侧链含氮原子磺化聚酰亚胺膜材料的制备及其性能研究

以对苯二酚为原料经过三步反应,合成了含叔胺取代基的二胺单体2,5-二((二甲氨基)亚甲基)-1,4-二(对氨基苯氧基)苯(DMAPB),并与1,4,5,8-四酸萘二酐(NTDA)、磺化二胺4,4'-二氨基二苯醚-2,2'-二磺酸(ODADS)高温聚合,通过改变磺化二胺单体(ODADS)的含量,制备了一系列具有不同磺化度的侧链含氮原子磺化聚酰亚胺.采用间甲酚为溶剂,通过溶液浇铸法制备成膜.由于将N-原子引入到聚酰亚胺的侧链,使得其与磺酸基更易形成较强的离子交联,从而有效地控制膜溶胀,提高了膜稳定性.新的磺化聚酰亚胺的热稳定性高达330℃并显示了良好的氧稳定性,其阻醇性能也得到了提高,在20℃下,膜的甲醇渗透系数为2.05×10-7至5.11×10-7cm2/s,远低于Nafion 117(2×10-6cm2/s)一个数量级.磺化度40%的磺化聚酰亚胺膜在100℃去离子水中测试1000 h以上仍能保持较好的机械性能.膜在高湿条件下也显示了良好的机械性能.然而,膜的质子传输率有所下降,这应该是较强的离子交联导致膜产生较致密的结构,减少了含水量并阻碍了水和H+的移动.同时,磺酸基与氮原子发生离子交联,减少了参与质子传输的磺酸基数量,降低了聚合物膜的酸性.     

燃料电池用磺化聚酰亚胺质子交换膜材料的制备与性质

以联萘二酐、磺化二胺和含咪唑基团的非磺化二胺单体为原料,制备了一系列高相对分子质量的磺化聚酰亚胺,该类聚合物具有优异的溶解性和良好的成膜性.得到的质子交换膜具有优异的水解稳定性.苯并咪唑碱性基团的存在提高了磺化聚酰亚胺质子交换膜膜的溶胀稳定性和热稳定性、降低了膜的甲醇透过率.质子导电率测试结果表明,IEC值为2.55mequiv·g-1的膜室温条件下的质子导电率为0.121 S·cm-1,高于在相同测试条件下Nafion 117膜的质子导电率(0.09 S·cm-1).     

含甲基磺化杂萘联苯聚醚砜酮质子交换膜材料的合成与性能

以4-(3,5-二甲基-4-羟基苯基)2,3-二氮杂萘-1-酮,3,3′-二磺酸钠-4,4′-二氟苯甲酮和4,4′-二氯二苯砜为原料,利用亲核缩聚反应,通过改变磺化单体的含量,制备出一系列不同磺化度的杂萘联苯聚醚砜酮(SPPESK-DM).采用FTIR、1H-NMR表征了聚合物的结构,热失重分析仪研究了聚合物的耐热稳定性,以N-甲基-2-吡咯烷酮为溶剂采用溶液浇铸法成膜研究该系列聚合物膜的性能.结果表明,SPPESK-DM磺酸基的热分解温度在260℃以上,主链分解温度在410℃以上;膜的吸水率、溶胀率、离子交换容量和质子传导率均随着磺化度的增大而增大,磺化度为1.0的SPPESK-DM50的质子传导率达到1.08×10-2S/cm(85℃),且甲醇渗透系数为2.06×10-7cm2/s,低于Nafion117膜的甲醇渗透系数(2×10-6cm2/s).此系列膜的耐氧化性比较优异,可望用于质子交换膜燃料电池中.     

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.     

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。     

新型磺化聚酰亚胺膜的合成与表征

合成了4,4’-二(间氨基苯氧基)联苯-3,3’-二磺酸(mBAPBDS)单体, 采用红外光谱和核磁共振等方法对其结构进行了表征. 使用mBAPBDS, 2-(对胺基苯基)苯并噁唑-5-胺(APBA)和1,4,5,8-萘四甲酸二酐(NTDA)共聚合成了含有噁唑结构的新型磺化聚酰亚胺(NTDA-mBAPBDS/APBA), 通过控制磺化二胺与非磺化二胺的比例来控制磺化程度. NTDA-mBAPBDS/APBA共聚物表现出较好的溶解性、成膜性能和良好的热稳定性, 其磺酸基团分解温度高于300 ℃. 采用溶液浇铸法制备了磺化聚酰亚胺(SPIs)膜, 对膜的吸水率、溶胀度和质子电导率等性能进行了初步的研究. 结果表明, SPIs膜具有适当的吸水率和良好的尺寸稳定性, 其室温电导率在4.72×10－3和9.60×10－3 S/cm之间, 接近于相同条件下Nafion®117的电导率(9.80×10－3 S/cm).     

