【作者】 于明华；

【导师】 卿凤翎；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2008， 博士

【摘要】 众所周知,氟碳化合物具有极低的表面张力,因此广泛用于拒水拒油整理。随着人们生活水平的提高,一方面人们对拒水拒油整理效果提出了更高的要求,另一方面人们对具有新功能的含氟整理剂也提出了需求。因此,找到能够提高拒水拒油效果的技术和开发出具有新功能的含氟整理剂显得犹为重要。在本论文中我们合成了几种含氟整理剂,采用直接或与其它表面改性技术结合的方法对棉织物、玻璃、单晶硅片进行改性,赋予它们不同的功能,并对改性后的效果进行了测试。本论文由以下几部分工作构成:1.目前,超疏水表面的制备方法已经成为了人们的研究热点。在本论文中我们将溶胶-凝胶技术与含氟整理剂相结合在织物上制备出具有超疏水和疏油性能的涂层。在正硅酸乙酯,乙醇和水三者的比例不变的实验条件下,通过改变催化剂氨水的量成功制备了一系列不同粒径的SiO₂溶胶样品sol 1-5,这些样品中的颗粒粒径均在100—200nm之间。我们同时合成了含全氟烷基季铵盐硅烷偶联剂PFSC,并将溶胶样品和PFSC共同应用于织物整理。经H₂O和CH₂I₂接触角测试和拒水拒油等级测试结果发现,只有溶胶样品sol 4的粒径大小合适,可以显著增加表面粗糙度,经其整理的织物样品通过含全氟烷基季铵盐硅烷偶联剂PFSC修饰后比只经PFSC整理的棉织物样品的拒水拒油性能得到提高,H₂O的接触角从133°提高到145°,接近于超疏水性能,CH₂I₂的接触角从125°提高到131°;拒水拒油级别分别从3级、4级提高到4级、5级。而经另外四个溶胶样品和PFSC共同整理的织物样品的拒水拒油效果没有得到提高。2.通常具有低表面自由能的含氟聚合物材料不易吸附环境中的尘埃或污物粒子。但是一旦被污染,由于它们的高疏水性使得此类材料沾污后很难用水清洗。为了弥补这个不足就需要制备出具有疏水/疏油-亲水可逆转换性能的智能表面,这样就既可以减少在空气中的沾污,又方便沾污后的清洗。在本论文中我们将含全氟烷基丙烯酸酯与丙烯酸采用乳液聚合方式合成了聚（全氟烷基丙烯酸酯-丙烯酸）（PPFAA-AA）,并通过传统的轧-烘-焙过程将聚合物乳液整理到棉织物上,形成的涂层具有疏油/疏水-亲水可逆转换功能。在乳化剂量不变条件下,通过改变单体的重量比,得到PPFAA-AA聚合物样品copoly1-4,其中copoly2整理的织物具有明显的疏水-亲水转换性能,水的接触角从刚开始的127°在30min内迅速减小到33°。根据该现象,提出了疏水.亲水转换机理,通过XPS测试润湿前后织物表面PPFAA-AA涂层不同深度化学组成含量变化,验证了该机理。3.日常生活中透明基材的上雾现象和衣服上起静电现象经常困扰着人们,其中一个解决方法就是用亲水整理剂进行亲水化处理。基于这个需求在本论文中我们设计了一个亲水拒油聚合物Rf-（DMDAAC）n-Rf,亲水性可以起到防雾和抗静电效果,拒油性可以防止污染减少清洗次数,使整理效果持久。首先合成了全氟聚醚二酰基过氧化物（RfCOO）₂,并用来引发二甲基二烯丙基氯化铵（DMDAAC）聚合,得到含有全氟烷氧基末端基团的二甲基二烯丙基氯化铵聚合物（Rf-（DMDAAC）n-Rf）。通过传统的轧-烘-焙过程将其整理到棉织物上,整理后织物具有亲水拒油性,对水的接触角为0°,对正十六烷的接触角为117.5°。4.自组装技术在表面改性中得到了广泛的应用。在本论文最后我们在玻璃和单晶硅基底上将含全氟烷基的化合物利用自组装技术接到基底表面,以期降低表面自由能,实现超薄拒水拒油膜的制备。我们采用自组装方法制备了PFOA-APTES和PFOA-TESPA自组装双层膜。通过原子力显微镜（AFM）、椭圆偏光仪（Ellipsometry）和X-射线光电子能谱（XPS）对PFOA-APTES自组装双层膜的膜性能进行了测试与表征,证明PFOA-APTES自组装双层膜制备成功。利用接触角测试对PFOA-APTES自组装双层膜的拒水拒油性能进行了研究,发现在PFOA与APTES-SAF反应12h后形成的双层膜具有较好的拒水拒油性能。有关PFOA-TESPA自组装双层膜,我们主要是对TESPA-SAF和PFOA-TESPA的制备条件进行了摸索。但从拒水拒油效果来看,PFOA-TESPA自组装双层膜的制备不是很成功。更多还原

