【作者】 甘胜华；

【导师】 杨万泰；

【作者基本信息】 北京化工大学 ， 高分子化学与物理， 2009， 博士

【摘要】 有机聚合物具有成本低、易加工、透明性好、柔软、质轻、可回收、易降解等优异性能,以聚合物基材为基底的现代材料引起了人们的广泛关注,如在聚合物基材表面制备金属纳米粒子,功能化修饰的金属纳米粒子具有独特的光学、磁学、催化和电学性能,在化学、材料科学、生物学、纳米技术等领域得到了广泛应用。此外,在有机聚合物基材表面制备一层无机氧化物进而组成有机/无机复合层及对其表面进一步功能化具有重要的理论意义和研究价值。有机/无机复合物不仅具备有机聚合物的优良性能,同时也具备无机氧化物的一些特性,如高反应性,易对其表面进行分子设计等,因而常用于分子自组装、包装材料、生物技术、传感器及光电器件领域。然而这种复合材料制备的一个关键问题就是有机、无机两相的粘接性,因此需要预先对有机基材表面进行改性。有机聚合物基材表面接枝聚合物刷改性以提高有机聚合物表面的生物相容性、或进行表面分子设计以便固定蛋白质也是有机聚合物基材应用的重要方面。本文基于上述考虑,进行了如下工作:1.通过硅烷偶联剂在通用聚合物膜表面制备一层近单分子层过渡层进而组装金纳米颗粒,得到尺寸约为20nm的金纳米颗粒。前期改性过程中使用不同形状光掩模可很容易的在改性膜表面得到大范围、均匀、效果良好的图案化金纳米颗粒。由于前期反应的普遍性,基底可以是任何有机聚合物。同时由于硅氧烷种类较多,因此可制备末端带有巯基、环氧基、羧基等系列单层膜进而组装金属纳米颗粒。2.有机/无机复合膜制备研究:（a） BOPP/SiO_x复合膜的制备研究:利用“界面定向溶胶-凝胶法”在通用聚合物膜表面制备了高质量的SiO_x层并使其图案化,该方法具备以下优点:制备条件温和,不需要真空等苛刻条件,在常温下就能简单、快速、廉价制备;不会像高能辐射等方法造成基体降解;通过共价键使SiO_x层与功能化聚合物表面紧密结合;通过超声或胶带撕拉可在表面制备低扩散（＜5%）和大尺寸（cm²）的清晰图案;通过旋涂可在表面获得平整SiO_x层（RMS＜9（?））,其衍生性好,可以同样制备TiO₂无机层;可在表面引入可进一步应用的各种功能性基团。因此,以所得聚合物为基体的柔软、透明电学或生物材料具有广泛的研究价值和工业前景。（b） BOPP/SiO_x/TiO₂复合膜制备研究:在制备BOPP/TiO₂复合膜的过程中引入一层无机SiO_x过渡层,可以获得BOPP/SiO_x/TiO₂复合膜。SiO_x过度层对表面沉积TiO₂的性质无影响,SiO_x不会破坏有机聚合物基底,同时又能在TiO₂无机层下稳定存在,所以增加过渡层不会改变原有良好的反应性质,同时还起到了保护基底的作用。3.利用表面光反应改性方法,以过硫酸铵水溶液为反应液,在通用聚合物膜材料（聚酯PET、双向拉伸聚丙烯BOPP、流延聚丙烯CPP）表面引入了单层酸根离子或羟基基团,然后研究了所得膜材料对3种代表性蛋白质（木瓜蛋白酶,牛血清白蛋白和抗体IgG）的非特异性吸附。采用称重法、付立叶红外光谱仪（FTIR-ATR）、水接触角（CA）、荧光显微镜等测试手段对表面改性效果和非特异性吸附强弱进行了表征。结果表明:改性和未改性PET膜对3种蛋白质的非特异性吸附均较小;表面硫酸化BOPP膜对抗体IgG的非特异性吸附较小;表面羟基化CPP膜对牛血清白蛋白的非特异性吸附较小。以二苯甲酮为光引发剂,通过表面光接枝改性在聚丙烯膜表面分别接枝一层聚丙烯酸（PAA）、聚丙烯酰胺（PAM）和聚马来酸酐（PMAH）,然后分别在上述接枝层表面固定牛血清白蛋白（BSA）。采用称重法、付立叶红外光谱仪、水接触角测试仪、紫外-可见光谱等测试手段对表面改性效果和固定蛋白量进行表征。结果表明上述接枝改性聚丙烯膜表面都可固定BSA,固定效率比较为:PP-g-PMAH＞PP-g-PAA＞PP-g-PAM。引入功能性基团改性表面已经被广泛用于生物医学领域。本论文研究了一种经硅烷化处理向聚合物表面快速、简单引入各种分子级功能基团的方法。在羟基化PP膜表面通过羟基与3-APTES分子中硅氧烷反应引入较高覆盖率的伯氨基,再利用戊二醛进行活化,通过醛胺缩合反应,将蛋白质（IgG）有效固定在聚合物基体表面。借由不同末端功能基团的硅氧烷分子可向任何惰性表面引入各种功能基团,广泛用于微排列,生物传感器,过滤膜和微分离等领域。有机/无机复合膜表面无机层上引入功能基团使表面反应像在无机基体表面一样进行。比较了BOPP/SiO_x表面和石英表面的性能,将石英表面发生的化学反应引入到复合膜表面,得到很好的重复性,因而可说该复合膜表面具备了石英一样的性能,能够应用于生物芯片等领域。更多还原