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).     

含二氮杂萘酮结构磺化聚酰亚胺共聚物的合成及其膜性能研究

将磺化二胺单体4,4′-二(4-氨基苯氧基)联苯-3,3′-二磺酸(BAPBDS),含二氮杂萘酮结构的二胺1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基]-二氮杂萘-1-酮(DHPZDA)和1,4,5,8-萘四甲酸二酐(NTDA)进行缩合聚合反应,通过改变磺化二胺单体BAPBDS的含量,合成了一系列不同磺化度的聚酰亚胺(SPIs).采用FT-IR,1H-NMR表征了聚合物的结构,热重分析仪(TGA)研究了聚合物的耐热稳定性.以间甲酚为溶剂,通过溶液浇铸法成膜研究了该系列聚合物膜的性能.结果表明,与其它磺化聚酰亚胺相比,该系列磺化聚酰亚胺的溶解性以及在高温下(80℃)水解稳定性有较大提高.     

直接甲醇燃料电池中的膜性能比较

制备了磺化聚醚醚酮(SPEEK)和磺化酚酞型聚醚砜(SPES-C)两种质子交换膜,考察了其质子导电和阻醇性能.实验发现,两种新型质子交换膜具有一定的化学稳定性和质子电导率,尤其在高温下两种新膜的质子电导率与Nafion膜接近.两种新膜的甲醇透过系数要比Nafion膜的低1～2个数量级.分别以两种新型膜和Nafion115膜为电解质制备了直接甲醇燃料电池膜电极,讨论了膜材料的性能对直接甲醇燃料电池性能的影响.结果表明,膜材料的阻醇性越好,电池的开路电压越高;膜的电导率越高,在较高电流密度区域内电池的性能越好.     

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 characterization of sulfonated polyimide membranes for direct methanol fuel cell

The sulfonated polyimide (SPI) membranes for direct methanol fuel cell (DMFC) were synthesized with 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 2,2′-benzidinedisulfonic acid (BDSA), 4,4′-oxydianiline (ODA) through classical two-step methods: (1) preparation of sulfonated poly(amic acid) (SPAA) precursors with different sulfonation levels by controlling the molar ratio of BDSA to ODA, and (2) thermal imidization of the SPAA films. The chemical structure and the imidization from SPAA membranes were characterized by FT-IR with temperature, and the sulfonation levels were determined by elemental analysis. The thermal stability of the membranes was also characterized by TGA. From water uptake and small angle X-ray scattering (SAXS) experiments for different sulfonation levels, it was found that the number of water clusters in SPI membranes increased as the water uptake of membranes increased, but the size of water cluster was not changed with the sulfonation levels. The proton conductivity and the methanol permeability of SPI membrane showed a sudden leap like a percolation phenomenon around 35 mol% of sulfonation level. The SPI membranes exhibited relatively high proton conductivity and extremely low methanol permeability, and showed the feasibility of suitable polymer electrolyte membranes (PEM) for DMFC.     

Synthesis and Characterization of Novel Sulfonated Polyimides from 4,6-Bis（4-aminophenoxy）-naphthalene-2-sulfonic Acid

A novel sulfonated diamine monomer, 4,6-bis（4-arninophenoxy）-naphthalene-2-sulfonic acid（BAPNS）, was synthesized. A series of sulfonated polyimide copolymers was prepared from BAPNS, 1,4,5,8-naphthalenetetracarboxylic dianhydride（NTDA） and nonsulfonated diamine 4,4＇-diaminodiphenyl ether（ODA）. Flexible, transparent, and mechanically strong membranes were obtained. The novel sulfonated polyimide（SPI） membranes show higher conductivity, for example, SPI-100 shows a conductivity of 0.0698 S/cm at 80℃（SPI-X： Xrefers to molar fraction of BAPNS）. The membranes exhibit the permeability of methanol from 2.18×10^-7 cm2/s to 2.57×10^-7 cm2/s, which is much lower than that of Nafion（2.00×10 6 cm^2/s）. The copolymers were thermally stable up to 330℃. The sulfonated polyimide copolymers also show reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 100%（molar fraction） BAPNS is 1.35 GPa under high moisture condi- tions. The optimum concentration of BAPNS was found to be 100%（molar fraction） from the view point of proton conductivity, methanol permeability, and membrane stability.     

