用于高分子材料改性领域的无机纳米填料化学改性方法

综述了对高分子材料中广泛使用的无机纳米填料进行表面化学改性的方法,包括偶联剂改性法、酯化改性法等小分子改性剂法,以及表面原位接枝聚合改性等大分子接枝法。这些方法不仅解决了无机纳米填料易团聚、分散性差及与高分子材料复合相容性不佳的问题,而且有效地提升了其在电子、催化、能源、生物医学等领域的应用性能。同时介绍了各种方法的改性机理、适用条件和优缺点,并对改性方法的工艺优化和发展研究方向进行了展望。     

无机粒子阻燃剂表面改性研究进展

本文通过综述近年来关于无机粒子阻燃剂改性的相关文献,分析了无机粒子阻燃剂表面改性的方法,并重点阐述了表面活性剂法、表面接枝法、机械力化学法、沉淀法等对无机粒子表面改性及其在聚合物阻燃领域的应用。最后,对未来无机粒子基阻燃高分子材料的发展方向和研究趋势进行了展望。     

功能聚氨酯材料在生物医学工程中的研究进展及应用

讨论了提高聚氨酯材料生物相客性和生物稳定性的改性方法,如表面活性端基改性、表面接枝聚合、表面形成互穿网络、使用表面活性剂、与纳米无机材料共混,介绍了功能性聚氨酯材料在生物医学工程中的应用及研究进展,表明聚氨酯材料的功能化改性仍然是今后的发展方向。     

重氮盐静电自组装的研究与应用

综述了重氮盐静电自组装反应的特点,重点介绍了重氮盐与几种负离子如羧基、磺酸基、氧负离子和磷酸根之间发生自组装反应的研究情况,以及近几年来重氮盐静电自组装技术在碳纳米管、C60、石英、金属这些无机材料表面改性上的应用。     

医用聚乳酸材料改性方法及研究进展

主要介绍了医用聚乳酸(PLA)的化学改性和物理改性研究进展情况。化学改性主要包括与小分子共聚改性、嵌段共聚改性、接枝改性和交联改性等,其中,接枝改性包括本体接枝改性与表面接枝改性,这两者根据主要实施方法包括自由基链转移法、等离子接枝法、紫外光氧化接枝法、辐射接枝法等。物理改性则包括无机填料改性与有机共混改性。最后指出了物理及化学改性方法的优缺点,并对医用PLA改性的研究前景进行了展望。     

无机固体表面的电化学改性技术研究进展

大多数不经处理的无机固体材料在实际应用中都存在缺陷.解决上述问题最行之有效的办法,就是对无机固体材料进行表面改性,使其在应用上发挥最大的作用.无机固体表面改性的方法有很多,包括表面活性剂法、偶联剂法、表面接枝法等.各种改性方法均有优劣,在实践中人们致力于寻找更为有效的表面改性方法.电化学改性法因具有反应易于控制、操作连续简单、效果显著等特点受到广泛关注.在固体颗粒表面特性和改性技术基础上,着重介绍了其电化学改性技术的研究进展.分别从粉体颗粒、碳纤维以及体材料三个方面,阐述了其电化学改性的国内外研究进展,并提出了固体颗粒电化学改性技术的未来工作重点和新的研究方向.     

聚合物表面光接枝改性研究进展

表面光接枝主要是用芳酮引发有机材料产生自由基，从而引发单体聚合产生表面接枝链。表面光接枝应用领域广泛．可用于聚合材料的表面改性以及表面功能化。综述了紫外光引发接枝改性聚合物表面的研究进展，包括光接枝聚合机理、改性方法、影响因素等，并对其应用前景及研究方向进行了介绍。     

PVDF超滤膜亲水性改性研究进展

随着近些年超滤膜的发展,人们对膜性能的要求越来越高,改善膜性能的研究不断深入。当今在对聚偏氟乙烯(PVDF)超滤膜的改性过程中经常使用的方法有膜表面改性方法以及膜材料改性方法。膜表面改性的方法主要有物理改性、表面接枝改性、等离子体改性等;而膜材料改性的方法主要包括有小分子无机粒子共混改性和膜材料本体的化学改性。改性之后的PVDF膜亲水性会增强,水通量升高,膜的抗污染性也有了一定的提升,进而增加了膜的使用寿命。     

