【作者】 孙扶；

【导师】 董擎之；

【作者基本信息】 华东理工大学 ， 材料学， 2010， 博士

【摘要】 本文应用原子转移自由基聚合(ATRP)、点击化学及超临界二氧化碳(scCO2)技术制备了基于水凝胶(hydrogel)和聚苯胺(PANI)的复合材料,选取以下几种结构体系进行研究,从各个角度阐述了ATRP和点击化学技术在合成两亲稳定剂方面独具的优势,并且拓展了scCO2介质在特殊材料制备过程中的应用范围,证明了scCO2并非惰性的溶剂,而是具有显著功效的反应媒介。第一章调研了当前国内外对于水凝胶、聚苯胺、scCO2、ATRP以及点击化学的研究现况,分析了利用以上技术合成hydrogel-PANI复合材料的可行性和优越性。第二章联合链转移聚合和ATRP技术合成了分子量可控的,分子量分布较窄并且原料来源丰富、价格低廉的聚醋酸乙烯酯-聚甲基丙烯酸二甲氨基乙酯嵌段共聚物(PVAc-b-PDMAEMA),以此为稳定剂,在scCO2中分散聚合制备了粒径及粒径分布比较理想的聚甲基丙烯酸羟乙酯-聚甲基丙烯酸缩水甘油酯-聚N-乙烯基吡咯烷酮(P(HEMA-GMA-NVP))微球,再以这种微球的水凝胶薄膜HMM为基材,scCO2介质中沉积一层聚苯胺-全氟辛酸(PANI-PFOA),通过摩尔引力常数的方法从理论上探讨了PANI-PFOA在scCO2中形成胶束的可行性,并且同时比较了水相中和异辛烷相中的情况,发现scCO2介质中以PFOA为掺杂剂和分散剂的PANI在HMM上沉积可以得到比较均匀致密,并且具有微观束状结构的表面。第三章使用价廉易得的琥珀酸二异辛酯磺酸钠(AOT)和聚醚接枝的硅油(PeSi)作为H2O/CO2反相乳液的表面活性剂,聚合制备了PANI-SC,与异辛烷介质中合成的PANI-CON相比较,PANI-SC具有更多络合的AOT,更高的结晶度,更好的乙醇分散性以及更高的电导率,同时应用合成的含氟蒙脱土(FMMT)及含不同化学基团的蒙脱土,以H2O/CO2反相乳液的方法制备各种PANI-MMT复合插层材料,发现片层中含有胺基的蒙脱土(NHMMT)和FMMT即使在高蒙脱土含量下也能在PANI聚合中被完全剥离,均匀分散在基体中,得到的PANI-MMT具有较高的热稳定性和室温导电性。第四章应用ATRP技术合成了三臂刷状氟化侧链季铵聚合物(PF-PHEMA)3-TAI-Q,以此作为大分子表面活性剂,在H2O/CO2反相乳液中对壳聚糖(CS)进行聚2-丙烯酰胺基-2-丙磺酸(PAMPS)的接枝反应,得到的CS-g-PAMPS具有接枝率高,水乳液稳定性好、胶束粒径较小等优点；将CS-g-PAMPS和PANI-FMMT导电微粒复合,制得了具有优良导电性能、较高的力学强度以及比CS水凝胶更大溶胀度和更快溶胀速率的功能复合体。第五章应用点击化学反应联结炔基改性的nylon纤维和叠氮改性的樟脑磺酸-聚苯胺(CSA-ANI),制备了表面负载CSA-ANI单体的nylon-CSA-ANI纤维,然后以此纤维作为基质,以合成的全氟壬烯氧基苯磺酸(PFNOBSA)为掺杂酸和稳定剂,在scCO2介质中其表面成功聚合包覆了PANI-CSA和PANI-PFNOBSA成为复合纤维,最后在scCO2介质中,复合纤维上包覆羧甲基纤维素钠(CMC)水凝胶层,制备了三层复合的功能纤维。第六章应用点击化学反应联结乙二胺四乙酸(EDTA)的丙炔醇(Pg-OH)酯化产物EDTA-4C≡CH和叠氮化的全氟辛基碘代烷PFO-N3,再进行季铵化,制备了具有四枝状含氟侧链Gemini型表面活性剂EDTA-4PFO-2Q,同时应用ATRP方法制备了两亲嵌段聚磺化苯乙烯-聚甲基丙烯酸全氟辛基乙酯(PSS-b-PFOMA),应用EDTA-4PFO-2Q和PSS-b-PFOMA在scCO2为介质中,分别依次对玻璃基片GS实施了PAMPS和聚甲基丙烯酸乙酯基二甲基苄基溴化铵(PEMAQ)水凝胶膜的交替层层自组装和PANI的负载,得到表面疏水且导电的复合功能基片。并且通过比较正己烷介质中的反相乳液沉积自组装,发现在scCO2介质中更容易得到表面具有细致颗粒结构的凝胶薄膜。第七章应用ATRP方法,将甲基丙烯酸甲酯(PMMA)和甲基丙烯酸八氟戊酯(PFPMA)链段引入β环糊精(β-CD)的表面,得到β-CD-PMMA-r-PFPMA,以此为稳定剂和交联剂在scCO2介质中进行甲基丙烯酸叔丁酯(tBMA)的聚合,得到β-CD包含某几个tBMA链节的具有拓扑活动交联环的PtBMA弱凝胶微球,并分析了其形成过程及呈现的特殊性能如超疏水性,然后将转化后的聚丙烯酸(PAAc)弱凝胶微球作为内核在scCO2介质中把PANI包覆到其表面,溶蚀内核弱凝胶部分,最终得到了具有中空结构的PANI微球。第八章应用ATRP方法制备了不同分子量且含有端炔基的聚丙烯酸叔丁酯(Pg-PtBA),与通过叠氮改性的二氧化硅包覆四针状氧化锌晶须微粒(T-ZnOw-SiO2-N3)进行了点击反应联结,得到不同分子量聚合物链接枝的杂化T-ZnOw-SiO2·PtBA微粒,保持T-ZnOw所特有的四针状结构,表面接枝聚合物含量也较高,并且相比纯PtBA具有更高的热稳定性,PtBA水解中和之后,利用PANa分子链的水溶性,得到在水中能优良分散的T-ZnOw-SiO2·PANa微粒,能在水凝胶合成体系中作为增强组分。第九章实施酯化反应合成出丙烯酸丙炔酯(PA),然后分别将其与VAc和DMAEMA共聚,得到带有多个炔基侧基的PVAc-r-PPA和PDMAEMA-r-PPA共聚物；另外利用衰减链转移聚合和叠氮化制备了带有叠氮端基的PVAc-N3和PDMAMEA-N3聚合物,通过点击化学将PVAc-r-PPA与PDMAMEA-N3联结,PDMAEMA-r-PPA与PVAc-N3联结,再经季铵化,制备出一种主链为亲CO2的PVAc,侧链为亲水的PDMAQ,另一种主链为亲水的PDMAQ,侧链为亲CO2的PVAc两种梳形共聚物PVAc-c-PDMAQ和PDMAQ-c-PVAc,并且通过1H NMR和GPC表征了梳形共聚物的分子结构,再以这两种梳形聚合物为CO2/H2O体系的表面活性剂,利用正相乳液模板制备了轻质多孔水凝胶PAAc-gel,最后在scCO2中将ANI渗入PAAc-gel基体,通过控制反应时间、CO2压力以及ANI浓度制备出具有不同PANI渗入深度、不同导电率的渐变导电功能复合凝胶。第十章对全文作了总结,展望了下一步的研究工作。更多还原

