【作者】 李国伟；

【导师】 张文勤；

【作者基本信息】 天津大学 ， 有机化学， 2012， 博士

【摘要】 腈纶纤维因其独特的结构和性能被广泛应用于纺织和服装领域，近年来腈纶纤维的功能化发展非常迅速并成为化学家研究的热点。本论文在腈纶纤维功能化的研究基础上，通过对腈纶纤维的有效修饰，得到了重金属离子吸附变色纤维、酸碱双变色纤维、叔胺功能化纤维催化剂、多胺功能化纤维催化剂和脯氨酸功能化纤维催化剂。设计合成了4-（2-吡啶偶氮）间苯二酚（PAR）功能化的重金属离子吸附变色纤维，并通过表征证实了PAR通过C–N共价键连接到纤维上，对该功能化纤维吸附金属离子的变色性能和吸附变色机理进行了系统的研究；发现该PAR功能化纤维在pH=6的条件下只对重金属离子吸附变色(如Hg²⁺、Pb²⁺、Cd²⁺、Zn²⁺、Ni²⁺、Cu²⁺等)，对轻金属离子不变色(如Ca²⁺、Mg²⁺、Al³⁺等)；其选择性随着pH的下降而提高，当pH=3时，该纤维只对Hg²⁺和Cu²⁺选择性变色；裸眼检测限达1×10^–6mol/L；具有很高的重复变色性能（50次以上）；很好的耐日光性（日光照射30天，吸附变色性能不变）。设计合成了具有双变色功能基团的酸碱变色纤维，并通过表征证实了乙基橙和酚酞基团通过C–N共价键连接到纤维上；对该功能化纤维的光谱性质、变色性能和变色机理进行了系统的研究；发现该酸碱双变色纤维在中性条件下为鲜黄色，遇酸变为深粉色，遇碱变为深紫色，颜色变化明显，易区分，pH变色范围分别为0-1和13-14；该纤维对多种酸碱溶液均响应变色（如柠檬酸、盐酸、硫酸、氢氧化钠、氢氧化钙、磷酸钠等等）；可重复变色300次以上；且对强酸强碱和光都具有很好的稳定性（日光照射60天，变色不受影响）。设计合成了系列单胺型和多胺型的功能化纤维催化剂。首次对单胺型含有伯、仲、叔胺基团的功能化纤维催化剂催化Knoevenagel反应的活性进行考察和筛选，对催化效果最好的叔胺功能化纤维催化剂进行了深入的研究，对叔胺功能化纤维催化剂的结构和表面形貌等进行了系统表征。对其催化Knoevenagel缩合的反应条件、溶剂适用性、底物的扩展、可重复使用性等进行了系统的研究。实验发现该纤维催化剂可在多种有机溶剂中高效催化Knoevenagel缩合反应，收率均在90%以上；底物的适用性非常广泛；纤维催化剂重复使用10次，催化性能几乎不变。在合成的一系列多胺（如二乙烯三胺、三乙烯四胺等）功能化纤维催化剂中，选择对Knoevenagel反应催化效果最好的三乙烯四胺功能化纤维催化剂进行深入的研究；对三乙烯四胺功能化纤维催化剂的结构和表面形貌等进行了系统表征。对其催化Knoevenagel缩合反应条件、溶剂适用性、底物的扩展、可重复使用性等都分别进行了系统的研究。实验发现该纤维催化剂可在水中高效催化Knoevenagel缩合反应，收率均在94%以上；以水作为溶剂绿色、经济、环保；底物的适用性非常广泛；纤维催化剂重复使用21次，催化活性略有下降，但适当延长反应时间，反应收率仍接近定量（98%）。最后，本文首次将催化领域研究热点的脯氨酸引入到纤维上，设计合成了脯氨酸功能化纤维催化剂，并对该纤维催化剂的结构和表面形貌等进行了系统表征。对其催化Knoevenagel缩合反应的反应条件、溶剂适用性、底物的扩展、可重复使用性等进行了系统的研究。实验发现该纤维催化剂可在醇类溶剂中高效催化Knoevenagel反应，收率均在92%以上，底物的适用性广泛，催化剂用量少（2mol%），甚至当纤维催化剂为0.5mol%时，通过延长反应时间，收率仍可接近定量（98%）。该脯氨酸功能化纤维催化剂可重复使用20次以上。更多还原

