【作者】 Wael Abd El-Kader El-Saved El-Saved Amer；

【导师】 王立； 俞豪杰；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2013， 博士

【摘要】 尽管二茂铁基聚合物在几十年前就已经被发现,对于它的研究仍然快速地进行着,这是因为它们在当今的生活中仍然具有很宽广的应用。这些应用都是基于二茂铁基聚合物的一些特殊性质,例如液晶性质、电化学性质、热稳定性以及良好的溶解性。这些应用具体主要有结晶聚合物的构建、燃料电池、电流型生物传感器、DNA和蛋白质传感器、乙肝表面抗原的免疫传感器(HBsAg)、CO传感器以及阴离子传感器等。另外,二茂铁基聚合物可以被用在光逻辑器件的创建、表面凹凸光栅以及光电二极管器件的制造等。因此,有关二茂铁和二茂铁基聚合物合成和应用的文章数量在过去的二十年中呈指数增长。热致液晶材料(包括液晶化合物和聚合物)是一种软材料,它们的分子自组装成各向异性的宏观有序结构。另外,这种液晶材料在光学、化学以及生物学等不同领域中的各种功能强大的技术应用中都具有重要作用,在学术和工业层面都创造出新的途径。关于热致液晶的主要应用之一就是液晶显示器的制造,这已经很普遍并且有可能在将来成为平板显示器的主流,因此通过开发和合成新型热致液晶结构和聚合物来提升它们的性能还存在很大的努力空间。另外,在过去的几十年里,金属配位聚合物引起了很大的关注。其中,二茂铁基液晶聚合物(例如二茂铁基聚酯、有机磷聚合物、聚硅氧烷以及聚(二茂铁硅烷)代表了最有价值的介晶材料之一。对这类聚合物的研究兴趣主要集中在它们在甲醇燃料电池中作为聚合物膜中的潜在应用。该应用主要是因为这类聚合物具有潜在的形成有序质子通道的能力,从而不受溶剂的影响,进而促进燃料电池中质子的传递,并有可能减少甲醇渗透过聚合物膜而降低燃料电池效率的问题。二茂铁基团的氧化态(二茂铁鎓离子)和还原态均被证明具有化学稳定性。尽管过去的的几十年世界各地的研究小组对于二茂铁基液晶聚合物的合成、性质及应用进行了大量的研究,合成新型液晶二茂铁基聚合物并研究它们的性质仍然是用来预测它们潜在应用的热点主题。在二茂铁基液晶聚合物领域,从它们的合成、性质到应用仍然存在着很多挑战。在本文中,一些新型主链二茂铁基聚合物利用1,1’-二茂铁二羧酸酰氯和不同单体进行溶液缩聚反应被成功合成。一般来说合成方法分为两类,即溶液缩聚和界面缩聚。接下来,所合成的二茂铁基聚合物的主链化学结构利用诸如’H核磁共振(1H NMR)光谱、紫外-可见分光光谱(UV-VIS)及红外光谱(FTIR)进行表征。另外.所合成聚合物的结晶度利用X-射线衍射进行确定。结构表征过后,又利用循环伏安法研究了合成聚合物的电化学性质,同时研究了不同参数(包括有机溶剂、扫描速率、电解液浓度的影响及具有电活性的二茂铁单体浓度)对所合成聚合物循环伏安行为的影响。其次,所合成聚合物的热学性质利用热重分析(TGA)及差热分析(DTA)进行研究。最后,利用差示扫描量热法(DSC)和偏光显微镜技术(POM)研究了聚合物的液晶性质。(1)通过溶液缩聚反应合成了液晶(PDEFD)和(PHOSFD)。HOS通过双酚S以8-氯代-1-正辛醇作为反应物,DMF作为溶剂合成。对PDEFD和PHOSFD利用1H NMR光谱、UV-VIS分光光谱及FTIR光谱进行结构表征。PDEFD和PHOSFD的分子量分别为11587和6155。XRD测试结果表明PDEFD和PHOSFD几乎都是无定型的聚合物。这种无定型特性证明了所合成聚合物的热致液晶特性。另外,分别对PDEFD和PHOSFD的电化学行为以及多种参数,包括溶剂、扫描速率以及电解质浓度进行了研究。PDEFD和PHOSFD这两种聚合物的CV曲线的形状均受到溶剂极性的影响。这两种聚合物的CV曲线显示出它们的共平面结构,该结构使聚合物与电极表面紧密接触。另外,PDEFD和PHOSFD的溶液的峰电流值随扫描速率增加,且与扫描速率的平方根呈直线关系。更进一步,PDEFD和PHOSFD溶液的电化学过程既不是可逆的,也不是完全不可逆的。大体上说,PDEFD和PHOSFD的电化学性质比较接近。此外,TGA及DTA测试结果表明了它们具有相对的热稳定性。尽管PHOSFD的聚合物主链上有两个苯环,但具有脂肪族主链的PDEFD被发现具有更高的热稳定性,此外,PDEFD的玻璃化转变温度也比PHOSFD要高。所合成聚合物的液晶性质通过DSC和POM技术来检测。两种所合成的聚合物在加热及冷却时都具有向列相结构出现,并显示出相错的纹理。(2)三种新型主链二茂铁基聚酯：PPFD、PHDFD和PMFD分别通过1,1’-二茂铁二甲酰氯和苯基二乙醇胺(PDE)、双酚-P (bisphenol-P)与N-甲基二乙醇胺(MDE)的溶液缩聚法合成。第一种聚合物(PPFD)在两种不同条件下制得,并对所得的两种产物(PPFD1and PPFD2)进行了比较。所合成聚合物的结构通过1H NMR光谱进行表征。利用凝胶渗透色谱(GPC)技术确定了聚合物的分子质量。GPC结果显示,所合成聚合物更准确的来说应该是低聚物而不是高分子聚合物。产物高分子的特性利用FTIR和UV-VIS分光光谱来检测。XRD结果显示四种合成的主链二茂铁基聚合物基本上是无定型的,但有些结晶度。这种无定型性质表现在聚合物在许多不同极性的溶剂中都具有良好的溶解性。更进一步,聚合物的化学结构及合成条件都会影响其结晶度。我们利用循环伏安法研究了聚合物分别在CH2C12、CHC13、THF、DMF和DMSO中的电化学性质,结果发现在高极性溶剂如DMF和DMSO中循环伏安曲线的峰型更为紧凑。这说明在高极性溶剂中聚合物的极化过程的可逆性更好。聚合物在CH2C12中在不同扫描速率下的电化学行为显示所合成的聚合物的电化学过程既不是完全不可逆,但其可逆性也不是很好。另外,对电解质浓度及[Fe]单元浓度对聚合物电化学行为的影响也进行了研究。随着电解质浓度的提高,聚合物CV曲线上氧化还原峰值间的间隔△Ep在大体上有所减小,这说明在聚合物在高电解质浓度下极化过程的可逆性更好。随着[Fe]单元浓度的提高,峰值电流大体上也有所增加。所有所合成的聚合物在加热与冷却的过程中都具有向列相,并且显示出相错的纹理。聚合物在冷却及加热扫描过程中一直保持着有序结构。(3)三种新型偶氮苯侧链主链二茂铁基聚酯(MFPAS):硝基偶氮苯性能化的PPFD (PPFD-NT)、4-羧基偶氮苯功能化的PPFD (PPFD-CA)和4-氰基偶氮苯功能化的PPFD(PPFD-CN)通过利用PPFD分别与4-硝基苯胺、4-氨基苯甲酸及氨基苄腈的后聚合偶氮偶联反应成功制得。所合成聚合物的结构通过1H NMR光谱确定。MFPAS的功能化程度通过1H NMR光谱确定,结果分别为66%(PPFD-NT)、34%(PPFD-CA)和54%(PPFD-CN)。所合成聚合物的特性利用FTIR和UV-VIS分光光谱进行探讨。XRD结果显示三种合成的MFPAS均为无定型结构。