有机／无机抗菌剂复合改性硅橡胶导尿管材料的制备及其对绿脓杆菌生物膜形成的影响

以加成型双组分硅橡胶作制造导尿管的材料,在其表面涂覆含磷酸锆负载银离子的双组分硅凝胶;硫化后浸泡饱和季铵盐溶液,再经等离子处理,接枝上季铵盐,制得有机/无机抗菌剂复合改性硅橡胶.考察了有机/无机抗菌剂复合改性对硅橡胶力学性能、疏水性能、抗菌性能的影响,并用扫描电镜和红外光谱对改性硅橡胶进行了表征.结果表明,无机抗菌粉体在硅橡胶表面的分散比较均匀,季铵盐接枝到硅橡胶表面;硅凝胶涂层对硅橡胶力学性能影响很小;有机/无机抗菌剂复合改性能降低硅橡胶的表面接触角,等离子体处理距离为25 mm时含无机抗菌粉体的硅橡胶的表面接触角均≤90°;有机/无机复合改性硅橡胶对绿脓杆菌的抑制率比传统导尿管大大提高,其中含30%无机抗菌粉体的硅橡胶的抑制率到达87%,达到国家标准要求.     

亲水改性PVDF膜材料及其膜生物反应器应用

膜生物反应器（MBR）技术中最常用的膜材料是聚偏氟乙烯（PVDF）,然而由于PVDF膜的疏水性,使其在用于MBR的运行过程中存在易污染、通量低等缺陷,因此对PVDF膜材料进行亲水改性是近年来国内外研究的热点。本文首先介绍了PVDF膜材料典型的表面涂覆改性和表面化学接枝改性这两种亲水改性方法,然后概述了随着纳米科学技术的兴起,采用无机纳米材料如碳材料氧化石墨烯（GO）、无机抑菌材料纳米银粒子及二氧化钛纳米颗粒等进行功能化复合制备PVDF膜材料等亲水改性方法。研究进展表明,新型亲水改性PVDF膜材料不仅在MBR污/废水处理中优势明显,而且在可再生生物能源生产等可持续发展领域极具潜力。     

In situ generation of diazonium cations in organic electrolyte for electrochemical modification of electrode surface

The modification of glassy carbon electrode was achieved by electrochemical reduction of in situ generated diazonium cations in acetonitrile. The in situ generation of 4-nitrophenyl diazonium cations in acetonitrile was investigated by spectroscopic methods. UV-visible spectroscopy revealed slow kinetics for the reaction of 4-nitroaniline with tert-butylnitrite in acetonitrile to form the corresponding diazonium cation. As a result, a coupling reaction, which implies a consumption of the amine and loss of the already formed diazonium cations, was evidenced by ¹H NMR spectroscopy. This spectroscopic study allowed the optimization of the in situ diazonium cations generation prior to the modification step. The electrochemical modification of the carbon electrodes with 4-nitrophenyl, 4-bromophenyl and anthraquinone groups was characterized by cyclic voltammetry and the resulting grafted layer were characterized by electrochemical techniques. The cyclic voltammetric behaviour during the electrochemical grafting was very similar to the one observed for an isolated diazonium salt dissolved in acetonitrile. In the case of the anthraquinone-modified electrode, the use of acetonitrile, into which the corresponding amine is soluble but not in aqueous media, allowed for its grafting by the in situ approach. The barrier properties of these grafted layers are similar to those obtained from isolated diazonium salts. Finally, the chemical composition of the grafted layers was determined by X-ray photoelectron spectroscopy and surface coverage in the range 5-7 × 10⁻¹⁰ mol cm⁻² was estimated for films grown in our experimental conditions.     

Electrochemical signature of the grafting of diazonium salts: A probing parameter for monitoring the electro-addressed functionalization of devices

The reciprocal influence of the phenylsubstituents and diazonium groups allows to monitor the diazonium reactivity and to electrochemically detect the grafting reaction. Extended understanding concerning the grafting of para substituted tetrafluoroborate aryl diazonium salts p-(R-Ph-N₂⁺, BF₄⁻) was obtained by studying comparatively four compounds (R = NO₂, NEt₂, NHPh, NPh₂) by electrochemistry. For R = NEt₂, the grafted molecules showed no reversible electroactivity whereas for the aminophenyl substituents, the first oxidation process induced chemical modification of the deposited layers before being totally reversible. The compound with electron withdrawing group (NO₂) was the only one able to create spontaneous covalent bounding with the glassy carbon electrode (GCE). We observed that the substituent directly acts upon the diazonium reactivity. This effect can be directly monitored through the potential onset value of the diazonium reduction. In addition, the elimination of the diazonium group during electrografting induces a cathodic shift of the electroactivity of the aminodiphenyl and aminotriphenyl groups covalently attached onto the carbon electrode surface. The shift between these electrochemical values may be considered as a signature of the grafting reaction.     

