磺化杂萘联苯聚醚酮酮及聚酰亚胺质子交换膜的研究
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摘要
质子交换膜燃料电池(PEMFC)是目前世界上最成熟的一种能将氢气与空气中的氧气化合成洁净水并释放出电能的技术，由于其具有能量密度高、无噪音、工作温度低等特点和优势，而成为发展最快、应用最广和最有前途的燃料电池，是具有能源革命意义的新一代能源动力系统。目前PEMFC中主要使用的是全氟磺酸型质子交换膜，但价格昂贵、使用温度低以及甲醇渗透率高等缺点限制了它们的广泛应用。因此，以成本低廉的碳氢主链以及主链含杂原子的芳香性聚合物为原料，通过磺化、掺杂无机电解质等方法制备质子交换膜成为学术界的研究热点。
本文以4，4′-(4-氟苯甲酰基)苯(DFKK)、3，3′-二磺酸钠-4，4′-(4-氟苯甲酰基)苯(SDFKK)、六氟双酚A(BPAF)和4-(4-羟苯基)二氮杂萘酮(DHPZ)为单体，通过溶液亲核取代逐步聚合的方法合成了一系列不同磺化度高分子量的磺化聚醚酮酮(SPPFEKK)。聚合物的特性粘度在1．29～1．53 dL/g之间，通过溶液铸膜法制备的高分子量聚合物均质膜均表现出了较好的韧性。通过FT-IR，~1H-NMR等手段对SPPFEKK的结构进行了表征，并研究了膜的性能。结果表明，SPPFEKK磺酸基的热分解温度在340℃，主链分解温度在550℃以上；拉伸强度在57．1～69．2 MPa之间；膜的质子传导率和甲醇渗透系数均随着磺化度的增大而增大，磺化度(DS)为1．2的SPPFEKK-120膜的质子传导率(σ)达到1．0×10~(-1)S／cm(95℃)；甲醇渗透系数在1．58×10~(-7)～2．76×10~(-7)cm~2／s，比Nation(?)117膜(10~(-6)cm~2／s)降低了一个数量级。
以磺化度为1．0的SPPFEKK和SPPEKK(以DFKK，SDFKK和DHPZ为单体合成的磺化聚醚酮酮)为基体，采用溶胶凝胶法制备了有机-无机复合膜，并引入正硅酸乙酯以及能与无机质子导体作用的硅烷偶联剂γ-氨丙基三乙氧基硅烷(AS)进行水解缩合，进一步将无机质子导体“固定”在硅胶空间网状结构中。考察了PWA／AS／SiO_2的加入对复合膜的性能的影响。实验证明，与直接掺杂以及溶胶共混法掺杂杂多酸无机质子导体相比，PWA／AS／SiO_2的加入更加有效地抑制了PWA的渗漏。PWA／AS／SiO_2加入量为15％的SPPFEKK-15和SPPEKK-15在95℃的质子传导率分别达到1．0×10~(-1)S／cm和8．9×10~(-2)S／cm，比纯膜提高了近一倍；复合膜的5％热失重温度分别为308和304℃；拉伸强度为76．7和70．8 MPa。通过连续测试7天来考察复合膜中PWA在水中的溶出性，发现PWA的溶出主要发生在前三天，每天的溶出量为0．7％左右，三天后PWA的溶出速度明显减小，每天的溶出量低于0．3％，测试七天时PWA在水中几乎不再溶出，溶出量低于0．1％，且复合膜仍具有较高的质子传导率(>6．1×10~(-2)S／cm)。
以50％发烟硫酸为磺化剂，2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基1-二氮杂萘-1-酮(DHPZDA)为原料，合成了一种新型的磺化二胺单体2-(2-磺酸基-4-氨基苯基)-4-[4-(2-磺酸基-4-氨基苯氧基)-苯基]-二氮杂萘-1-酮(S-DHPZDA)，并对其合成工艺条件进行了优化。以4,4′-Z氨基二苯醚-2,2′-二磺酸基(ODADS)，4,4′-二(4-氨基苯氧基)-2,2-′二磺酸基联苯(BAPBDS)，S-DHPZDA为磺化二胺单体，4,4′-二氨基二苯醚(ODA)，4,4′-二(4-氨基苯氧基)联苯(BAPB)，DHPZDA为非磺化共聚二胺单体，1,4,5,8-萘四甲酸二酐(NTDA)为二酸酐单体，采用一步聚合法合成了六个系列不同磺化度的磺化聚酰亚胺(SPI-1～6)，并通过溶液铸膜法制备了聚合物膜。对其结构进行了表征，并研究了溶解性、耐热稳定性、水解和抗氧化稳定性、含水率、尺寸稳定性、力学性能、阻醇性能以及质子传导率等性能与其结构的关系。结果表明，与其它磺化聚酰亚胺相比，扭曲非共面的二氮杂萘酮的引入极大地提高了SPI的溶解性能，随着磺化度增大，SPI-1～6可以溶解在N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)等非质子极性溶剂中；SPI膜具有优异的热稳定性能，磺酸基的降解温度均在310℃以上，且随着DS的增大而升高，主链的降解温度在560℃以上；SPI的质子传导率随DS的增大而增大，当DS大于0．6时，95℃时SPI的质子传导率达到10~(-2)S／cm；通过在SPI的主链中引入柔性基团以及碱性较强的磺化二胺单体可以提高SPI的水解稳定性能，高磺化度的SPI-6-80达到了1280 h；低磺化度的SPI均具有较好的水解稳定性能，SPI-6-20的水解稳定性达到6000 h以上；SPI的拉伸强度在50．1～98．1 MPa；SPI具有优异的阻醇性能，其甲醇渗透系数在10~(-8)～10~(-7) cm~2／s，比Nation(?)117膜(10~(-6)cm~2／s)降低了1～2个数量级。
Proton exchange membrane fuel cells (PEMFC) are one of the most full-blown technologies which can convert the chemical energy from the reaction of the hydrogen and oxygen into electrical energy. The only byproducts from PEMFC systems are the water and heat. They have been the most promising fuel cells because of their high power density, no noise, low working temperature, etc. Until now, perfluorosulfonic acid membranes have been almost the only PEM used either in practical systems or academics. However, they have disadvantages of high cost, high methanol permeability and reduced proton conductivity at high temperature which limited their abroad applications especially in high temperature fuel cell operation. Therefore, extensive attempts have been performed to the preparation of proton exhange membrane (PEM) by polymers with low cost through sulfonation or adulterating inorganic proton conductors.