【Abstract】 Plastics-supported modern material has received increasing attentions because polymers have unique benefits including low cost, easy processability, high transparency, flexibility, light-weight, recyclability and disposability. For example, metal nanoparticles were fabricated on the surface of polymer-supported. Metal nanoparticles have drawn considerable interest in various fields of chemistry, materials, biology and nano-technology because of their unique physical and chemical properties in optical, magnetic catalyse and electronics. In addition, the fabrication of organic/inorganic hybrid materials, and the surface functionalization of polymer-supported. The fabrication of an inorganic oxide layer on organic-supported surface for organic/inorganic compound layers and its surface functionalization has an important theory significance and worthiness. The compound materials have not only the excellent characters of organic polymers, but also the outstanding characteristics of inorganic oxide. That is high and activity reaction, and it is easy to design surface on molecule level. It has found a wide range of applications in colloid self-assembly, packaging, biotechnology, sensors, and opt-electronic devices. However, an important factor restricting the development of the compound material was the low viscidity between organic phase and inorganic phase. Therefore the surface of organic-supported was used to be modified before the compound material fabrication. It was also an important aspect for application that the surface of organic materials was grafted polymer brushes modification in order to the biocompatibility and molecule design for immobilization protein.Base on thinking above, the main contents of this thesis were as follows:1. An approximately monolayer was fabricated on polymer film surface by silanization for assembly golden nanoparticles. The size of particles was about 20 nm. It is easy that golden nanoparticles pattern was gained on the surface by photomask on the process of modification. The effect of pattern was very nice and uniformity on quite bounty area. Owing to the method’s catholicity and applicability to all of inert organic surfaces which have similar alkyl C-H structures, meanwhile the existence of the well-established silanes library, it is no doubt that a variety of functional groups hence could be attached onto inert polymer surface for assembly different metal nanoparticles.2.The research of organic/inorganic compound film: （a） The fabrication of BOPP/SiO_x compound film. Here demonstrate a new method, named as "interface-directed sol-gel" is capable of fabricating high quality silicon oxide （SiO_x） film and its patterning onto various commodity plastics. Our method has at least seven advantages than current techniques: simple and fast process at low cost without the need of vacuum devices and cleanroom facilities; mild process without the damage on the substrate because of the exclusion of high-energy species and photolithography; strong interfacial adhesive strength between SiO_x and polymer substrate due to the formation of covalent bond on functionalized surface; easy to obtain clear pattern in large area （cm²） with low line edge variation （<5%） by simple ultrasonic washing or adhesive tape peeling; very smooth SiO_x surface （RMS<9A by AFM） could be obtained by spin-coating; good generality to extend other oxide layer fabrication, for example TiO₂ pattern fabrication shown in this study; versatile functions could be conducted on such SiO_x-coated polymer matrix, as also partially demonstrated by protein immobilization and oxygen barrier test in this study. On the basis of the above merits, we are fully confident that this method would draw a myriad of attentions from academic and industrial fields in that it is highly desirable and important for polymer-supported flexible optical, electrical and biomedical materials, （b） The fabrication of BOPP/SiO_x/TiO₂ compound film: The BOPP/SiO_x/TiO₂ compound film was fabricated by adding a SiO_x transition layer on the process of fabricating BOPP/SiO_x. It was found that the SiO_x has not affected the property of TiO₂. Not destroying the organic-supported, the SiO_x layer can exist stably below TiO₂ layer. The transition layer can play an important role in protecting the organic-supported.3.The research of biocompatibility and surface functionalize about polymer-supported. Monolayer vitriol acid radical or hydroxyl on polymer films （PET、BOPP、CPP） have been synthesized by surface photoreaction modification method using Ammonium persulfate as reagent. The non-specific adsorption has been studied between these films and three kinds of protein （Enzyme, BSA and anti-body IgG）. The effect of the surface modification and protein adsorption was determined by Weightiness, FTIR-ATR, Water Contact Angle and fluorescence microscope （Olympus IX-81）. As a result, the non-specific adsorption of unmodified and modified PET to three kinds of protein is less. The fewer non-specific adsorption was happen between acidified BOPP and anti-body IgG. It was also appeared between hydroxyl CPP and BSA. Layers of poly （acrylic acid） （PAA）, polyacrylamide （PAM） and maleic anhydride （PMAH） have been synthesized on polypropylene （PP） films by a surface photografting modification method using benzophenone （BP） as photoinitiator. Bovine serum albumin （BSA） was subsequently grafted onto these films. The effect of the surface modification and protein adsorption was determined by weight changes, FTIR-ATR, water contact angle measurement s and UV-visible spect-roscopy. The extent of grafting of BSA on the modified PP films decreased in the order PP-g-PMAH > PP-g-PAA > PP-g-PAM.Surface modification through implanting functional groups has been demonstrated to be extremely important to biomedical applications. Here report the potential to perform silanization techniques on alkyl polymer surface, which provide a simple, fast, inexpensive and general method to decorate versatile functional groups at molecular level. As an example, high-density primary amines could be obtained on a model polymer, polypropylene substrate through the reaction between amine-capped silane, 3-aminopropyltriethoxysilane （APTES） and hydroxylated polypropylene surface. A model protein, immunoglobulin （IgG）, could be effectively immobilized on the surface after transforming amines to aldehydes by the aldehyde-amine condensation reaction between glutaraldehyde （GA） and amines. The routes we reported here could directly makes use of the benefits from well-developed silane chemistry, and hereby is capable to graft any functionalities on inert alkyl surface via changing the terminal groups in silanes, which should stimuli instantly the development of many realms such as microarrays, immunoassays, biosensors, filtrations, and microseparation.Functionality groups were introduced on the organic/inorganic compound film surface. Make the reaction happen on organic/inorganic compound film surface the same as inorganic-supported surface. Comparing BOPP/SiO_x surface with quartz surface, many characters have the same. The reaction happened on quartz surface had echoed well on organic/inorganic compound film surface. So it can be applied on biochips’ area as quartz.更多还原