这种无定型性质表现在MFPAS在许多不同极性的溶剂中都具有良好的溶解性。MFPAS在其DMF溶剂中在紫外光的照射下展示出顺式到反式的光学异构。这种主链含偶氮苯的二茂铁基聚酯同时被发现显示出在HCl的存在下出现红移,这是因为在盐酸的存在下形成了离子,这种现象使这种聚合物有可能成为pH指示剂很好的候选材料。所合成聚酯的热学性质显示出PPFD-CA和PPFD-CN在热力学上比PPFD-NT更稳定。PPFD的玻璃化转变温度被发现比MFPAS的要低,这是由于MFPAS中的偶氮苯基团的存在。所有所合成的聚合物在加热与冷却的过程中都具有向列相,并且显示出相错的纹理。聚合物在冷却及加热扫描过程中一直保持着有序结构。(4)四种新型以脂肪族单元为骨架,主链二茂铁基聚合物被成功合成,包括PSPUFD、 PDAFD、PDMFD和PHPFD。PSPUFD和PDAFD分别利用1,1’-二茂铁二羧酸酰氯和3,9-二(1,1-二甲基-2-羟乙基)-2,4,8,10-四环氧基-[5,5]-十一碳烷(SPU)及二异丙醇胺(DA)进行溶液缩聚反应制得。PSPUFD与PDAFD分子质量分别为4107和1338。为了提高分子量,另两种聚合物PDMFD和PHPFD通过1,1’-二茂铁二羧酸酰氯分别和二乙基双(羟甲基)丙二酸酯(DM)及2,2-二(羟甲基)丙酸(HP)进行界面缩聚反应制得。所合成聚合物的结构通过诸如1H NMR光谱、UV-VIS吸收光谱和FTIR光谱等手段进行说明。所合成聚合物的X-射线衍射图样显示出聚合物的无定型特征,这表现为聚合物在很多溶剂中都具有良好的溶解性。所合成聚合物的电化学性质利用循环伏安法进行测定。更进一步,对于有机溶剂、扫描速率、电解质浓度及[Fe]浓度对所合成聚合物的氧化还原行为的影响也进行了研究。所合成聚合物的氧化还原行为被发现既不是可逆也不是完全不可逆。另外,这些聚合物的热力学性质利用TGA和DTA进行研究,其结果显示出它们的相对热稳定性。最后,通过偏光显微镜(POM)观察聚合物的液晶性质,结果显示出所合成的聚合物具有向列相及交错纹理,且其在加热和冷却过程中有很长的相持续时间。(5)四种以新型芳香单元为骨架,主链二茂铁基聚合物：PCPFD、PCRFD、PQDFD和PSOFD被成功合成。前两种聚合物PCPFD和PCRFD通过1,1’-二茂铁二羧酸酰氯分别与o-甲酚肽(CP)和甲酚红(CR)利用溶液缩聚反应制得。PCPFD和PCRFD被发现分子量很小,分别只有2398和1727。为了获得具有更高分子量的聚合物,利用1,1-二茂铁二甲酰氯分别与2,4二羟基喹啉(QD)和苏丹橙G(SO)通过界面缩聚制得PQDFD和PSOFD。所合成聚合物的化学结构通过诸如1H NMR光谱、UV-VIS吸收光谱和FTIR光谱等手段进行说明。所合成聚合物的X-射线衍射图样显示出聚合物的无定型特征,这表现为所合成聚合物在很多溶剂中都具有良好的溶解性。所合成聚合物的电化学性质利用循环伏安法进行测定。更进一步,对有机溶剂、扫描速率、电解质浓度及[Fe]浓度对于所合成聚合物的氧化还原行为的影响也进行了研究。所合成聚合物的氧化还原行为被发现既不是可逆也不是完全不可逆。另外,这些聚合物的热力学性质利用TGA和DTA进行研究,其结果显示出它们的相对热稳定性。同时,POM观察结果显示出所合成的聚合物具有向列相结构且其相结构在加热及冷却过程中都很能稳定地保持。更多还原

【Abstract】 Even though ferrocene-based polymers have been discovered from many decades, the research into ferrocene-based polymers continues apace, due to their incorporation into a wide variety of applications in the modern life. These applications have been based on the properties of the ferrocene-based polymers like the liquid-crystalline properties, the electrochemical properties, the thermal stability and the good solubility.Thermotropic liquid crystals (including liquid crystalline compounds and polymers) are soft materials in which their molecules self-assemble into macroscopically ordered structures with anisotropic properties. In addition, this type of liquid crystals has assumed great importance in many powerful technological applications in different fields like optics, chemistry and biology, which has created new avenues in academic and industrial research. Therefore, there exist many efforts to improve the properties of liquid crystals via developing and synthesizing of novel thermotropic liquid crystalline compounds and polymers.In the past few decades, metallomesogenic polymers have attracted much attention. Among them, ferrocene-based liquid crystalline polymers represent one of the most valuable mesomorphic materials.Several novel main-chain ferrocene-based polymers were synthesized employing the solution polycondensation of1,1’-ferrocenedicarbonyl chloride with different monomers. Two different routes were exploited for the synthesis of the polymers including the solution polycondensation route and the