A series of sulfonated copoly (phthalazinone ether ketone ketone)s (SPPFEKK) were synthesized from 4-(4-hydroxyphenyl)-1(2H)-phthalazinone (DHPZ), 4,4'-hexafiuoroiso-propylidenediphenol (BPAF), 1,4-bi(4-fluorobenzoyl) benzene (DFKK) and 1,4-bi(3-sodium sulfonate-4-fluorobenzoyl) benzene (SDFKK) by direct nucleophilic polycondensation reaction. Their inherent viscosity values are ranged from 1.29 to 1.53 dL/g. The flexible SPPFEKK membranes are prepared by solution casting method from N-methyl-2- pyrrolidone (NMP). The chemical structures of the SPPFEKK are characterized by ~1H-NMR and FT-IR, and the properties of the membranes are investigated too. The results indicated that the decomposed temperatures of sulfonic group and the main chain in the SPPFEKK membranes are above 340℃and 550℃, respectively. The tensile strength of the membranes in dry state varies from 57.1 to 69.2 MPa. The proton conductivity and the methanol permeability are increasing with the sulfonation degree (DS) of the membranes. The proton conductivity of the SPPFEKK with sulfonation degree (DS) of 1.2 is 1.0×10~(-1) S/cm at 95℃. The methanol permeabilities of the SPPFEKK membranes rise from 1.58×10~(-7) cm~2/s to 2.76×10~(-7) cm~2/s with the increment of DS, which is considerably lower than that of Nafion(?) 117.
Organic-inorganic hybrids of SPPFEKK or SPPEKK, heteropoly acids (PWA) and silica were prepared by in situ growth of the inorganic network by hydrolysis and condensation of tetraethoxy silane (TEOS) and 3-aminopropyltrimethoxysilane (AS). The AS has the interaction with the PWA and TEOS, which could fix the PWA in the net structure of the SiO_2. The influence of the introduction of the PWA/AS/SiO_2 in the composite membranes is investigated. The data proves that the introduction of the PWA/AS/SiO_2 can restrain the leak of the PWA. The proton conductivities of the SPPFEKK-15 and SPPEKK-15 are 1.0×10~(-1) S/cm and 8.9×10~(-2) S/cm at 95℃, which multiply one-fold comparing with pure membranes. The 5% weitht loss temperatures of the composite membranes are 308℃and 304℃. The tensile strength values of them are 76.7 MPa and 70.8 MPa. The stability of the PWA in the composite membranes is characterized by immersing the membranes in water for 7 days and tests the PWA concentration of the water everyday. The result shows that the leakness of the PWA mainly happens in the first three days, and the leak percentage is lower than 0.7%/day. Then the speed of the leakness becomes lower, and the leak percentage is less than 0.3%/day. At the 7th days, PWA in composite membranes gets to stable and the composite membranes still have considerable high proton conductivity (above 6.1×10~(-2) S/cm).
