含氟聚氨酯的研究进展

综述了溶剂性、水性含氟聚氨酯的合成及研究，并进行了讨论。     

Synthesis of novel perfluoroalkyl ether derivatives

A series of novel fluoroether-containing monomers has been designed and prepared based on the commercially available perfluoroalkyl ether acid fluoride. Treating acid fluoride with allyl alcohol, 2-hydroxyethyl methacrylate or N-allylmethylamine allowed for the direct formation of corresponding vinyl-containing fluorinated monomers. High yields of the fluorinated epoxy monomers could be obtained from acid chloride with glycidol; meanwhile, fluorinated diol was prepared from diethanolamine or 3-amino-1,2-propanediol. Moreover, fluorinated monoamine, fluorinated monoalcohol and fluorinated dichloride were also obtained. Most of these fluorinated monomers were liquid at room temperature and exhibited good solubility in common organic solvents.     

Monolayers made from fluorinated amphiphiles

Monolayers of fluorinated amphiphiles present specific structure and properties, due to differences in chain stiffness and molecular interactions between fluorinated and hydrogenated amphiphiles. The combined hydrophobicity and lipophobicity of fluorinated chains result in lateral and vertical micro phase separation when fluorinated and hydrogenated amphiphiles are mixed. Monolayers of fluorinated amphiphiles have potential applications in materials and biological sciences, including for two-dimensional protein crystallization and microelectronics.     

光固化含氟聚合物的合成进展

综述了自由基光固化和阳离子光固化含氟聚合物的合成进展,并对其进行了讨论.     

硬段侧链含有氟化双季铵盐的聚氨酯表面性能及抗菌性能分析

研究了硬段侧链含有氟化双季铵盐的系列聚氨酯(FQPUs)的表面性能和抗菌性能. 水接触角测试和表面自由能测试结果表明, 加入少量氟化双季铵盐扩链剂, 可以使聚氨酯表面富集氟碳链, 氟化双季铵盐聚氨酯表面自由能很低, 具有很好的抗黏附性能. 迁移到表面的两条氟碳链在常温下不会发生链反转, 使材料的抗黏附性能得以保持. 同时, 使材料表面形成一层疏水层, 减小材料的吸水率. XPS研究结果表明, 氟碳链的-CF₃位于材料的最外层, 材料的次表面是具有良好杀菌性能的双季铵盐, 这样形成了具有多重抗菌性能的表面. 另外, XPS研究结果表明, 材料表面化学结构与材料本体的微相分离结构相关. 抗菌性能测试结果表明, 氟化双季铵盐聚氨酯抗金黄色葡萄球菌的能力很强, 对于大肠杆菌的抗菌效果有所下降, 但相对于单季铵盐聚氨酯的抗菌效果有一定提高.     

Synthesis of Highly Functionalized Fluorinated Porphyrins

Highly functionalized fluorinated porphyrins were synthesized by a convergent strategy. Nucleophilic substitution using fluorinated branched unit and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin afforded highly functionalized fluorinated porphyrin 8 containing 24 fluorinated chains in the peripheral region.     

Chiral side-chain liquid crystalline polysiloxanes bearing fluorinated mesogens and cholesteryl groups

A series of chiral side-chain liquid crystalline (LC) polysiloxanes bearing fluorinated mesogens were synthesized with a cholesteric LC monomer and a fluorinated nematic LC monomer. They were characterized by use of various experimental techniques, and effect of fluorinated mesogens on characteristic of LC polysiloxanes was studied as well. In photoluminescence spectra, a narrow and a broad peak occur at around 270-317 nm, originated, respectively, from fluorinated phenyl groups and the conjugated xenene structure. The specific rotation analysis of all polymers showed negative values, but absolute values were lower than those of the chiral monomers. All polymers showed smectic LC phase with very wide temperature ranges on heating and cooling cycles. Especially, only polymers bearing more fluorinated component exhibited smectic-cholesteric phase transition when they were heated. As the polymers contained more fluorinated mesogens, segregation of the fluorinated segment to the surface should occur at mesomorphic temperature. The highly ordered lamellar mesogen-siloxane matrix systems should be disturbed severely by separation of fluorinated mesogens, suggesting mesogenic orders transition from lamellar smectic to cholesteric phase.     

Synthesis of New Fluoropolymers: Tailoring Macromolecular Properties with Fluorinated Substituents

The challenges and opportunities in the preparation of new fluoro- polymers are illustrated by the synthesis of fluorinated poly(ether sulfones), polyimides, and polyethers. Synthetic methods used for the preparation of new fluorinated monomers and polymers include anion-radical substitutions of perfluoroalkyl diiodides, nucleophilic additions to fluorinated olefins, perfluoroalkylsulfonyl-mediated nucleophilic sub-stitutions, and direct fluorinations with elemental fluorine. Properly placed fluorinated substituents can have significant effects on the dielectric properties, thermal stability, moisture absorption, permeability, phase transitions, and reactivity of the resulting polymers. In addition, fluorinated groups can enhance nonlinear optical effects and provide a method for chromophore alignment. The special behavior of partially fluorinated substituent groups offers unique tools for tailoring macro-molecular properties.     

