【作者】 张德锁；

【导师】 陈宇岳；

【作者基本信息】 苏州大学 ， 纺织工程， 2013， 博士

【摘要】 超支化聚合物由于其丰富的末端官能团、近似球形的三维立体结构、内部大量空腔、高溶解性、低粘度、高反应活性等物理、化学特征，在涂料工业、流变学改性剂、纳米技术、超分子化学、膜材料、生物医用材料、光学及电学材料等多个领域有着广泛的应用前景。基于超支化聚合物内部的空腔结构，利用其作为模板可以有效控制制备纳米材料。本研究以二乙烯三胺和丙烯酸甲酯为原料，通过缩聚法合成制备了端基为氨基的超支化聚酰胺HB-PA，并在HB-PA的合成制备过程中添加一定量的丁二酸酐，使得HB-PA支链间发生交联，制备了具有三维网络结构的改性端氨基超支化聚合物PNP。利用HB-PA和PNP在溶液中控制制备了纳米银和纳米ZnO，比较研究了两者对控制纳米材料粒径大小和稳定性的作用。同时，将超支化聚合物控制制备纳米材料的特性与纺织品的功能化整理相结合，利用控制制备的纳米银和纳米ZnO整理织物，以赋予织物优异的抗菌、抗紫外性能。研究结果表明，HB-PA控制制备的纳米银水溶液稳定性较差，所制备的纳米银在放置7h后就发生了团聚变色现象。而利用PNP控制制备的纳米银，不仅可以控制纳米银的大小，而且能够最大程度的保护所制备的纳米银。通过调节氨基和银离子的摩尔比为1:1和5:1，分别在水溶液中制得了平均粒径为13.23nm和4.34nm的纳米银，其放置6个月后平均粒径变为18.83nm和8.99nm，无变色和沉淀现象。各种表征手段证明所制得的纳米银为具有较好结晶性的单质银纳米颗粒，其具有优异的抗菌性能，对金黄色葡萄球菌和大肠杆菌的最小抑菌浓度均为2ppm。以HB-PA和PNP做为保护剂和分散剂，在乙醇溶液中采用溶胶-凝胶法制备了纳米ZnO，实验表明HB-PA和PNP可以有效控制纳米ZnO的粒径，所制备的纳米ZnO粒径分别为3.84nm和1.89nm，且具有较好的稳定性，放置一个月后无明显变化。而在无聚合物条件下制备的纳米ZnO粒径为5.60nm，放置一周后即变浑浊并沉淀。通过调节反应中碱试剂的量，制备了不同粒径大小，具有从深蓝色到黄色荧光颜色的纳米ZnO溶液。由于HB-PA和PNP中均含有大量的氨基，其在水溶液中质子化后显碱性，利用其作为碱试剂可与Zn(NO3)2在水溶液中直接反应制备纳米ZnO。在反应中HB-PA和PNP不仅作为反应试剂直接参加反应，而且作为保护和控制性聚合物对纳米ZnO的生成起控制作用，以制备具有一定粒径大小和稳定性的纳米ZnO水溶液。同制备纳米银相似，PNP能够控制生成更小的纳米ZnO，在最优条件下HB-PA可以控制制备100nm左右的纳米ZnO，而PNP能够控制制备出平均粒径为5.9nm的纳米ZnO，并且在水溶液中保持一周以上的稳定性。制备得到的纳米ZnO具有一定的抗菌性能，其对金黄色葡萄球菌的抑菌性优于对大肠杆菌的抑菌性。利用PNP对真丝织物进行纳米银抗菌整理，比较研究了浸渍法和汽蒸原位生成法整理真丝织物的效果。结果表明，原位生成法整理能够获得更高的纳米银含量，且整理后纳米银具有更好的牢度。整理的真丝织物纤维表面均匀分布了粒径大约为50nm左右的纳米颗粒，XPS测试表明其为单质纳米银。当整理液中Ag+浓度仅为0.05mM时，整理的真丝织物对金黄色葡萄球菌和大肠杆菌的抑菌率就分别达到了99.87%和99.52%，且此时织物的白度仅从90.47下降到86.49，影响不大，30次洗涤后其抑菌率仍能保持在98%以上。利用HB-PA或PNP和Zn(NO3)2为原料在棉织物上原位生成沉积纳米ZnO整理棉织物，通过优化整理工艺得到了不同纳米ZnO含量的棉织物，整理棉织物的UPF值从几十到一百多不等。经原位生成沉积纳米ZnO整理的棉织物不仅具有优异的紫外线防护性能，而且具有很好的抗菌性能，其对金黄色葡萄球菌的抑菌率均在99%左右，而对大肠杆菌的抑菌率只有在其ZnO含量达到一定值时才能达到90%以上。原位生成沉积纳米ZnO整理的棉织物具有一定的耐洗牢度，经30次洗涤后其UPF值能够保持在30左右。利用微波法可以方便、快捷地将纳米ZnO整理到棉织物中，通过调节反应物浓度，整理出具有不同ZnO含量和UPF值的棉织物。其具有较原位生成沉积法纳米ZnO整理的棉织物好的耐洗牢度，30次洗涤后其UPF值从99.65下降到37.45。另外，通过微波法可一步原位生成纳米Ag-ZnO复合整理棉织物，经纳米Ag-ZnO复合整理的棉织物不仅具有优异的紫外线防护性能，同时还具有优异的抗菌性能，对金黄色葡萄球菌和大肠杆菌的抑菌率均能达到99.99%。更多还原