A novel sulfonated diamine, 1,2-dihydro-2-(2-sulfonic-4-amino-phenyl)- 4-[4-(2-sulfonic-4-aminophenoxy)-phenyl]-phthalazin-1-one (S-DHPZDA), is successfully synthesized from 1,2-dihydro-2-(4-amino-phenyI)-4-[4-(4-aminophenoxy)-phenyl]-phthalazin-1-one(DHPZDA) by direct sulfonation. Six series of sulfonated polyimides (SPI-1-6) are prepared by sulfonated diamines, S-DHPZDA, 4,4'-bis(4-aminophenoxy)biphenyl-3,3'-disulfonic acid (BAPBDS), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), nonsulonated diamines, 4,4'-diaminodiphenyl ether (ODA), 4,4'-bis(4-aminophenoxy) biphenyl (BAPB), DHPZDA and 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) by "one-step" copolymerization. The results demostrate that compared to other SPI, SPI-1-6 have improved solubility because of the introduction of the noncoplanar and twist structure phthalazinone moieties in the polymers main chain. The SPI-1-6 could soluble in aprotic organic solvents like m-cresol, NMP, DMSO. The decomposed temperatures of sulfonic group and the main chain in the SPI-1-6 membranes are above 310℃and 560℃, respectively. When the DS is higher than 0.6, the proton conductivity of the SPI reached to 10~(-2) S/cm at 95℃. The hydrolytic stability of the SPI membranes can be enhanced by inducting flexible bones and more basic sulfonated diamine to the SPI's main chain. SPI-6-80 with high DS (0.8) has the hydrolysis stability of 1280 h, while the SPI-6-20 can maintain its mechanical strength in the water for more than 6000 h at 80℃. The tensile strength of the SPI-1-6 membranes varies from 50.1 to 98.1 MPa. The methanol permeabilities of the SPPFEKK membranes rise from 10~(-8)～10~(-7) cm2/s with the increment of DS.
本文以4，4′-(4-氟苯甲酰基)苯(DFKK)、3，3′-二磺酸钠-4，4′-(4-氟苯甲酰基)苯(SDFKK)、六氟双酚A(BPAF)和4-(4-羟苯基)二氮杂萘酮(DHPZ)为单体，通过溶液亲核取代逐步聚合的方法合成了一系列不同磺化度高分子量的磺化聚醚酮酮(SPPFEKK)。聚合物的特性粘度在1．29～1．53 dL/g之间，通过溶液铸膜法制备的高分子量聚合物均质膜均表现出了较好的韧性。通过FT-IR，~1H-NMR等手段对SPPFEKK的结构进行了表征，并研究了膜的性能。结果表明，SPPFEKK磺酸基的热分解温度在340℃，主链分解温度在550℃以上；拉伸强度在57．1～69．2 MPa之间；膜的质子传导率和甲醇渗透系数均随着磺化度的增大而增大，磺化度(DS)为1．2的SPPFEKK-120膜的质子传导率(σ)达到1．0×10~(-1)S／cm(95℃)；甲醇渗透系数在1．58×10~(-7)～2．76×10~(-7)cm~2／s，比Nation(?)117膜(10~(-6)cm~2／s)降低了一个数量级。