含氟芳杂环高分子及其在微电子工业中的研究进展

综述了近年来国内外在含氟芳杂环高分子方面的研究及应用进展情况。主要介绍了含氟聚苯并睬咪唑(PBI)、聚苯并喏唑(PBO)、聚芳醚(PAE)及其衍生物等材料。从含氟单体的合成、聚合物的合成及其应用等几个方面进行了阐述。     

A fluorinated masked o-benzoquinone

A fluorinated masked o-benzoquinone has been prepared by oxidation 4-fluoro-2-methoxyphenol in methanol with phenyliodine diacetate. The fluorinated diene reacts in situ in normal Diels-Alder reactions with various dienophiles. The sequence provides new fluorinated building blocks for the synthesis of a variety of fluorinated compounds.     

含氟聚酰亚胺及其在微电子工业中的研究进展I含氟单体及聚酰亚胺的合成

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况。主要从含氟二胺单体、二酐单体及含氟聚酰亚胺在合成方面的研究进展情况进行了详细的综述。重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况，并指出为了推动含氟聚酰亚胺这类具有优良综合性能的功能材料在工业上的广泛应用，就必须首先解决含氟单体种类较少这个制约含氟聚酰亚胺发展的瓶颈问题。     

Reactions of enamines with fluorinated acyl chlorides----Synthesis of fluorinated 1,3-diketones and 1,3-keto-aldehydes

The reactions of enamines (1a-b,4,6) with fluorinated acyl chlorides (2a-d) produced fluorinated 1,3-diketones (3a-f) and 1,3-keto-aldehydes (7a-c) in good yields as well as byproducts fluorinated acylamides (5a-c).It is proposed that the reactions involve nucleophilic attack by the C-atora and/or N-atom of the enamines on acyl carbon of the fluorinated acyl chlorides.     

Controlled immobilization of palladium nanoparticles in two different fluorinated polymeric aggregate cores and their application in catalysis

Fluoroalkyl end-capped betaine-type cooligomeric nanocomposites-immobilized palladium nanoparticles were prepared by the reactions of palladium chloride with sodium acetate in the presence of sodium chloride and the corresponding fluorinated cooligomers. Outer blocks of poly(2,3,4,5,6-pentafluorostyrene)-containing ABA-triblock copolymeric nanocomposites-immobilized palladium nanoparticles were prepared by the use of the corresponding block copolymers under similar conditions. TEM images showed that palladium nanoparticles can be immobilized outside the fluorinated cooligomeric nanocomposite cores; in contrast, palladium nanoparticles can be effectively immobilized inside these fluorinated ABA-triblock copolymeric nanocomposite cores. Thus, these two different fluorinated copolymers enabled the controlled immobilization of palladium nanoparticles in the fluorinated nanocomposite cores. These fluorinated nanocomposites-immobilized palladium nanoparticles were also applied to the catalysts for Suzuki-Miyaura cross-coupling reaction, and the different reactivity between these nanocomposites was observed.     

活性聚合法合成结构精确的含氟嵌段共聚物

结构精确的含氟嵌段共聚物具有优异而独特的化学和物理性能,有广阔的应用前景,因此受到广泛的关注.含氟嵌段共聚物可分为两类,一类是侧基含氟嵌段共聚物,另一类是主链含氟嵌段共聚物.活性聚合为嵌段共聚物的合成提供了最为重要的方法,利用它可以合成结构精确、分子量可控、分子量分布窄的嵌段共聚物.根据单体的反应特性选择不同的聚合方法,可以得到不同的含氟嵌段共聚物.本文主要综述了近几年利用各种活性聚合方法合成结构精确的含氟嵌段共聚物方面的进展.     

Synthesis and characterization of fluorinated polyurethane with fluorine-containing pendent groups

A novel fluorinated polyurethane （FPU） with fluorine-containing pendent groups was prepared by using fluorinated polyether glycol （PTMG-g-HFP） as a soft segment, 1,6-hexamethylene diisocyanate （HDI） or toluene diisocyanate （TD1） as a hard segment and 1,4-butanodiol （BDO） as a chain extender. FTIR, ^1H NMR, ^13C NMR and GPC were used to characterize the structure of the fluorinated polyurethane. Thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by TGA. XPS analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. The results showed the fluorine enrichment on the surface of FPU.     

核壳型含氟丙烯酸酯共聚物的合成及性能

采用饥饿态半连续种子乳液聚合方法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 分别选用甲基丙烯酸三氟乙酯(TFEM)、甲基丙烯酸六氟正丁酯(HFBM)和甲基丙烯酸十二氟庚酯(DFHM)为含氟单体, 合成以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)和含氟单体为原料的核壳型结构含氟丙烯酸酯共聚物乳液. FTIR, 1H NMR, TEM和DSC分析结果显示, 获得了BA/MMA/含氟单体的共聚物乳液, 且乳液具有明显的核壳结构. DSC, TGA和SEM-EDX的分析显示, 核壳型结构的共聚物具有优异的热力学稳定性能和成膜性能; 长侧链或短侧链含氟单体对共聚物的热稳定性影响不明显, 但侧链较长的含氟单体所获得的聚合物在成膜过程中更易向表面迁移, 更能体现含氟聚合物的优点.     