interfacial polycondensation route. Afterwards, the chemical structure of the synthesized main-chain ferrocene-based polymers was elucidated using many techniques involving1H NMR spectra, UV-VIS absorption spectra and the FTIR spectra. In addition, the X-ray diffractograms of the synthesized polymers were measured to determine their crystallinity degree. Following the characterization, the electrochemical properties of the synthesized polymers were studied using the technique of cyclic voltammetry and the effect of many parameters (involving the effect of organic solvents, the effect of scan rate, the effect of the electrolyte’s concentration and the effect of the concentration of the electroactive ferrocene moiety) on the cyclic voltammetric behavior of the synthesized polymers was investigated. The thermal properties of the synthesized polymers were examined employing the TGA and DTGA techniques. Finally, the liquid crystalline properties of the synthesized polymers were explored via the DSC and the POM techniques.(1) Liquid crystalline poly(diethyleneglycol1,1’-ferrocene dicarboxylate)(PDEFD) and poly(bis(4-hydroxyoctoxyphenyl)sulfone1,1’-ferrocene dicarboxylate)(PHOSFD) were synthesized successfully by solution polycondensation reaction of1,1’-ferrocenyl chloride with diethylene glycol and bis(4-hydroxyoctoxyphenyl)sulfone (HOS), respectively. HOS was synthesized from bisphenol S using8-chloro-l-octanol as a reagent in DMF. PDEFD and PHOSFD were characterized via the measurement of their1H NMR spectra, UV-VIS absorption spectra and FTIR spectra. PDEFD and PHOSFD possessed a molecular weight of11587and6155, respectively. The XRD measurements showed that PDEFD and PHOSFD are almost amorphous polymers. The electrochemical behaviors of PDEFD and PHOSFD were investigated and the influence of many parameters, including the solvent, the scan rate and the electrolyte concentration, was studied. The shape of the CV peaks, of both polymers, was affected by the polarity of the solvents. The CV of PDEFD and PHOSFD indicate their coplanar structures that make the polymers tightly contacted with the surface of the electrode. In addition, the peak current values of PDEFD and PHOSFD solutions increased with increasing the scan rate and had a linear relationship with the square root of scan rate. Furthermore, the electrochemical processes of PDEFD and PHOSFD solutions are neither reversible nor totally irreversible. Generally, the electrochemical properties of PHOSFD and PDEFD are similar to each other. Moreover, the measurement of TGA and DTGA of PDEFD and PHOSFD indicated their relative thermal stability. In spite of the presence of two phenyl rings in the polymer backbone of PHOSFD, PDEFD with aliphatic backbone was found to be more thermally stable than PHOSFD and the Tg value of PDEFD were higher than that of PHOSFD. The liquid crystalline properties of the synthesized polymers were examined exploiting the DSC and the POM techniques. Both of the polymers possessed nematic phases during heating and cooling and they exhibited textures with schlieren disclinations. The synthesized polymers possessed high phase duration and the clearing point is above the decomposition temperature of the polymers.