以磺化度为1．0的SPPFEKK和SPPEKK(以DFKK，SDFKK和DHPZ为单体合成的磺化聚醚酮酮)为基体，采用溶胶凝胶法制备了有机-无机复合膜，并引入正硅酸乙酯以及能与无机质子导体作用的硅烷偶联剂γ-氨丙基三乙氧基硅烷(AS)进行水解缩合，进一步将无机质子导体“固定”在硅胶空间网状结构中。考察了PWA／AS／SiO_2的加入对复合膜的性能的影响。实验证明，与直接掺杂以及溶胶共混法掺杂杂多酸无机质子导体相比，PWA／AS／SiO_2的加入更加有效地抑制了PWA的渗漏。PWA／AS／SiO_2加入量为15％的SPPFEKK-15和SPPEKK-15在95℃的质子传导率分别达到1．0×10~(-1)S／cm和8．9×10~(-2)S／cm，比纯膜提高了近一倍；复合膜的5％热失重温度分别为308和304℃；拉伸强度为76．7和70．8 MPa。通过连续测试7天来考察复合膜中PWA在水中的溶出性，发现PWA的溶出主要发生在前三天，每天的溶出量为0．7％左右，三天后PWA的溶出速度明显减小，每天的溶出量低于0．3％，测试七天时PWA在水中几乎不再溶出，溶出量低于0．1％，且复合膜仍具有较高的质子传导率(>6．1×10~(-2)S／cm)。
以50％发烟硫酸为磺化剂，2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基1-二氮杂萘-1-酮(DHPZDA)为原料，合成了一种新型的磺化二胺单体2-(2-磺酸基-4-氨基苯基)-4-[4-(2-磺酸基-4-氨基苯氧基)-苯基]-二氮杂萘-1-酮(S-DHPZDA)，并对其合成工艺条件进行了优化。以4,4′-Z氨基二苯醚-2,2′-二磺酸基(ODADS)，4,4′-二(4-氨基苯氧基)-2,2-′二磺酸基联苯(BAPBDS)，S-DHPZDA为磺化二胺单体，4,4′-二氨基二苯醚(ODA)，4,4′-二(4-氨基苯氧基)联苯(BAPB)，DHPZDA为非磺化共聚二胺单体，1,4,5,8-萘四甲酸二酐(NTDA)为二酸酐单体，采用一步聚合法合成了六个系列不同磺化度的磺化聚酰亚胺(SPI-1～6)，并通过溶液铸膜法制备了聚合物膜。对其结构进行了表征，并研究了溶解性、耐热稳定性、水解和抗氧化稳定性、含水率、尺寸稳定性、力学性能、阻醇性能以及质子传导率等性能与其结构的关系。结果表明，与其它磺化聚酰亚胺相比，扭曲非共面的二氮杂萘酮的引入极大地提高了SPI的溶解性能，随着磺化度增大，SPI-1～6可以溶解在N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)等非质子极性溶剂中；SPI膜具有优异的热稳定性能，磺酸基的降解温度均在310℃以上，且随着DS的增大而升高，主链的降解温度在560℃以上；SPI的质子传导率随DS的增大而增大，当DS大于0．6时，95℃时SPI的质子传导率达到10~(-2)S／cm；通过在SPI的主链中引入柔性基团以及碱性较强的磺化二胺单体可以提高SPI的水解稳定性能，高磺化度的SPI-6-80达到了1280 h；低磺化度的SPI均具有较好的水解稳定性能，SPI-6-20的水解稳定性达到6000 h以上；SPI的拉伸强度在50．1～98．1 MPa；SPI具有优异的阻醇性能，其甲醇渗透系数在10~(-8)～10~(-7) cm~2／s，比Nation(?)117膜(10~(-6)cm~2／s)降低了1～2个数量级。
Proton exchange membrane fuel cells (PEMFC) are one of the most full-blown technologies which can convert the chemical energy from the reaction of the hydrogen and oxygen into electrical energy. The only byproducts from PEMFC systems are the water and heat. They have been the most promising fuel cells because of their high power density, no noise, low working temperature, etc. Until now, perfluorosulfonic acid membranes have been almost the only PEM used either in practical systems or academics. However, they have disadvantages of high cost, high methanol permeability and reduced proton conductivity at high temperature which limited their abroad applications especially in high temperature fuel cell operation. Therefore, extensive attempts have been performed to the preparation of proton exhange membrane (PEM) by polymers with low cost through sulfonation or adulterating inorganic proton conductors.