含氨基磺化聚芳醚酮砜质子交换膜的制备与性能

通过四元缩聚的方法合成了带有氨基的磺化度可控的磺化聚芳醚酮砜共聚物(Am-SPAEKS). 采用红外光谱和核磁共振谱表征了Am-SPAEKS共聚物的结构. 该共聚物膜具有较好的热性能、尺寸稳定性、较高的质子传导率和阻醇能力. 在80℃时Am-SPAEKS-1膜的质子传导率达到0.0894 S/cm, 而其甲醇渗透系数在25℃时为0.24×10^-6 cm²/s, 低于相同温度下SPAEKS膜(0.87×10^-6 cm²/s)和Nafion膜(2×10^-6 cm²/s). 结果表明, Am-SPAEKS膜能够满足质子交换膜燃料电池(PEMFC)的使用要求.     

磺化酚酞型聚醚砜膜的制备及其阻醇和质子导电性能

直接甲醇燃料电池 (Directmethanolfuelcell,DMFC)以高效、清洁和燃料储运方便等优点适宜于作为各种用途的可移动动力源 ,成为 2 0世纪 90年代以来研究与开发的热点[1,2 ] .目前 ,这种电池的研究难点主要集中在催化剂不稳定和质子交换膜透醇上 .一张好的DMFC膜不但要可传递质子、绝缘电子 ,还应具有良好的阻醇性能 .如果膜的阻醇性能不好 ,甲醇会穿过膜到达阴极 ,与氧直接反应而不产生电流 ,不但造成燃料的浪费 ,同时也影响阴极的正常反应 ,使电池效率下降[3 ] .目前广泛应用于燃料电池中的Nafion 系列膜是由美国DuPont公司生产的一种…     

Synthesis and characterization of novel sulfonated naphthalenic polyimides as proton conductive membrane for DMFC applications

To prepare proton conductive membrane for direct methanol fuel cells (DMFC), a novel sulfonated aromatic diamine monomer, 1,4-bis(4-amino-2-sulfonic acid-phenoxy)-benzene (DSBAPB) was synthesized and characterized by ¹H NMR and FT-IR. Then a series of sulfonated polyimides (SPIs) were prepared from DSBAPB with 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA) and a non-sulfonated diamine, 4,4′-oxydianiline (ODA) via one-step high-temperature polymerization method. The sulfonation degree of the SPIs can be controlled by changing the mole ratio of sulfonated monomer to non-sulfonated monomer. The obtained SPI membranes exhibit desirable proton conductivity ranged from 7.9 × 10⁻³ to 7.2 × 10⁻² S cm⁻¹ and low methanol permeability of less than 2.85 × 10⁻⁷ cm² s⁻¹. Furthermore, the hydrolysis stability of the obtained SPIs is better than the BDSA based SPIs caused by the flexible structure.     

磺化聚芳醚砜/磺化聚酰亚胺复合质子交换膜的制备与性能研究

利用溶液浇铸法制备了一系列双磺化型磺化聚芳醚砜/磺化聚酰亚胺(SPAES/SPI)复合质子交换膜.扫描电子显微镜(SEM)结果显示复合膜不存在明显的相分离,表明二者具有很好的相容性.由于SPI的引入,复合膜在甲醇中稳定性较纯SPAES具有大幅的提高,比Nafion112低得多的甲醇吸收率表明了这些复合膜具有比后者更低的甲醇透过率.复合膜显示了与单组分膜相类似的高温分解稳定性,磺酸基团的分解温度达到了290℃以上.复合膜显示出远高于纯SPAES膜的尺寸稳定性能,在130℃高温中200h处理后,所有的复合膜均保持了高的机械性能,而此时纯SPAES膜已经溶解于水中.而且由于两种磺化聚合物间的复合,复合膜维持了较高的IEC水平,显示了较高的质子导电率,在80%相对湿度时的质子导电率与Nafion112相近,而在水中的质子导电率均高于Nafion112.     

