.0%。方法能满足食品接触材料中二苯砜和4,4’-二氯二苯砜的检测要求。     

Synthesis and properties of aromatic poly (ether sulfone)s and poly (ether ketone)s based on methyl-substituted biphenyl-4,4′-diols

Novel methyl-substituted aromatic poly (ether sulfone)s and poly (ether ketone)s were synthesized from combinations of 3,3′,5,5′-tetramethylbipheny-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol, and 4,4′-dichlorodiphenyl sulfone and 4,4′-difluorobenzo-phenone by nucleophilic aromatic substitution polycondensation. The polycondensations proceeded quantitatively in a N-methyl-2-pyrrolidone-toluene solvent system in the presence of anhydrous potassium carbonate to afford the polymers with inherent viscosities between 0.86 and 1.55 dL/g. The methyl-substituted poly (ether sulfone)s and poly (ether ketone)s showed good solubility in common organic solvents such as chloroform, tetrahydrofuran, pyridine, m-cresol, and N,N-dimethylacetamide. The tetramethyl- and hexamethyl-substituted aromatic polyethers had higher glass transition temperatures than the corresponding unsubstituted polymers, and did not decompose below 350°C in both air and nitrogen atmospheres. The films of the methyl-substituted poly (ether ketone)s became insoluble in chloroform by the irradiation of ultraviolet light, indicating the occurrence of photochemical crosslinking reactions. © 1994 John Wiley & Sons, Inc.     

聚醚砜醚酮的合成与性能

以4,4′-二羟基二苯砜和4,4′-二氟二苯酮为单体, 通过溶液缩聚合成了聚醚砜醚酮(PESEK), 其分子结构相当于聚醚砜(PES)与聚醚醚酮(PEEK)的交替共聚物. 在共聚物分子中, 存在砜基、醚基和酮基, 整个结构单元形成了大共轭体系, 聚合物属无定形聚合物, 玻璃化转变温度(Tg)为198 ℃, 介于PEEK和PES的Tg之间, 其热稳定性和加工性能优于PES, 而力学性能与PES接近.     

Synthesis and Properties of Aromatic Poly(Ether Sulfone)s and Poly(Etherketone)s Containing Naphthalene or Quinoline Units,and Methyl-Substituted Biphenyl-4,4′-Diols

Abstract

A series of poly(ether sulfone)s and poly(ether ketone)s were synthesized from combinations of 1,5- and 2,6-bis(4-fluorosulfonyl)naphthalene, 2,6-bis(4-fluorobenzoyl)naphthalene, and 2,6-bis(4-fluorobenzoyl)quinoline with 3,3′,5,5′-tetramethylbiphenyl-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol. The polycondensations proceeded quantitatively in diphenylsulfone in the presence of anhydrous potassium carbonate to afford polymers with inherent viscosities between 0.40 and 1.28 dL/g measured in N-methyl-2-pyrrolidone or concentrated sulfuric acid. The tetramethyl- and hexamethyl-substituted aromatic polyethers exhibited good thermal stability, did not decompose below 330°C in both air and nitrogen atmospheres, and had higher glass transition temperatures than the corresponding unsubstituted polymers. The methylsubstituted poly(ether sulfone)s and poly(ether ketone)s showed good solubility in such common organic solvents as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, tetrahydrofuran, chloroform, and 1,4-dioxane.     

3种新型聚苯基醚喹噁啉的合成

用4,4′-二氟代二苯甲酰与双酚A的溶液缩聚制得聚醚苯偶酰(PEB),经邻苯二胺改性后,通过两步法得到聚苯基醚喹噁啉（PEQ-1）。 在PEB的改性反应中加入质量分数分别为1.0%和1.3%的3,3′,4,4′-四胺基二苯醚,可有效增加聚苯基醚喹噁啉的相对分子质量,得到PEQ-2和PEQ-3（总收率≥90%）,其质均相对分子质量分别为7.492×104和1.486×105。 并用IR、 NMR等对这些聚合物进行了表征。 该法操作简便,具有潜在的应用价值。     

Preparation of Anion Exchange Membrane Based on Imidazolium Functionalized Poly(arylene ether ketone)

The authors presented a novel synthetic route for the imidazolium functionalized poly(arylene ether ketone)s, derived from an engineering plastics polymer, a poly(arylene ether ketone) with 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl moiety(PAEK-TM). The preparation of anion exchange membranes comprised converting benzylic methyl groups to bromomethyl groups by a radical reaction, followed by the functionalization of bromomethylated PAEK with alkyl imidazoles, i.e., methyl, butyl or vinyl imidazole. The structure of imidazolium functionalized PAEK was proved by ¹H NMR spectra. A class of flexible and tough membranes was then achieved by subsequent film-forming and anion exchange processes. The water uptake and hydroxide conductivities of membranes are comparable or superior to those of quaternary ammonium(QA) anion exchange membranes. This work demonstrated a new route for non-QA anion exchange membrane design, avoiding the chloromethylation reagent and precisely controlling the degree and location of imidazolium groups.     