A series of sulfonated copoly (phthalazinone ether ketone ketone)s (SPPFEKK) were synthesized from 4-(4-hydroxyphenyl)-1(2H)-phthalazinone (DHPZ), 4,4'-hexafiuoroiso-propylidenediphenol (BPAF), 1,4-bi(4-fluorobenzoyl) benzene (DFKK) and 1,4-bi(3-sodium sulfonate-4-fluorobenzoyl) benzene (SDFKK) by direct nucleophilic polycondensation reaction. Their inherent viscosity values are ranged from 1.29 to 1.53 dL/g. The flexible SPPFEKK membranes are prepared by solution casting method from N-methyl-2- pyrrolidone (NMP). The chemical structures of the SPPFEKK are characterized by ~1H-NMR and FT-IR, and the properties of the membranes are investigated too. The results indicated that the decomposed temperatures of sulfonic group and the main chain in the SPPFEKK membranes are above 340℃and 550℃, respectively. The tensile strength of the membranes in dry state varies from 57.1 to 69.2 MPa. The proton conductivity and the methanol permeability are increasing with the sulfonation degree (DS) of the membranes. The proton conductivity of the SPPFEKK with sulfonation degree (DS) of 1.2 is 1.0×10~(-1) S/cm at 95℃. The methanol permeabilities of the SPPFEKK membranes rise from 1.58×10~(-7) cm~2/s to 2.76×10~(-7) cm~2/s with the increment of DS, which is considerably lower than that of Nafion(?) 117.
Organic-inorganic hybrids of SPPFEKK or SPPEKK, heteropoly acids (PWA) and silica were prepared by in situ growth of the inorganic network by hydrolysis and condensation of tetraethoxy silane (TEOS) and 3-aminopropyltrimethoxysilane (AS). The AS has the interaction with the PWA and TEOS, which could fix the PWA in the net structure of the SiO_2. The influence of the introduction of the PWA/AS/SiO_2 in the composite membranes is investigated. The data proves that the introduction of the PWA/AS/SiO_2 can restrain the leak of the PWA. The proton conductivities of the SPPFEKK-15 and SPPEKK-15 are 1.0×10~(-1) S/cm and 8.9×10~(-2) S/cm at 95℃, which multiply one-fold comparing with pure membranes. The 5% weitht loss temperatures of the composite membranes are 308℃and 304℃. The tensile strength values of them are 76.7 MPa and 70.8 MPa. The stability of the PWA in the composite membranes is characterized by immersing the membranes in water for 7 days and tests the PWA concentration of the water everyday. The result shows that the leakness of the PWA mainly happens in the first three days, and the leak percentage is lower than 0.7%/day. Then the speed of the leakness becomes lower, and the leak percentage is less than 0.3%/day. At the 7th days, PWA in composite membranes gets to stable and the composite membranes still have considerable high proton conductivity (above 6.1×10~(-2) S/cm).
A novel sulfonated diamine, 1,2-dihydro-2-(2-sulfonic-4-amino-phenyl)- 4-[4-(2-sulfonic-4-aminophenoxy)-phenyl]-phthalazin-1-one (S-DHPZDA), is successfully synthesized from 1,2-dihydro-2-(4-amino-phenyI)-4-[4-(4-aminophenoxy)-phenyl]-phthalazin-1-one(DHPZDA) by direct sulfonation. Six series of sulfonated polyimides (SPI-1-6) are prepared by sulfonated diamines, S-DHPZDA, 4,4'-bis(4-aminophenoxy)biphenyl-3,3'-disulfonic acid (BAPBDS), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), nonsulonated diamines, 4,4'-diaminodiphenyl ether (ODA), 4,4'-bis(4-aminophenoxy) biphenyl (BAPB), DHPZDA and 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) by "one-step" copolymerization. The results demostrate that compared to other SPI, SPI-1-6 have improved solubility because of the introduction of the noncoplanar and twist structure phthalazinone moieties in the polymers main chain. The SPI-1-6 could soluble in aprotic organic solvents like m-cresol, NMP, DMSO. The decomposed temperatures of sulfonic group and the main chain in the SPI-1-6 membranes are above 310℃and 560℃, respectively. When the DS is higher than 0.6, the proton conductivity of the SPI reached to 10~(-2) S/cm at 95℃. The hydrolytic stability of the SPI membranes can be enhanced by inducting flexible bones and more basic sulfonated diamine to the SPI's main chain. SPI-6-80 with high DS (0.8) has the hydrolysis stability of 1280 h, while the SPI-6-20 can maintain its mechanical strength in the water for more than 6000 h at 80℃. The tensile strength of the SPI-1-6 membranes varies from 50.1 to 98.1 MPa. The methanol permeabilities of the SPPFEKK membranes rise from 10~(-8)～10~(-7) cm2/s with the increment of DS.
引文
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