新型炭材料的表面电接枝及其应用

电接枝技术能够对很多基底材料如碳材料、金属及其氧化物等进行表面修饰,使其具有更好的理化性质和机械性能,而重氮化电接枝修饰方法因其操作简便、可控性好、应用广泛而成为当今材科学和生物医学的一大热点。主要介绍新型炭材料如纳米金刚石、碳纳米管和石墨烯等的重氮化电接枝修饰、电接枝机制和应用,并加以比较;同时对重氮化电接枝修饰技术的应用前景做了展望。     

An insight into the functionalisation of carbon nanotubes by diazonium chemistry: Towards a controlled decoration

The derivatisation of materials including iron, gold, and carbon by addition of diazonium salts is a reliable process to tune their interfacial interaction with the surrounding media. In this regard, the functionalisation of carbon nanostructures by diazonium chemistry is a versatile strategy to obtain soluble nanomaterials with degrees of functionalisation among the highest ever reported. Starting from these premises we have studied the functionalisation of multi-walled carbon nanotubes by addition of the aryl diazonium salts generated in situ by treatment of 4-methoxyaniline with isopentylnitrite. Following a thorough purification and characterisation protocol (UV–vis, TGA, ATR-IR, cyclic voltammetry, AFM and other surface analytical techniques), we have investigated the key parameters to obtain both functionalised multi-walled carbon nanotubes, where the amount of functional groups anchored to the carbon surface is less than a monolayer, and superfunctionalised carbon nanotubes, with a carbon nanotube core and a multilayered aryl coating. The results outlined provide the basis for the design and controlled processing of novel decorated carbon nanostructures that would be useful for a number of technological applications.     

Modification of hydrophobic/hydrophilic properties of Vulcan XC72 carbon powder by grafting of trifluoromethylphenyl and phenylsulfonic acid groups

Carbon supports (glassy carbon and Vulcan XC72 powder) were modified by electrochemical and spontaneous grafting of phenylsulfonic acid (PSA) or trifluoromethylphenyl (TFMP) groups via diazonium ion reduction. The effectiveness of the grafting was confirmed electrochemically, by XPS measurements and elemental analyses. The hydrophobic or hydrophilic character of carbon surfaces was evidenced by measuring the contact angles of drops of different liquids (water, ethylene glycol and glycerol) in heptane. The surface energy was calculated and it was found, for example, that spontaneous grafting of a glassy carbon surface by PSA groups led to an increase by a factor 20 of the surface energy compared with an unmodified glassy carbon surface. The study of the grafting of such groups on XC72 carbon powder indicated that a very low grafting ratio (in wt%) led to a significant change in the macroscopic properties of the powder. Thermogravimetric analysis coupled with mass spectroscopy measurements (TGA-MS) showed that these grafted layers were thermally stable even in the presence of dispersed platinum nanoparticles. It was shown by cyclic voltammetry that the carbon substrate modification did not affect the electrochemical behavior of platinum catalyst, since the same active surface area was determined on Pt-XC72, Pt-PSA-XC72 and Pt-TFMP-XC72 catalysts.     

聚偏氟乙烯膜亲水化改性研究进展

为弥补强疏水性聚偏氟乙烯(PVDF)膜在实际应用中的缺陷,从膜本体及膜表面2个角度入手,阐述了国内外对PVDF膜亲水化改性的主要方法。膜本体改性主要是将膜材料与亲水性聚合物或无机纳米材料共混,从而改善PVDF膜的亲水性能;而膜表面改性则主要是通过表面涂覆改性与表面接枝改性来实现。PVDF膜亲水性的增强,能有效改善膜的抗污染能力,从而大大提高膜的过水通量,并延长其使用寿命。     

无机材料表面接枝引发体系的研究进展

无机材料表面接技改性在工业上有良好的应用前景，80年代以来得到了人们的关注。为寻找合适的引发体系,人们进行了各种尝试。着重总结了接枝的化学引发方法，分自由基、阳离子、阴离子聚合引发体系三大类进行讨论。     

导电聚苯胺／无机复合材料的研究进展

结合导电聚苯胺／无机复合材料的研究进展,综述了聚苯胺与金属、氧化物、碳、无机盐等复合材料的合成方法、特性及应用;同时也概括了原位聚合法、溶胶-凝胶法、电化学聚合法、共混法和自组装法的优缺点。概述了聚苯胺／无机复合材料的发展方向和应用前景。