全氟羧酸单体合成的研究进展

全氟羧酸单体是合成全氟离子交换膜的重要单体。本文介绍了国内外全氟羧酸单体（全氟烷基乙烯基醚）的多种合成技术及进展,并对各条合成路线进行了分析,同时国内的研究也有很大的进展。     

全氟羧酸的制备方法

全氟羧酸是一类用途较广的含氟化合物,可用作表面活性剂、憎水憎油剂,以及合成氟聚物的中间体。其主要工业合成方法是电化学氟化法,即电化氟化辛酰氯制备全氟     

氟化工专利精选

含氟羧酸酯的制造方法 提供了1种从含氟醚通过一步反应可得到目标的含氟羧酸酯，不需要复杂的工序和繁杂的操作．而且无需消耗过量的能源的制造方法。将通式R1 HCFCF2OR2（其中，R1表示氟原子和碳原子数1-4的全氟烷基中的任意1个，     

全氟甲基乙烯基醚合成的研究进展

目前,全氟甲基乙烯基醚作为一种重要的含氟单体,在新型的氟塑料和氟橡胶合成中具有广泛的应用价值。本文对近年来发表的文献和专利进行了总结,将现有的合成全氟甲基乙烯基醚方法分析归纳为：四氟乙烯法、热解法、还原法和六氟环氧丙烷法。通过对上述4种合成方法地详细介绍,较全面地综述了全氟甲基乙烯基醚4种合成方法的研究进展,并讨论分析了不同的合成方法在工业应用上的利弊,认为改进提高新的实验室合成技术是今后实现全氟甲基乙烯基醚大规模工业化应用的一个主要途径。     

五氟丙酰氟的制备及应用

综述了以六氟环氧丙烷及其低聚物、三氟甲基三氟乙烯基醚、全氟丙酸全氟丙酯及丙酸丙酯、丙酸酐为原料制备五氟丙酰氟的方法及其优缺点,概述了五氟丙酰氟下游含氟精细化学品的的应用前景,为五氟丙酰氟的制备及应用提供参考。     

氧杂全氟羧酸双季戊四醇酯的制备

研究了一种新型含氟表面活性剂氧杂全氟羧酸双季戊四醇酯的合成方法。以六氟环氧丙烷齐聚体混合物和双季戊四醇为原料,在缚酸剂存在下,有机溶剂中进行酯化反应,得到氧杂全氟羧酸双季戊四醇酯。经红外光谱(FT-IR)和质谱(ESI-MS)表征了产物分子结构,优化了酯化反应工艺条件:n[(HFPO)n]∶n(双季戊四醇)=2∶1,DMF为溶剂,三乙胺为缚酸剂,在80℃下反应5 h,收率可达86.9%。     

含氟聚合物及其涂料

201305007具有优异耐候性的太阳能电池背板用核壳结构含氟聚合物涂料：KR2012-103856[韩国专利公开]／韩国Korea Research Institute of Chemical Technology（Lee．Su Bok等）.-2012.09.20.-11页.-21 756（2011.03.11）：IPC C08FI4／18 题述含氟聚合物包含（A）含氟聚合物组成的核和（B）氟乙烯基醚（CFz：CFOCFzCF。艮）组成的壳，其中Rf为C1-3，的全氟烷基或全氟烷氧基。例如，将蒸汽压为300psi的偏二氟乙烯在6.3mL 20％的全氟辛酸铵水溶液、1.0mL氯仿及620mL水的混合液中，于80℃下加热。     

气相色谱-质谱联用定性全氟羧酸丁基酯

全氟羧酸化合物(PFCAs)作为全氟化合物(PFCs)其中的一种,具有了全部持久性有机污染物的特点:半挥发性、半衰期长、难降解、生物富集、较强毒性等。本实验应用离子对试剂四丁基硫酸氢铵(TBAHS),对PFC6A-PFC12A等七种全氟羧酸化合物进行离子对萃取,以及气相色谱进样口的衍生,在EI+全扫描的条件下对衍生产物进行了定性分析。结果表明:[C4H9]+m/z=57,[CF3]+m/z=69,[C2F4]+m/z=100,[C2F5]+m/z=119,[C3F5]+m/z=131,[C3F7]+m/z=169,[C4F7]+m/z=181,这几种碎片为所有全氟羧酸丁基酯的共有碎片,可对全氟羧酸丁基酯进行简单快捷的定性。     

全氟二元酰氟的合成

全氟二元酰氟是合成含氟聚酯，聚酰胺及带二个不同官能团单体的重要化合物。以通式FOC（CF2）nCOF为原料来合成高性能功能含氟高分子材料是当今材料科学研究课题之一。已合成了全氟羧酸型离子交换树脂，全氟醚橡胶等。而对新的带功能团的共聚单体及其共聚物的开发正方兴未艾。因此对该化合物的合成方法一直受到人们的关注。通式中n数的奇偶取决于合成方法。相对而言，n为偶数的二元酰氟合成较易。文介绍以四氟乙烯为原料，n为偶数的二元酰氟的合成方法。1碘化物法该法是碘经光照或加热形成自由基，再与四氟乙烯发生加成反应生成二碘四氟…     