【Abstract】 A series of hydrogel-polyaniline-based composites have been prepared by atom transfer radical polymerization (ATRP), click chemistry and supercritical carbon dioxide (scCO2) techniques, some following composite systems were selected to expound the unique advantages of ATRP and click chemistry in synthesis of amphiphilic stabilizer, on the other hand, scCO2 technique has also been developed in fabrication of some specialty materials, which indicated that scCO2 was a reaction media with outstanding functions, instead of an inert solvent.In the first chapter, the recent research achievements and development trends on hydrogels、polyaniline(PANI)、scCO2、ATRP and click chemistry were described in great details, the feasibility and advantages of utilization of these techniques to synthesize hydrogel-PANI composites were also analyzed.In the second chapter, firstly, a sort of poly(vinyl acetate)-poly(2-(dimethylamino) ethyl methacrylate) block copolymer (PVAc-b-PDMAEMA) with controlled molecular weight and narrow molecular weight distribution from abundant, widely available, and inexpensive raw materials were synthesized. In the presence of the copolymer stabilizer, poly(2-hydroxyethyl methacrylate)-poly(glycidylmethacrylate)-poly(N-vinyl-2-pyrrolidone)(P(HEMA-GMA-NVP ))microspheres were synthesized by dispersion polymerization in scCO2 and these microspheres showed ideal particle size and narrow particle size distribution. Polyaniline-pentadecafluorooctanoic acid (PANI-PFOA) was also deposited on HMM hydrogel membranes which were prepared by microspheres mentioned above. Theoretic calculation result of the molar attraction constant revealed the formation process of PANI-PFOA micelle in scCO2. At the same time, the scCO2 preparation system was compared with that in water and isooctane media, the deposition using PFOA as dopant and dispersant in scCO2 could form a more uniform and compact PANI surface with fine fasciculate structure.In the third chapter, PANI nanoparticles were prepared in H2O/scCO2 inverse emulsion (denoted as PANI-SC) with bis(2-ethylhexyl)s-sodium sulfosuccinate (AOT) and polyether graft silicone oil (PeSi) as surfactants. Compared to PANI prepared in isooctane(denoted as PANI-CON), PANI-SC incorporated more AOT component, exhibited higher crystallinity, better dispersibility in ethanol and excellent conductivity. On the other hand, different polyaniline-montmorillonite (PANI-MMT) composites were prepared