【Abstract】 It has been known that fluorocarbons have an extremely low surface free energy and they are widely applied for water and oil repellent finishing.Along with the improvement of people’s living standard,fluorine-containing finishing agents with excellent water and oil repellency and（or）new function are demanding.The employment of other modification technique to improve water and oil repellency and development of fluorine-containing finishing agents with new functions are needed to meet the above demand.In this study,several kinds of fluorine-containing finishing agents were synthesized,applied on cotton fabric,glass and crystal silica substrates directly or combining other surface modification technique.The properties of the treated substrates were studied.The main work is described as follows.1.At present,the method for the fabrication of superhydrophobic surface has already become the research hot spot.In this study,sol-gel technique was employed and combined with fluorine-containing finishing agents to fabricate superhydrophobic cotton fabric coating.By changing the concentration of NH₃·H₂O catalyst,a series of silica sol samples（sol 1-5）with different silica nanoparticle sizes between 100 and 200nm were prepared successfully.Perfluorooctylated quaternary ammonium silane coupling agents PFSC was synthesized and applied on cotton fabrics with silica sol samples.The hydrophobic and oleophobic properties were determined in terms of H₂O and CH₂I₂ contact angle measurements and water and oil repellency rating measurements.As a result,silica sol sample sol 4 with appropriate size of silica nanoparticles was effective for increasing surface roughness,and the cotton fabric treated with it and PFSC showed better water and oil repellency than with PFSC alone. The H₂O contact angles increased from 133°to 145°,which was nearly superhydrophobic;and the CH₂I₂ contact angle increased from 125°to 131°.The water and oil repellency ratings increased from class 3 to 4 and class 4 to 5 respectively.The cotton fabric treated with other four silica sol samples and PFSC showed no increase in water and oil repellency.2.Usually the dirt particles do not adhere to low-energy surfaces of fluorinated polymers.However,once it was dirty,it is difficult to clean with water due to its good water repellent property.In light of this limitation,the smart surface exhibiting oleophobic/hydrophobic to hydrophilic switching property was demanded for minimizing adhesion in air and facilitating soil release in water.In this study, poly（perfluoroalkylated acrylate-acrylic acid）（PPFAA-AA）copolymers were prepared by the emulsion copolymerization of perfluoroalkylated acrylate and acrylic acid and applied on cotton fabric by pad-dry-cure process,the PPFAA-AA coating thus obtained exhibited oleophobic/hydrophobic to hydrophilic switching property, With the constant concentration of emulsifying agents,PPFAA-AA samples （eopolyl-4）were synthesized by changing the weight ratios of the two monomers, The copoly2 showed the best hydrophobic to hydrophilic switching property among these samples,and the water contact angles decreased from 127°to 33°within 30min. The hydrophobic to hydrophilie switching mechanism was proposed and verified by XPS measurements of chemical composition changes at different depth of the dry and wet PPFAA-AA coatings on cotton fabrics respectively.3.In the daily life,the fog on the transparent substrate and the static on the textile embarrassed people.One solution is to modify the surface with hydrophilic finishing agents.In this study,the polymer Rf-（DMDAAC）n-Rf with hydrophilic and oleophobic properties was designed,the hydrophilicity was used for antifogging and antistatic;the oleophobicity was used for antisticking,so the washing times can be reduced and the finishing effect was prolonged.First,the perfluoropolyether diacyl peroxide（（RfCOO）₂）was synthesized and then used for initiating the polymerization of dimethyldiallyl ammonium chloride（DMDAAC）to give the perfluoroalkoxyl end-capped polymer Rf-（DMDAAC）n-Rf.The polymer was applied on cotton fabric by pad-dry-cure process.The treated cotton fabric showed hydrophilic and oleophobic, the water and hexadecane contact angles on the surface were 0°and 117.5°respectively.4.Self-assembly technique is widely used in surface modification.At the end of this study,perfluoroalkyl-containing compound was introduced to the surface of the glass and single crystal silicon substrates by self-assembly technique to lower the surface free energy and prepare ultra-thin water and oil repellent films.Self-assembled dual layer films PFOA-APTES on single crystal silicon and PFOA-TESPA on glass substrate were prepared respectively.The structure and morphology of the dual layer film PFOA-APTES were characterized by means of atomic force microscopy（AFM）, ellipsometry and X-ray photoelectron spectroscopy（XPS）and the results demonstrated that the dual layer film was prepared successfully.The water and oil repellency of PFOA-APTES were measured in terms of contact angle measurements. The dual layer film PFOA-APTES obtained by reaction of PFOA with APTES-SAF for 12h showed better water and oil repellency than others.About self-assembled dual layer film PFOA-TESPA,the preparation conditions of TESPA-SAF and PFOA-TESPA were mainly studied.But the water and oil repellency measurements indicated that the preparation was not very successful.更多还原