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首页> 外文学位 >Part A: Synthesis, characterization, and phase behavior of fluoroalkyl and hydrocabron poly(p-phenylenes). Part B: Synthesis of azobenzene contaning organic polymers and their third-order nonlinearity studies.
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Part A: Synthesis, characterization, and phase behavior of fluoroalkyl and hydrocabron poly(p-phenylenes). Part B: Synthesis of azobenzene contaning organic polymers and their third-order nonlinearity studies.

机译：A部分：氟代烷基和氢卡宾聚对苯撑的合成，表征和相行为。 B部分：含偶氮苯的有机聚合物的合成及其三阶非线性研究。

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Part A. A series of fluoroalkyl and alkyl 2,5-dichlorobenzoates were synthesized for future aryl chloride polymerization and to examine their supercritical solvent solubility. The fluorinated alkyl 2,5-dichlorobenzoates investigated in this study is highly soluble in CO2 at modest conditions. The solubility of the hydrocarbon alkyl 2,5-dichlorobenzoates decreases significantly as the alkyl chain length increases. Alkyl and fluoroalkyl ester substituted poly(p-phenylene)s (PPP) were synthesized by aryl halide coupling using a nickel catalyst and zinc. The solubilities of the alkyl and fluoroalkyl PPPs were studied in supercritical solvents. The propyl, butyl, pentafluoropropyl, and heptafluorobutyl ester substituted PPPs were not soluble in sc-ethane, sc-propane, sc-butane, or SC-CO2 at high pressures and high temperatures. The pentyl, hexyl, and octyl ester substituted PPPs were soluble in sc-ethane, sc-propane, and sc-butane. A series of polymer analogues with H-H and T-T connectivities were synthesized in the form of dimers. The dimers included octyl and tridecafluorooctyl ester moieties. The dimers were synthesized because the polymer 1H NMR showed regioirregularities in the polymer backbone.; A polymer study was initiated to attempt to increase the regioregularity in the aryl chloride coupling of alkyl and fluoroalkyl 2,5-dichlorobenzoates. The study was completed by varying the ligand (dppf, dppp, PPh3, or PPh3/bpy,) in the coupling reaction, using the hexyl, octyl, nonafluorohexyl, and tridecafluorooctyl 2,5-dichlorobenzoates. A completely regioregular polymer was not formed in the varying ligand study, therefore the regioregularity can not be generated from the nickel catalyst alone. The supercritical solubility of the biphenyl 2,3'-dicarboxylic acid dioctyl ester showed a ∼400 bar higher maximum pressure than the biphenyl-2,2'-dicarboxylic acid dioctyl ester. The biphenyl-2,3 '-dicarboxylic acid di-tridecafluorooctyl ester showed a ∼50 bar higher maximum pressure than the biphenyl-2,2'-dicarboxylic acid di-tridecafluorooctyl ester. The T-T dimers displayed higher solubility than the H-H due to the ability of the T-T dimers to have a planar conformation.; Part B. An azobenzene monomer with methoxy and hexyloxy substitutents were synthesized by a diazotination reaction of 3-bromo-4-methoxy phenol and 4-bromo aniline, and then alkylated with hexyliodide. The polymer was synthesized in a palladium-catalyzed reaction to yield the first conjugated organic polymer that contains an azo linkage in the backbone. The polymer exhibited excellent third-order nonlinear properties in THF. (Abstract shortened by UMI.)
机译：A部分。合成了一系列氟代烷基和2,5-二氯苯甲酸烷基酯，用于未来的芳基氯聚合反应，并研究它们的超临界溶剂溶解度。在这项研究中研究的氟化2，5-二氯苯甲酸烷基酯在适度条件下极易溶于CO2。烃基2,5-二氯苯甲酸酯的溶解度随着烷基链长的增加而显着降低。烷基和氟代烷基酯取代的聚（对亚苯基）（PPP）是使用镍催化剂和锌通过芳基卤化物偶联合成的。在超临界溶剂中研究了烷基和氟烷基PPPs的溶解度。丙基，丁基，五氟丙基和七氟丁基酯取代的PPP在高压和高温下不溶于sc-乙烷，sc-丙烷，sc-丁烷或SC-CO2。戊基，己基和辛基酯取代的PPP可溶于sc-乙烷，sc-丙烷和sc-丁烷。以二聚体的形式合成了具有H-H和T-T连接性的一系列聚合物类似物。二聚体包括辛基和十三氟辛基酯部分。合成二聚体是因为聚合物的1 H NMR在聚合物主链中显示出区域不规则性。开始进行聚合物研究，以尝试增加烷基和2，5-二氯苯甲酸氟烷基酯的芳基氯偶合中的区域规则性。通过使用己基，辛基，九氟己基和十三氟辛基2,5-二氯苯甲酸酯在偶联反应中改变配体（dppf，dppp，PPh3或PPh3 / bpy）来完成研究。在可变配体研究中没有形成完全的区域规则聚合物，因此不能仅由镍催化剂产生区域规则性。联苯2,3'-二羧酸二辛酯的超临界溶解度比联苯-2,2'-二羧酸二辛酯的最高压力高约400 bar。联苯-2,3'-二羧酸二-三氟二氟辛酯的最大压力比联苯-2,2'-二羧酸二-三氟二氟辛酯的最大压力高约50 bar。由于T-T二聚体具有平面构象的能力，所以T-T二聚体显示出比H-H更高的溶解度。部分B.通过3-溴-4-甲氧基苯酚和4-溴苯胺的重氮化反应，然后用己碘化物烷基化，合成具有甲氧基和己氧基取代基的偶氮苯单体。该聚合物是在钯催化的反应中合成的，以产生在主链中包含偶氮键的第一共轭有机聚合物。该聚合物在THF中显示出优异的三阶非线性特性。 （摘要由UMI缩短。）

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