employing fluorinated-MMT and different chemical group modified MMT in H2O/CO2 inverse emulsion. The characterization results showed that aminated MMT and fluorinated-MMT could been completely exfoliated and dispersed in PANI matrix uniformly even with high MMT loading, the PANI-MMT composites revealed high thermal stability and excellent room temperature conductivity.In the fourth chapter, firstly, three-arm-like polymer quaternary ammonium salt with fluorinated side chains (PF-PHEMA)3-TAI-Q was synthesized, with this amphiphilic polymer as surfactant, chitosan (CS) grafted poly(2-acrylamide-2-methylpropanesulfonic acid) (PAMPS) was synthesized in H2O/CO2 inverse emulsion. The product CS-g-PAMPS exhibited high graft ratio and excellent water dispersion stability. CS-g-PAMPS hydrogels could be modified by adding PANI-MMT nanoparticles and showed more excellent conductivity, more remarkable mechanical strength, better gel swelling and higher swelling speed than pure CS and CS-g-PAMPS without PANI-MMT.In the fifth chapter, firstly, functionalized nylon fiber coated with camphorsulfonic acid-aniline (CSA-ANI) was prepared via click reaction, then CSA-PANI and p-perfluorous nonenoxybenzenesulfonate acid-polyaniline (PFNOBSA-PANI) were grafted on functionalized nylon fiber surface by in-situ polymerization in scCO2 with PFNOBSA as dopant and stabilizer. Carboxymethyl cellulose sodium salt (CMC) hydrogel layer could also be loaded on PANI-nylon composite fiber to be nylon-PANI-CMC three layers composite fiber.In the sixth chapter, firstly, four-branch-like gemini surfactant EDTA-4PFO-2Q with fluorinated side chains was prepared via click reaction to combine propynyl group modified ethylenediaminetetraacetic acid (EDTA) and azide group modified 1-Iodo-1H,1H,2H,2H-perfluorodecane (PFO), followed by quaternization. At the same time, poly(sulfonated styrene)-poly(perfluoroalkylethyl acrylate) block copolymer (PSS-b-PFOMA) was synthesized by ATRP technique. Self-assembly layer by layer process of PAMPS and poly(methacrylatoethyl dimethyl benzyl ammonium bromide) (PEMAQ) hydrogel membranes with EDTA-4PFO-2Q as emulsifier were performed on glass substrates (GS) in H2O/CO2 inverse emulsion. Finally, PANI-PSS-b-PFOMA was coated on glass GS-hydrogel membranes with PSS-b-PFOMA as stabilizer in scCO2 media, and superhydrophobic conducting composite functional substrates (CFS-sc) was obtained. Compared to CFS prepared in hexane media, CFS-sc revealed finer surface granule structure.In the seventh chapter, firstly, poly(methyl methacrylate)(PMMA) and