(2) Three novel main-chain ferrocene-based liquid-crystalline polyesters poly (N-phenyldiethanolamine1,1’-ferrocene dicarboxylate)(PPFD), poly(α,α’-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene1,1’-ferrocene dicarboxylate)(PHDFD), and poly(methyldiethanol amine1,1’-ferrocene dicarboxylate)(PMFD) were synthesized successfully using the solution polycondensation method of1,1’-ferrocenyl chloride with phenyldiethanolamine (PDE), α,α’-bis(4-hydroxyphenyl)-1,4-diisopropyl benzene (bisphenol-P), and N-methyldiethanolamine (MDE), respectively. The first polymer (PPFD) was synthesized in two different conditions and the properties of the two products (PPFD1and PPFD2) were compared. The structure of the synthesized polymers was characterized by’H NMR spectroscopy. The molecular weight of the polymers was determined via the GPC technique. The GPC results showed that they are mostly oligomers rather than polymers. The polymers were also characterized via the measurement of their FTIR and UV-VIS spectroscopy and the properties were structurally dependent. The XRD results showed that the four synthesized main-chain ferrocene-based polymers are mostly amorphous but have some degree of crystallinity. This amorphous nature was reflected in the polymers’good solubility in many solvents with different polarities. Furthermore, both of the chemical structure and the synthesis conditions affect the crystallinity degree of the polymers. The cyclic voltammetry was employed to study the electrochemical properties of the polymers in CH2Cl2, CHCl3, THF, DMF and DMSO. The shape of the peaks was found to be compact in high polar solvents including DMF and DMSO. The electrochemical behavior of the polymers was investigated in CH2Cl2at different potential scan rates and the results indicated that the electrochemical processes of the synthesized polymers were neither totally irreversible nor perfectly reversible. The influence of the concentration of the electrolyte and the concentration of [Fe] unit was also studied. With increasing the concentration of the electrolyte, the peak-to-peak potential separation decreased in a general trend, which indicates that the reversibility of the electrode process becomes better at high electrolyte concentrations. With increasing the concentration of the [Fe] unit, the peak currents increased generally. All the synthesized polymers possessed nematic phases during heating and cooling and they exhibited textures with schlieren disclinations. The ordered structures were permanently retained in the cooling and the heating scan cycles. (3) Three novel main-chain ferrocene-based polyesters with azobenzene in the side-chain (MFPAS):4-nitrophenylazo-functionalized-PPFD (PPFD-NT),4-carboxyphenylazo-functionalized-PPFD (PPFD-CA), and4-cyanophenylazo-functionalized-PPFD (PPFD-CN) were synthesized successfully using the post-polymerization azo-coupling reaction of PPFD with4-nitroaniline,4-aminobenzoic acid and4-aminobenzonitrile, respectively. The synthesized polymers were characterized by’H NMR spectroscopy. The degrees of functionalization of the MFPAS were determined from the1H NMR analysis and they were found to be66%,34%and54%for PPFD-NT, PPFD-CA and PPFD-CN, respectively. The synthesized polymers were also characterized via the measurement of their FTIR and UV-VIS spectroscopy. The XRD results showed that the three synthesized MFPAS were amorphous. This amorphous nature was reflected in the MFPAS’good solubility in many solvents with different polarities. The MFPAS exhibited trans to cis photoisomerization upon the irradiation of their DMF solutions with UV light. The azobenzene-containing main-chain ferrocene-based polyesters were also found to display bathochromic shifts upon the addition of HCl due to the formation of the azonium ions that make these polymeric species good candidates as pH indicators. The thermal properties of the synthesized polyesters showed that PPFD-CA and PPFD-CN were thermally more stable than PPFD-NT. The Tg of PPFD was found to be lower than those of the MFPAS due to the presence of the azo phenyl group in the MFPAS. All the synthesized polymers possessed nematic phases during heating and cooling and they exhibited textures with schlieren disclinations. The ordered structures were permanently retained in the cooling and the heating scans.(4) Four novel main-chain ferrocene-based polymers, including poly(3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxospiro-[5.5]-undecane1,1’-ferrocene dicarboxylate)(PSPUFD), poly(diisopropanolamine1,1’-ferrocene dicarboxylate)(PDAFD), poly(diethyl bis(hydroxymethyl)malonate1,1’-ferrocene dicarboxylate)(PDMFD), and poly(2,2-bis(hydroxymethyl) propionic acid1,1’-ferrocene dicarboxylate)(PHPFD), were successfully synthesized with aliphatic units. PSPUFD and PDAFD were synthesized using the solution polycondensation reaction of1,1’-ferrocenedicarbonyl chloride with3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxospiro-[5.5]-undecane (SPU) and diisopropanol amine (DA), respectively. PSPUFD and PDAFD were found to possess molecular weights of4107and 1338, respectively. To increase the molecular weight, the polymers PDMFD and PHPFD were synthesized via the interfacial polycondensation reaction of1,1’-ferrocenedicarbonyl chloride with diethyl bis(hydroxymethyl) malonate (DM) and2,2-bis(hydroxymethyl)propionic acid (HP), respectively. PDMFD and PHPFD were found to possess molecular weights of4456and6916, respectively. The structure of the synthesized polymers was elucidated by many techniques such as1H NMR, UV-VIS and the FTIR spectroscopy. The X-ray diffractograms of the