磺化侧苯基杂萘联苯聚芳醚质子交换膜的研究
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摘要
本文针对燃料电池用磺化聚芳醚质子交换膜的制备和性能开展深入研究,从分子设计的角度出发,合成了磺化含苯基侧基杂萘联苯聚芳醚酮和磺化含苯基侧基杂萘联苯聚芳醚砜。
以4-(3-苯基-4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ-O)、4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)、4,4’-二氯二苯砜(DCS)和4,4’-二氟二苯酮(DFK)为单体,通过亲核缩聚反应分别合成了含苯基侧基杂萘联苯聚醚砜(PPES-P)和含苯基侧基杂萘联苯聚醚酮(PPEK-P),GPC和特性粘度数据结果显示聚合物具有很高的分子量,利用FT-IR和’H-NMR对所合成的聚合物进行了结构表征。然后以95%-98%的浓硫酸为磺化剂,通过改变磺化温度和磺化时间来控制磺酸基的位置和磺化度,确定最优磺化条件,由亲电取代反应得到了一系列不同磺化度的磺化含苯基侧基杂萘联苯聚醚酮(SPPEK-P)和磺化含苯基侧基杂萘联苯聚醚砜(SPPES-P),实现了磺化聚合物的可控定位合成。利用FT-IR和’H-NMR对所合成的磺化产物进行了结构表征,表明得到了理想的聚合物。
用溶液浇膜法制备了SPPES-P和SPPEK-P质子交换膜,并且考察了质子交换膜的IEC、吸水性、溶胀率、质子传导率、甲醇渗透性能和耐氧化性能。结果表明,质子交换膜具有较低的溶胀率和较高的吸水率,IEC随着磺化度的增加而增加,磺化度在0.8以上的SPPES-P和SPPEK-P质子交换膜在85℃时的质子传导率都高于0.01 S·cm-1,并且具有良好的阻醇性能和耐氧化性。对两系列膜的性能进行了比较,SPPEK-P膜具有较高的断裂伸长率、质子传导率和耐氧化性能,而SPPES-P膜的拉伸强度和弹性模量更高一些,SPPES-P和SPPEK-P膜的5%热失重温度分别在392℃和395℃以上,具有良好的耐热性能。此外,与前人制备的磺酸基在聚合物主链上的磺化含苯基侧基杂萘联苯聚醚酮(SPPEK-O)相比,两个系列膜具有更好的耐氧化性、力学强度和质子传导率。综合性能表明基本满足了质子交换膜燃料电池的使用要求。
In this thesis, the synthesis and performance of sulfonated poly(phthalazinone ether) as proton exchange membranes have been studied deeply based on the molecular design principle under the background of the application in proton exchange membrane fuel cells(PEMFC). Two series of sulfonated poly(phthalazinone ether sulfone) containing pendant phenyl groups(SPPES-P) and sulfonated poly(phthalazinone ether ketone) containing pendant phenyl groups(SPPEK-P) were synthesized.
Poly (phthalazinone ether sulfone) containing pendant phenyl groups (PPES-P)and poly (phthalazinone ether ketone) containing pendant phenyl groups (PPEK-P) were synthesized respectively by aromatic nucleophilic substitution reaction from 4-(3-phenyl-4-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ-O) 4-(4-hydroxyphenyl)-2,3-phthalazin-l-one (DHPZ),4,4'-dichlorodiphenyl sulfone (DCS) and 4,4-difluorobenzophenone(DFK). The intrinsic viscosity and molecular weight of polymers have been measured respectively and the result indicated that these polymer had high molecular weight. FT-IR and'H-NMR are used to characterize the structures of polymers. Sulfonated poly (phthalazinone ether sulfone) containing pendant phenyl groups(SPPES-P) and Sulfonated poly (phthalazinone ether ketone) containing pendant phenyl groups (SPPEK-P) with different sulfonation degree are prepared by electrophilic substitution reaction with concentrated sulfuric acid as sulfonating agent, The optimized sulfonation conditions are determined by changing sulfonation temperature and time, and the sulfonated position are controlled successfully. Sulfonated polymers'structures are characterized by FT-IR and'H-NMR, and the result show that ideal polymers are obtained.
SPPES-P and SPPEK-P proton exchange membranes are prepared by solution casting method. The water uptake, swelling ratio, proton conductivity, methanol permeability, and oxidative stability of SPPES-P and SPPEK-P membranes were investigated. These membranes have excellent water uptake ratio and low swelling ratio,IEC increased with the increasing SD. When temperature is above 85℃, all membranes with SD more than 0.8 show good proton conductivities (>10-2 S·cm"1), The membranes showed high oxidative stability and good methanol permeability. The two series of membranes are given to make comparison, SPPEK-P membranes have higher break strain and better proton conductivities and better oxidative stability. However, the tensile strength and tensile modulus of SPPES-P membranes are better. The 5%weight loss temperature of SPPES-P and SPPEK-P membranes are above 375℃and 395℃indicated that they all have good thermal stabilities. Besides, these membranes indicated better oxidative stability, mechanical performance and higher proton conductivity compared with sulfonated poly(phthalazinone ether ketone) containing pendant phenyl groups (SPPEK-O) which were synthesized by previous researcher. All properties show that these membranes can be used in PEMFC application.
