【作者】 梅学华；

【导师】 张守海；

【作者基本信息】 大连理工大学 ， 高分子材料， 2008， 硕士

【摘要】 本论文是以磺化聚芳醚酮在质子交换膜燃料电池中的应用为研究背景,从分子设计角度合成了几种不同结构的磺化杂萘联苯聚芳醚酮酮（SPPEKKs）,并对其相关性能进行了研究,希望能够得到一种新的性能较好的质子交换膜材料。采用发烟硫酸作为磺化试剂,通过亲电取代反应,分别在1,4-二（4-氯代苯甲酰基）苯（BCBB）和1,4-二（4-氟代苯甲酰基）苯（BFBB）上引入磺酸钠基团,成功合成了1,4-二（3-磺酸钠基-4-氯代苯甲酰基）苯（SBCBB）和1,4-二（3-磺酸钠基-4-氟代苯甲酰基）苯（SBFBB）两种磺化单体,利用FT-IR和¹H-NMR对磺化单体进行了结构表征。通过亲核缩聚反应,调节SBCBB（SBFBB）与BFBB（BCBB）的比例与4-（4-羟基苯基）-2,3-二氮杂萘-1-酮（DHPZ）聚合,合成了不同磺化度的磺化聚芳醚酮酮（SPPEKK、SPPEKK-F）;不同比例的SBFBB和BFBB与含二甲基双酚单体（DMDHPZ）进行聚合,得到了不同磺化度的高分子量含二甲基磺化杂萘联苯聚醚酮酮（SPPEKK-D）;不同比例的SBFBB和DFBN与DMDHPZ进行聚合,得到了不同磺化度的高分子量磺化杂萘联苯聚醚腈酮酮（SPPENKK）。利用FT-IR和¹H-NMR对所合成的磺化杂萘联苯聚芳醚酮酮结构进行了表征。磺化杂萘联苯聚芳醚酮酮都溶于NMP、DMSO和DMAC等极性非质子性溶剂。利用溶液浇铸法制备了磺化聚芳醚酮酮膜。所制备的磺化聚芳醚酮酮都具有好的机械性能,拉伸强度在46Mpa以上,杨氏模量在1.5Gpa以上。测试了膜的吸水率、溶胀率、耐氧化性、离子交换容量和质子传导率等性能。吸水率、溶胀率和质子传导率随温度和磺化度的增加而增加。耐氧化性随磺化度的增加而降低。对不同结构磺化杂萘联苯聚芳醚酮酮的性能进行了比较。所制备磺化聚芳醚酮酮均具有良好的热稳定性,5%的热失重温度分别在448℃（盐型）和331℃（酸型）以上;由于甲基取代了酚氧原子邻位的活泼氢原子,SPPEKK-D具有最好的氧化稳定性。利用TEM对SPPEKKs膜的微观形态进行分析,同磺化度的SPPENKK由于氰基的引入,膜中的离子簇密度和尺寸变大,亲水相分布更为连续,表现出更好的相分离结构,具有更高的吸水率、离子交换容量和质子传导率。所有聚合物膜在磺化度大于0.8、温度高于80℃时,具有较高的质子传导率(＞10^-2S/cm),达到了质子交换膜燃料电池的使用要求。更多还原

【Abstract】 In this thesis,several kinds of sulfonated poly（phthalazinone ether ketone ketone）s （SPPEKKs）have been synthesized based on the molecular design principle under the background of the application of sulfonated poly（arylene ether keton）s in proton exchange membrane fuel cells（PEMFC）.Correlative performances of all polymers are studied in order to find a novel membrane material with good properties in PEMFC application.Two sulfonated monomers 1,4-bis（3-sodium sulfonate-4-chlorobenzoyl）bezene（SBCBB） and 1,4-bis（3-sodium sulfonate-4-fluorobenzoyl）bezene（SBFBB）are successfully prepared by sulfonation of 1,4-bis（4-chlorobenzoyl）benzene（BCBB）and 1,4-bis（4-fluorobenzoyl） benzene（BFBB）respectively with fuming sulfuric acid via aromatic electrophilic substitution reaction.FT-IR and ¹H-NMR are used to characterize the structures of sulfonated monomers’.Novel sulfonated poly（phthalazinone ether ketone ketone）（SPPEKK）with different sulfonation degree（SD）are synthesized via direct nucleophilic polycondensation from SBCBB（SBFBB）,BFBB（BCBB）and 4-（4-hydroxyphenyl）-2,3-phthalazin-1-one（DHPZ）; sulfonated poly（phthalazinone ether ketone ketone）（SPPEKK-D）containing dimethyl groups with different sulfonation degree and high molecular weight are prepared by direct aromatic nucleophilic polycondensation of SBFBB,BFBB and 4-（3,5-dimethyl-4-hydroxyphenyl）-2,3-phthalazin-1-one（DMDHPZ）;sulfonated poly（phthalazinone ether nitrile ketone ketone） （SPPENKK）containing dimethyl groups with different sulfonation degree and high molecular weight are obtained by direct nucleophilic polycondensation of SBFBB,2,6-difluoro benzonitrile（DFBN）and DMDHPZ.Polymers’ structures are characterized by FT-IR and ¹H-NMR.All polymers have good solubility in polar aprotic solvent such as NMP,DMAC and DMSO.Sulfonated poly（phthalazinone ether ketone ketone）s films are prepared by solution casting method.Membranes’ properties such as water uptake,swelling ratio,oxidative resistance,ion exchange capacity（IEC）and proton conductivities have been measured.Water uptake,swelling ratio,IEC and proton conductivity increased with the increasing SD. However,oxidative resistance decreased with SD increasing.The tensile test results show that tensile stress is above 46Mpa and Young’s Modulus is above 1.5Gpa,which indicates sulfonated poly（phthalazinone ether ketone ketone）s films have good mechanical stability. Polymers with different structures have different performances,and performance details are given to make some comparison.The 5%weight loss temperature of these polymers is above 448℃（in sodium form）and above 331℃（in acid form）,respectively,indicating they have good thermal stabilities.The SPPEKK-D membranes have the best oxidative stability, probably due to the introduction of dimethyl groups which substitute the active hydrogen atoms at the ortho position of phenolate oxygen atom.Transmission electron microscope （TEM）is used to study the membrane’s micro-morphology.Compared with other polymers, SPPENKK membrane with a same SD has a much higher water uptake,IEC value and proton conductivities;the ionic-clusters’ density in them is much higher and their average size becomes larger.Moreover,the hydrophilic phase becomes more continuous and the phase-separation becomes more obvious.This might because of the introduction of polar and hydrophilic cyano groups into SPPENKK’s main chain.When temperature is above 80℃,all polymers with SD more than 0.8 show good proton conductivities(＞10^-2S·cm^-1),which meets the requirement in PEMFC application.更多还原