synthesized polymers indicate the amorphous nature of these polymers, which was reflected in their good solubility in many solvents. The electrochemical properties of the synthesized polymers were investigated employing the cyclic voltammetry technique. In addition, the effect of the organic solvents, the scan rate, the electrolyte concentration and the effect of [Fe] concentration on the redox behavior of the synthesized polymers were examined. The electrochemical redox processes of the synthesized polymers were found neither reversible nor totally irreversible. The thermal properties of the synthesized polymers were studied via the TGA and DTGA techniques and the results indicated their relative thermal stability. The investigation of the liquid crystalline properties with the POM technique revealed that the synthesized polymers exhibited nematic phases with schlieren desclination during the heating and the cooling processes with high phase duration.(5) Four novel main-chain ferrocene-based polymers, including poly(o-Cresolphthalein1,1’-ferrocene dicarboxylate)(PCPFD), poly(Cresol Red1,1’-ferrocene dicarboxylate)(PCRFD), poly(2,4-quinolinediol1,1’-ferrocene dicarboxylate)(PQDFD), and poly(Sudan Orange G1,1’-ferrocene dicarboxylate)(PSOFD), were successfully synthesized with aromatic units. The first two polymers PCPFD and PCRFD were synthesized via the solution polycondensation reaction of1,1’-ferrocenedicarbonyl chloride with o-Cresolphthalein (CP) and Cresol Red (CR), respectively. PCPFD and PCRFD possessed low molecular weights of2398and1727, respectively. To obtain the other polymers with higher molecular weight, PQDFD and PSOFD were synthesized employing the interfacial polycondensation reaction of1,1’-ferrocenedicarbonyl chloride with2,4-quinolinediol (QD) and Sudan Orange G (SO), respectively. The molecular weights of PQDFD and PSOFD were determined to be8379and21576, respectively. The chemical structure was elucidated via the measurement of1H NMR spectra, UV-VIS absorption spectra and the FTIR spectra for the synthesized polymers. The X-ray diffractograms of indicate the amorphous nature of the synthesized polymers, which is reflected in their good solubility in many solvents. The electrochemical properties of the synthesized polymers were examined using the cyclic voltammetry technique. In addition, the effect of the organic solvents, the scan rate, the electrolyte concentration and the effect of [Fe] concentration on the redox behavior of the synthesized polymers were investigated. The electrochemical redox processes of the synthesized polymers were found neither reversible nor totally irreversible. The thermal properties of the synthesized polymers were studied using the TGA and DTGA techniques and the results indicated their relative thermal stability. The POM technique indicated that the synthesized polymers exhibited nematic phases during the heating and the cooling processes with high phase duration.更多还原