poly(1H,1H,5H-octafluoropentyl methacrylate)(PFPMA) molecular chains were introduced ontoβ-cyclodextrin by ATRP random copolymerization, the productβ-CD-PMMA-r-PFPMA could be employed to stabilize dispersion polymerization of tert-butyl methacrylate (tBMA) scCO2 media and PtBMA weak gel microspheres were obtained in whichβ-CD-PMMA-r-PFPMA served as mobile crosslink "ring". The formation process and special function of weak gel microspheres were also analyzed, such as their superhydrophobic property, then PtBMA microspheres were converted into poly(acrylic acid) (PAAc) weak gel microspheres and acted as the core of composite microspheres which were coated by PANI performed in csCO2 media, finally the hollow PANI microspheres were obtained after corrosion of PAAc core.In the eighth chapter, firstly, a series of poly(tert-butyl acrylate) (Pg-PtBA) containing propargyl end group with different molecular weight were synthesized by ATRP, then were incorporated to azide group modified zinc oxide whisker (T-ZnOw-SiO2-N3) via click chemisty and the product T-ZnOw-SiO2·PtBA hybrid particles with high content grafted PtBA were obtained, which exihibited better thermal stability than pure PtBA. The hydrolyzed product T-ZnOw-SiO2·PANa also showed excellent water dispersibility and could serve as component added to enhance the mechanical strength of hydrogel matrix in next research stage.In the ninth chapter, firstly, copolymers of propargyl acrylate (PA) and VAc or DMAEMA, PVAc-r-PPA or PDMAEMA-r-PPA with a certain number of propargyl side groups were synthesized. At the same time, PVAc-N3 and PDMAMEA-N3 with azide end group were also prepared by degenerative chain transfer radical polymerization, and then comb-like copolymer PVAc-c-PDMAQ (PDMAQ was the quaternization product of PDMAEMA) or PDMAQ-c-PVAc were obtained via click chemistry to incorporate PVAc-r-PPA and PDMAMEA-N3 or PDMAEMA-r-PPA and PVAc-N3. PVAc-c-PDMAQ contained CO2-philic PVAc main chain and hydrophilic PDMAQ side chain, PDMAQ-c-PVAc contained hydrophilic PDMAQ main chain and CO2-philic PVAc side chain. With these copolymers as surfactants of CO2/H2O emulsion template, light weight and porous PAAc hydrogel were prepared, followed by immersion polymerization of aniline into this hydrogel in scCO2 media, the PANI-hydrogel functionally gradient materials could be obtained by controlling some reaction conditions, such as immersion time, CO2 pressure and aniline concentration.In the tenth chapter, major conclusions in whole dissertation were summarized, and the next research works were also prospected.更多还原