磺化聚醚醚酮膜的制备及其阻醇和质子导电性能

直接甲醇燃料电池 (Ｄｉｒｅｃｔｍｅｔｈａｎｏｌｆｕｅｌｃｅｌｌ,ＤＭＦＣ)以高效、清洁和燃料储运方便等优点适宜于作为各种用途的可移动动力源 ,成为 2 0世纪 90年代以来研究与开发的热点[1,2 ] .目前 ,这种电池的研究难点主要集中在催化剂不稳定和质子交换膜透醇上 .一张好的ＤＭＦＣ膜不但要可传递质子、绝缘电子 ,还应具有良好的阻醇性能 .如果膜的阻醇性能不好 ,甲醇会穿过膜到达阴极 ,与氧直接反应而不产生电流 ,不但造成燃料的浪费 ,同时也影响阴极的正常反应 ,使电池效率下降[3] .目前广泛应用于燃料电池中的Ｎａｆｉｏｎ系列膜…     

Effect of Sulfonation Degree on Performance of Proton Exchange Membranes for Direct Methanol Fuel Cells

A series of proton exchange membranes based on sulfonated polyarylene ether ketones(SPAEKs) was used to study the effect of sulfonation degree on proton conductivity, methanol permeation and performance of direct methanol fuel cells(DMFCs). Dependences of physical characteristics of the membranes, i. e., proton conductivity, water uptake, swelling ratio, methanol permeability and ion exchange capacity(IEC) were systematically studied. Both methanol permeability and proton conductivity of the SPAEK membrane grow rapidly as the increase in sulfonation degree since methanol molecules and protons share the same transfer channel. However,the methanol permeability plays more important role comparing to proton conductivity. As a result, the SPAEK membrane with a medium sulfonation degree(60%) was found to yield the best performance in a DMFC due to the acquirement of balanced conductivity and methanol permeability.     

SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜研究

通过在磺化聚醚醚酮(SPEEK,DS=61.68%)中分别混入酚酞型聚醚砜(PES-C)、磺化酚酞型聚醚砜(SPES-C,DS=53.7%)制备出SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜.结果表明,共混的两种聚合物之间均具有较好的相容性.PES-C、SPES-C的混入能有效降低膜的溶胀及甲醇透过,且随着共混量的增加,这种作用越趋明显.纯SPEEK膜在75℃左右溶解,而SPEEK/PES-C(30wt%)、SPEEK/SPES-C(30wt%)共混膜在80℃时溶胀度仅为22.5%、26.32%.在室温至80℃范围内,纯SPEEK及共混膜的甲醇透过系数都在10-7cm2.s-1数量级上,远小于Nafion115膜.在饱和湿度下,温度大于90℃时,SPEEK/PES-C(20wt%)共混膜电导率超过Nafion115膜;温度大于110℃时,SPEEK/SPES-C(30wt%)共混膜电导率与Nafion115膜相当,达到0.11S.cm-1.高电导率,低透醇系数以及明显提高了的可使用温度表明该类共混膜有望在DMFC中使用.     

Synthesis and characterization of sulfonated naphthalenic polyimides based on 4,4′-diaminodiphenylether-2,2′-disulfonic acid and bis[4-(4-aminophenoxy)phenylhexafluoropropane] for fuel cell applications

The paper describes the synthesis and characterization of sulfonated polyimides based on 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA), 4,4′-diaminodiphenylether-2,2′-disulfonic acid (ODADS) and (bis[4-(4-aminophenoxy)phenylhexafluoropropane] (BDAF)). Several copolymer samples were prepared by varying the molar ratio of ODADS: BDAF (0.5:1.50, 0.75:1.25, 1:1 and 1.50: 0.5) in the initial monomer feed. Structural characterization of the copolymers was done using FT-IR and ¹H NMR. ¹H NMR was also used to calculate the copolymer composition. Thermal characterization was done using thermogravimertry and dynamic mechanical analysis. Polymer films were prepared by solution casting using m-cresol as solvent. The membranes thus prepared were characterized for water uptake, water stability, methanol permeability and proton conductivity. The obtained sulfonated polyimides (SPI’s) had proton conductivities in the range of 0.137-3.94 mS/cm. SPI’s with 50% degree of sulfonation had proton conductivity comparable to that of Nafion with methanol permeability lower than that of Nafion. It was found that the degree of sulfonation of polyimide had a large effect on the thermal stability, water uptake, ion-exchange capacity and proton conductivity.