以4-(3-苯基-4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ-O)、4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)、4,4’-二氯二苯砜(DCS)和4,4’-二氟二苯酮(DFK)为单体,通过亲核缩聚反应分别合成了含苯基侧基杂萘联苯聚醚砜(PPES-P)和含苯基侧基杂萘联苯聚醚酮(PPEK-P),GPC和特性粘度数据结果显示聚合物具有很高的分子量,利用FT-IR和’H-NMR对所合成的聚合物进行了结构表征。然后以95%-98%的浓硫酸为磺化剂,通过改变磺化温度和磺化时间来控制磺酸基的位置和磺化度,确定最优磺化条件,由亲电取代反应得到了一系列不同磺化度的磺化含苯基侧基杂萘联苯聚醚酮(SPPEK-P)和磺化含苯基侧基杂萘联苯聚醚砜(SPPES-P),实现了磺化聚合物的可控定位合成。利用FT-IR和’H-NMR对所合成的磺化产物进行了结构表征,表明得到了理想的聚合物。
用溶液浇膜法制备了SPPES-P和SPPEK-P质子交换膜,并且考察了质子交换膜的IEC、吸水性、溶胀率、质子传导率、甲醇渗透性能和耐氧化性能。结果表明,质子交换膜具有较低的溶胀率和较高的吸水率,IEC随着磺化度的增加而增加,磺化度在0.8以上的SPPES-P和SPPEK-P质子交换膜在85℃时的质子传导率都高于0.01 S·cm-1,并且具有良好的阻醇性能和耐氧化性。对两系列膜的性能进行了比较,SPPEK-P膜具有较高的断裂伸长率、质子传导率和耐氧化性能,而SPPES-P膜的拉伸强度和弹性模量更高一些,SPPES-P和SPPEK-P膜的5%热失重温度分别在392℃和395℃以上,具有良好的耐热性能。此外,与前人制备的磺酸基在聚合物主链上的磺化含苯基侧基杂萘联苯聚醚酮(SPPEK-O)相比,两个系列膜具有更好的耐氧化性、力学强度和质子传导率。综合性能表明基本满足了质子交换膜燃料电池的使用要求。
In this thesis, the synthesis and performance of sulfonated poly(phthalazinone ether) as proton exchange membranes have been studied deeply based on the molecular design principle under the background of the application in proton exchange membrane fuel cells(PEMFC). Two series of sulfonated poly(phthalazinone ether sulfone) containing pendant phenyl groups(SPPES-P) and sulfonated poly(phthalazinone ether ketone) containing pendant phenyl groups(SPPEK-P) were synthesized.
Poly (phthalazinone ether sulfone) containing pendant phenyl groups (PPES-P)and poly (phthalazinone ether ketone) containing pendant phenyl groups (PPEK-P) were synthesized respectively by aromatic nucleophilic substitution reaction from 4-(3-phenyl-4-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ-O) 4-(4-hydroxyphenyl)-2,3-phthalazin-l-one (DHPZ),4,4'-dichlorodiphenyl sulfone (DCS) and 4,4-difluorobenzophenone(DFK). The intrinsic viscosity and molecular weight of polymers have been measured respectively and the result indicated that these polymer had high molecular weight. FT-IR and'H-NMR are used to characterize the structures of polymers. Sulfonated poly (phthalazinone ether sulfone) containing pendant phenyl groups(SPPES-P) and Sulfonated poly (phthalazinone ether ketone) containing pendant phenyl groups (SPPEK-P) with different sulfonation degree are prepared by electrophilic substitution reaction with concentrated sulfuric acid as sulfonating agent, The optimized sulfonation conditions are determined by changing sulfonation temperature and time, and the sulfonated position are controlled successfully. Sulfonated polymers'structures are characterized by FT-IR and'H-NMR, and the result show that ideal polymers are obtained.
SPPES-P and SPPEK-P proton exchange membranes are prepared by solution casting method. The water uptake, swelling ratio, proton conductivity, methanol permeability, and oxidative stability of SPPES-P and SPPEK-P membranes were investigated. These membranes have excellent water uptake ratio and low swelling ratio,IEC increased with the increasing SD. When temperature is above 85℃, all membranes with SD more than 0.8 show good proton conductivities (>10-2 S·cm"1), The membranes showed high oxidative stability and good methanol permeability. The two series of membranes are given to make comparison, SPPEK-P membranes have higher break strain and better proton conductivities and better oxidative stability. However, the tensile strength and tensile modulus of SPPES-P membranes are better. The 5%weight loss temperature of SPPES-P and SPPEK-P membranes are above 375℃and 395℃indicated that they all have good thermal stabilities. Besides, these membranes indicated better oxidative stability, mechanical performance and higher proton conductivity compared with sulfonated poly(phthalazinone ether ketone) containing pendant phenyl groups (SPPEK-O) which were synthesized by previous researcher. All properties show that these membranes can be used in PEMFC application.
引文
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