【Abstract】 Hyperbranched polymers have widely potential applications in painting, additives,film, nanotechnology, supramolecular science, biomaterials, optical and electrical materials,due to their special structure, unique chemical and physical properties, such as abundant ofterminal functional groups, three-dimensional architecture, numerous interior cavities, highsolubility, low viscosity, and high reactivity. With numerous interior cavities, they can beused as templates to control synthesize nanoparticles. In this research, an amino terminatedhyperbranched polyamide polymer (HB-PA) was synthesized by polycondensation usingdiethylenetriamine and methyl acrylate as reagents. Meanwhile, a modified hyperbranchedpolymer with three-dimentional network structure (PNP) was also fabricated by addingsuccinic anhydride in the synthesis process of HB-PA to make the branches crosslinked.Based on the outstanding advantage of hyperbranched polymers on the control synthesis ofnano materials, Ag and ZnO nanoparticles were prepared in the solutions by HB-PA andPNP. On another hand, the prepared nanoparticles polymeric hybrids were applied to thefunctional finishing of textile to provide them with excellent antibacterial activities and UVprotective properties.The results indicated that Ag nanoparticles prepared by HB-PA were not stable inaqueous solutions which shown color change within7h after generation. However, PNPcan not only controlled the size of Ag nanoparticles, but also protected them to keep stable.When controlled the molar ratio between amino groups in the PNP and silver ions at1:1and5:1, the average size of synthesized Ag nanoparticles were13.23nm and4.34nm,respectively. After6months storage, the average size of them changed to18.83nm and8.99nm, and no color change and deposit could be observed. The prepared Agnanoparticles were confirmed as Ag0with well crystalline and have excellent antibacterialactivities. The Minimum inhibitory concentrations (MIC) of them were2ppm againstStaphylococcus aureus and Escherichia coli.With HB-PA and PNP as protect agents, ZnO nanoparticles were prepared in ethanolsolution by sol-gel method. The ZnO nanoparticles have average size at3.84nm and1.89 nm synthesized by HB-PA and PNP respectively, and have good stability. However, theZnO nanoparticles prepared without polymer have an average size at5.6nm and showndeposit after one week storage. The ZnO nanoparticles with different size and fluorescencecolor were prepared by adjust the quantity of alkaline reagent.The HB-PA and PNP aqueous solutions were alkali due to the protonation of aminogroups which located in the structure of them. They can reacted with Zn(NO3)2directly togenerate ZnO nanoparticles in aqueous medium. During the process, HB-PA and PNP notonly acted as the reagents to produce ZnO nanoparticles but also played an import role tocontrol the particle size and protect them for their stability. It is similar to the fabrication ofAg nanoparticles, ZnO nanoparticles prepared by PNP is smaller than that prepared byHB-PA. At the optimal reaction condition, HB-PA can get the ZnO nanoparticles with thesize around100nm. However, the PNP can control synthesize ZnO nanoparticles with anaverage size at5.9nm and keep stable in aqueous solution more than one week.PNP was applied to generate Ag nanoparticles for the antibacterial finishing of silkfabrics via immersion method and in situ synthesis method. The results demonstrated thatthe silk fabrics treated with Ag nanoparticles via in situ synthesis method have highersilver content and better durability than the treatment via immersion method. Then thetreated silk fabrics via in situ method were characterized and their antibacterial activitieswere measured. SEM image shown Ag nanoparticles well dispersed on the surface oftreated silk fibers at around50nm. XPS tests confirmed that the nanoparticles on the silkfibers are Ag0particles. The quantitative bacterial tests showed the bacterial reduction ratesof Staphylococcus aureus and Escherichia coli were able to reach above99%with nomore than0.05mmol/L of AgNO3. The whiteness of silk fabric only changed from90.47to86.49. The antibacterial activity of the treated silk fabric was maintained at98.86%reduction even after being exposed to30consecutive home laundering conditions.HB-PA and PNP were ultilized to react with zinc nitrate to in situ generate and depositZnO nanoparticles on cotton fabrics for their functional finishing. The treated cottonfabrics have different ZnO contents and UPF values. They not only shown excellent UVprotective properties but also have good antibacterial activities. The bacterial reductionrates of Staphylococcus aureus of all samples are around99%. However, only when thecontent of ZnO in the fabric reached a certain quantity, the bacterial reduction rates ofEscherichia coli can reached above90%. The UPF of treated cotton fabric was maintainedaround30after being exposed to30consecutive home laundering conditions which indicated in situ generated and deposited ZnO treated cotton fabrics has durability.Microwave treatment is a facile method to generate ZnO nanoparticles in cotton fabric.Treated cotton fabrics with different ZnO contents and UPF values can fabricated by adjustthe concentration of reagents which have better laundering durability than in situgeneration and deposition ZnO treated cotton fabrics. After being exposed to30consecutive home laundering conditions, the UPF value decreased from99.65to37.45.Otherwise, microwave method can also fabricate Ag nanoparticles and ZnO nanoparticlesin fabric by one-step treatment. The treated cotton fabrics got both excellent UV protectiveproperty and antibacterial activity. The bacterial reduction rates of Staphylococcus aureusand Escherichia coli both exceeded99.99%.更多还原