【Abstract】 Polyacrylonitrile fiber is widely used in textile and garment area for its uniquestructure and properties. In recent years, the functionalization of polyacrylonitrilefiber has been developed rapidly and become interest of the chemists. Based on thefunctionalization of polyacrylonitrile fiber, this paper provides a colorimetric fiber forheavy metal ions detection and adsorption, a dual colorimetric fiber for acids andbases detection, a tertiary-amine functionalized fiber catalyst, a series of polyaminefunctionalized fiber catalysts, and a proline functionalized fiber catalyst.A4-（2-pyridylazo）-1,3-benzenediol （PAR） functionalized colorimetric fiber forheavy metal ions detection and adsorption has been designed and synthesized. Thisfiber has been fully characterized and PAR has been confirmed to be covalentlygrafted on the fiber by the C–N bond formation. The color change capabilities andmechanism of the fiber have been systemically studied. After adsorbing heavy metalions at pH=6(such as Hg²⁺, Pb²⁺, Cd²⁺, Zn²⁺, Ni²⁺and Cu²⁺), this fiber changed itscolor from red orange to dark-brown. However, no color change was observed forlight metal ions such as Ca²⁺, Mg²⁺and Al³⁺. The selectivity of the fiber increasedwith the pH value decreased. The fiber changed its color only for Hg²⁺and Cu²⁺at pH=3. This fiber also presented a high visual detection limit (1×10^–6mol/L), excellentreusability （>50times） and high photostability （>30days under direct exposure tosunlight with no loss in capability of color change and adsorption for heavy metalions）.A dual colorimetric fiber based on ethyl orange and phenolphthalein for acids andbases has been designed and synthesized. This fiber has been fully characterized.Ethyl orange and phenolphthalein have been confirmed to be covalently grafted on thefiber by the C–N bond formation. The spectroscopic properties, color changecapability and mechanism of the fiber have been systemically studied. This fiberpresented a fresh yellow color in neutral condition, deep pink in acidic condition （pH=0-1） and dark violet in basic condition （pH=13-14）, which was easy to bedistinguished. The color change of the fiber could be induced by many acid or basesolutions such as citric acid, HCl, H2SO4, NaOH, Ca（OH）2and Na3PO4. This fiber also presented excellent reusability （>300times）, good stability in strong acid andbase, and high photostability （>60days under direct exposure to sunlight）.In addition, series of monoamine and polyamine functionalized fiber catalystshave been designed and synthesized. For the monoamine functionalized fiber catalystscontaining primary, secondary and tertiary-amine, the catalytic activities of these fibercatalysts have been evaluated and the tertiary-amine functionalized fiber catalyst withhighest catalytic activity was selected for detail research. The structure and surface ofthe fiber catalyst have been characterized. The Knoevenagel reaction conditions,solvent effect, substrate expansion and reusability have been systemically studied.This fiber catalyst could efficiently catalyze Knoevenagel condensation in variousorganic solvents （yield>90%）. This catalyst was applicable to many substrates andpresented excellent reusability （10times, almost no loss in catalytic activity）.For the polyamine （such as diethylenetriamine and triethylenetetramine）functionalized fiber catalysts, the catalytic activities of these fiber catalysts have beenevaluated and the triethylenetetramine fiber catalyst with the highest catalytic activitywas selected for detail research. The structure and surface of the fiber catalyst havebeen characterized. The reaction conditions, solvent effect, substrate expansion andreusability have been systemically studied. This fiber catalyst could efficientlycatalyze Knoevenagel condensation in water （yield>94%）. Water was used as thesolvent for its green, economic and eco-friendly. This fiber catalyst was applicable tomany substrates and presented excellent reusability （21times, a slightly decrease,after prolonging the reaction time, an almost quantitative yield98%was obatained）.Proline, which is one of the hotspots in the catalytic field, was firstly introducedinto the fiber and a proline functionalized fiber catalysts have been designed andsynthesized. The structure and surface of the fiber catalyst have been characterized.The reaction conditions, solvent effect, substrate expansion and reusability have beensystemically studied. This fiber catalyst could efficiently catalyze Knoevenagelcondensation in acohol （yield>92%）. This catalyst was applicable to many substratesand presented excellent reusability （20times, almost no loss in catalytic activity）.Catalyst loading was only2mol%. Even decreased the catalyst loading to0.5mol%,an almost quantitative yield98%was able to obtain by prolonging the reaction time.更多还原