Effect of substituents in directing the formation of benzochlorins and isobacteriochlorins in porphyrin and chlorin systems

[formula: see text] A first synthesis of free-base fluorinated benzochlorins by acid-catalyzed cyclization of 20-(2-trisiloxy-trifluoromethylvinyl)octaethylporphyrin++ + is achieved. Under similar reaction conditions, the purpurin-18-N-hexylimide analogues produced the corresponding fluorinated and nonfluorinated ethylidene-substituted isobacteriochlorins and fluorinated chlorin, respectively. The structure of the porphyrin based fluorinated benzochlorin was also confirmed by X-ray analysis.     

Architecture of linear arrays of fluorinated co-oligomeric nanocomposite-encapsulated gold nanoparticles: a new approach to the development of gold nanoparticles possessing an extremely red-shifted absorption characteristic

Fluoroalkyl end-capped co-oligomeric nanoparticles, which were prepared by the reaction of fluoroalkanoyl peroxide with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and 1-hydroxy-5-adamantylacrylate (Ad-HAc), were applied to the preparation of novel fluorinated co-oligomeric nanocomposite-encapsulated gold nanoparticles. These fluorinated gold nanocomposites were easily prepared by the reductions of gold ions with poly(methylhydrosiloxane) (PMHS) in the presence of the corresponding fluorinated nanoparticles and tri -n-octylamine (TOA) in 1,2-dichloroethane (DE) at room temperature. These fluorinated gold nanoparticles were isolated as wine-red powders and were found to exhibit good dispersibility in a variety of traditional organic solvents such as DE, methanol, and t-butyl alcohol to afford transparent wine-red solutions. The morphology and stability of these fluorinated co-oligomeic nanocomposite-encapsulated gold nanoparticles were characterized using transmission electron microscopy (TEM), dynamic light scattering measurements (DLS), and UV-vis spectroscopy. DLS measurements and UV-vis spectroscopy showed that these particles are nanometer-size-controlled very fine nanoparticles (185-218 nm) that exhibit a plasmon absorption band at around 530 nm. TEM images also showed that gold nanoparticles are tightly encapsulated into fluorinated co-oligomeric nanoparticle cores. Interestingly, these fluorinated co-oligomeric nanocomposites-encapsulated gold nanoparticles were found to afford linear arrays of these fluorinated nanoparticles with increases in the feed amounts of TOA. More interestingly, these fluorinated gold nanoparticles were able to afford the extremely red-shifted plasmon absorption band at around 960 nm.     

Preparation and applications of novel fluoroalkyl end-capped oligomers/calcium carbonate nanocomposites

Calcium chloride reacted with sodium carbonate in the presence of a variety of self-assembled molecular aggregates formed by fluoroalkyl end-capped acrylic acid, 2-methacryloyloxyethane sulfonic acid, dimethylacrylamide, and acryloylmorpholine oligomers in aqueous solutions to afford the corresponding fluorinated oligomers/calcium carbonate composites in excellent to moderate isolated yields. These fluorinated calcium carbonate composites thus obtained were shown to have a good dispersibility not only in water but also in traditional organic media including fluorinated solvents. Dynamic light scattering measurements (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that these fluorinated composites are nanometer-size-controlled particles and well dispersed in these media. Cross-linked fluoroalkyl end-capped acrylic acid co-oligomer containing poly(oxyethylene) units was also applied to the preparation of new cross-linked fluorinated calcium carbonate nanocomposites under similar conditions. The obtained cross-linked fluorinated calcium carbonate nanocomposites were found to have an extremely higher dispersibility in aqueous and organic media including fluorinated solvents, compared to that of the corresponding fluoroalkyl end-capped oligomer nanocomposites. In particular, it was verified that these fluorinated calcium carbonate nanocomposites are applicable to the dispersion above poly(methyl methacrylate) (PMMA) film surface. Interestingly, field-emission SEM (FE-SEM) images of the cross-section of the modified PMMA films showed that calcium carbonate particles dispersed into these PMMA films could be arranged regularly above the modified film surface. More interestingly, cross-linked fluorinated oligomeric aggregates were able to provide suitable host moieties for the crystallization of calcium carbonate.     

Interfaces with Fluorinated Amphiphiles: Superstructures and Microfluidics

This Minireview discusses recent developments in research on the interfacial phenomena of fluorinated amphiphiles, with a focus on applications that exploit the unique and manifold interfacial properties associated with these amphiphiles. Most notably, fluorinated amphiphiles form stable aggregates with often distinctly different morphologies compared to their nonfluorinated counterparts. Consequently, fluorinated surfactants have found wide use in high-performance applications such as microfluidic-assisted screening. Additionally, their fluorine-specific behaviour at solid/liquid interfaces, such as the formation of superhydrophobic coatings after deposition on surfaces, will be discussed. As fluorinated surfactants and perfluorinated materials in general pose potential environmental threats, recent developments in their remediation based on their adsorption onto fluorinated surfaces will be evaluated.