原子转移自由基聚合法制备侧链型磺化聚醚醚酮阳离子交换膜

以二氟二苯甲酮、双酚A和邻甲基氢醌为单体先经缩聚反应生成聚醚醚酮(PEEK),PEEK经修饰合成含有溴异丙基侧基的聚醚醚酮,以此为原子转移自由基聚合(ATRP)大分子引发剂,通过ATRP法聚合,在PEEK主链上接枝引入聚苯乙烯磺酸钠侧链,得到侧链型PEEK接枝聚合物(PEEK-g-StSO3Na)。 用傅里叶变换红外(FTIR) 光谱、核磁共振氢谱(1H NMR)、热重分析(TG)和扫描电子显微镜(SEM)等技术手段对PEEK-g-StSO3Na的结构进行表征。 结果表明,苯乙烯磺酸钠成功的被接枝到聚醚醚酮主链上,PEEK-g-StSO3Na膜具有明显的亲水疏水微相分离结构,磺酸基团相互聚集形成离子通道,离子交换容量为2.034 mmol/g的PEEK-g-StSO3Na膜的电导率为8.34×10-2 S/cm,膜的尺寸稳定性优于Nafion 117。     

含氟磺化双三蝶烯型聚芳醚砜质子交换膜的制备及性能

利用3,3,4,4-四氟二苯砜、十氟联苯、6F-双酚A及6,13-双三蝶烯二酚,通过亲核取代共聚及后磺化方法制备了2个系列不同磺化度的磺化双三蝶烯型聚芳醚砜,并通过氢核磁共振波谱(1H NMR)对其化学结构进行了表征.研究发现,所得磺化聚芳醚砜均表现出了优异的热稳定性.此类膜材料具有优良的机械性能、尺寸稳定性、氧化稳定性及高温低湿度条件下高的质子传导率.透射电子显微镜的结果表明,聚合物主链中大量氟原子的引入显著改善了聚合物的相分离结构,并且随着聚合物主链中氟含量的增加,亲水区域明显增大.这也是含氟磺化双三蝶烯型聚芳醚砜质子交换膜材料在高温低湿度条件下具有高质子传导率的主要原因.     

Synthesis and characterization of aromatic poly(ether sulfone)s containing pendant sodium sulfonate groups

Poly(ether sulfone)s containing pendant sodium sulfonate groups were prepared by the aromatic nucleophilic substitution reaction of 4,4′-dichlorodiphenylsulfone ( 1 ) and sodium 5,5′-sulfonylbis (2-chlorobenzenesulfonate) ( 2 ) with bisphenols ( 3 ) in the presence of potassium carbonate in N,N-dimethylacetamide. A new monomer 2 containing the sodium sulfonate groups was synthesized by the sulfonation of 1 with fuming sulfuric acid. The polycondensation proceeded smoothly at 170°C and produced the desired poly(ether sulfone)s containing the sodium sulfonate with inherent viscosities up to 1.2 dL/g. The polymers were quite soluble in strong acid, dipolar aprotic solvents, m-cresol, and dichloromethane. The thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight losses of the polymers were observed in the range above 460°C in nitrogen atmosphere. Both the glass transition temperatures and hydrophilicity of the polymers increased with increasing their concentrations of sodium sulfonate groups. © 1993 John Wiley & Sons, Inc.     

连茚四酮类有机磁性化合物的合成及性能

分别以邻苯二甲酸酐、4-甲基邻苯二甲酸酐和四氯邻苯二甲酸酐为原料, 采用Gabriel & Leupold法合成了3个连茚四酮类化合物, 即2,2′-二茚满-1,1′,3,3′-四酮(1)、5,5′-二甲基-2,2′-二茚满-1,1′,3,3′-四酮(2)和4,4′,5,5′,6,6′,7,7′-八氯-2,2′-二茚满-1,1′,3,3′-四酮(3). 元素分析、¹H NMR、FTIR 和MS测定分析表明, 此3个分子主要以烯醇式存在, 同时存在分子内氢键; 通过电子自旋共振(ESR)谱测定, 给出了各化合物的ESR谱参数值. 结果表明, 化合物1~3均有良好的ESR图谱, 是只含有C, H, O及Cl的纯有机磁性化合物, 分子内都含有稳定的自由基. 通过量子化学计算, 推测出了自由基可能形成的位置及此类化合物最可能的存在形式(烯醇式), 且证明分子内存在1个氢键.