氟树脂性能与加工应用 (续 8)

介绍了全氟代烷基乙烯基醚的物性和合成方法;叙述了四氟乙烯与全氟代烷基乙烯基醚共聚物非水溶液、水溶液聚合工艺。介绍了乙烯-四氟乙烯共聚物的聚合方法。     

A New Route to Perfluoro(Propyl Vinyl Ether) Monomer: Synthesis of Perfluoro(2‐propoxypropionyl) Fluoride from Non‐Fluorinated Compounds

Perfluoro(2‐propoxypropionyl) fluoride ( 1a ), which is the precursor of the perfluorinated propyl vinyl ether (PPVE) monomer of an industrially important perfluoroalkoxy copolymer (PFA), was synthesized by utilizing direct fluorination of the non‐fluorinated counterpart for the first time. The partially‐fluorinated ester 7 synthesized from the desired perfluorinated acid fluoride 1a itself and the non‐fluorinated alcohol 5 , which has a carbon skeleton corresponding to the desired compound 1a , was perfluorinated by liquid‐phase direct fluorination with elemental fluorine. Degradation of the resulting perfluorinated ester 8 gave 2 mols of the desired acid fluoride 1a . In a sense, this process can be called self‐multiplication of a perfluorinated acid fluoride from a non‐fluorinated alcohol.     

Polymeric systems for acoustic damping. III. Blends of poly(vinyl chloride), segmented poly(ether ester), and poly(methyl acrylate)

A solution blend of poly(vinyl chloride) and a segmented poly(ether ester) and blends containing these two polymers plus poly(methyl acrylate) were investigated by dynamic mechanical analysis and electron microscopy. The binary blend, which contained 75% by weight of the poly(ether ester), showed only one loss peak, but also evidence of some phase separation. It is believed that the polyether sequences of the poly(ether ester) are extensively mixed with poly(vinyl chloride). Poly(methyl acrylate) was added to spread the damping range and produce a material of potential use as an acoustic damper. It is evident from both electron microscopy and dynamic mechanical analysis that poly(methyl acrylate) is substantially incompatible in the other polymers.     

1-（1-乙氧基）-1H-吡唑-4-硼酸频哪醇酯的合成方法

用乙烯基乙醚保护吡唑氨基,制成格式试剂后与异丙醇硼酸频哪醇酯反应制得1-1-乙氧基）-1H-吡唑-4-硼酸频哪醇酯。     

Preparation of ester terminated poly(alkyl vinyl ether) oligomers and block copolymers using a combination of living cationic and group transfer polymerization

Summary This paper reports the synthesis and characterization of new, functionalized poly(alkyl vinyl ether) oligomers, and block copolymers containing poly(alkyl vinyl ether) and poly(methyl methacrylate). Using the HI/ZnI₂ initiating system in nonpolar solvents (hexane, toluene) at -15 °C, both monofunctional and difunctional poly(alkyl vinyl ether) oligomers of predicted molecular weights precisely terminated with ester end groups have been prepared. Novel diblock copolymers comprised of poly(methyl methacrylate) and poly(alkyl vinyl ether) have also been synthesized using a combination of living cationic and living group transfer polymerization (GTP) techniques.     

An investigation of vinyl–ester?styrene bulk copolymerization cure kinetics using Fourier transform infrared spectroscopy

A Fourier transform infrared (FTIR) spectroscopy technique was developed to investigate the effects of reaction temperature and reactant composition on the isothermal curing kinetics of commercial vinyl nester resins comprised of vinyl–ester monomer (dimethacrylate of diglycidyl ether of bisphenol A DGEBA) and styrene. This technique enables a more complete evaluation of the bulk copolymerization reaction of vinyl–ester styrene systems by monitoring the depletion of vinyl–ester and styrene double bonds independently. The results indicate that the rate of fractional conversion of styrene double bonds is initially less than that of vinyl–ester vinyl groups. However, styrene monomer continues to react after conversion of vinyl–ester double bonds has ceased. In addition, the overall extent of conversion was found to increase with increasing isothermal cure temperature, and it was observed that higher styrene concentration enhances final conversion of vinyl–ester double bonds and not styrene double bonds. Increasing styrene monomer concentration also resulted in lowering the apparent activation energy for the reaction of vinyl groups from both monomers as characterized by an empirical autocatalytic model used to fit the conversion results for styrene and vinyl–ester double bonds independently. The results of this work demonstrate that reaction temperature and resin composition significantly affect the cure behavior of vinyl–ester resins and provide insight into the development of the resulting network structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1572–1582, 2000     

Enhanced interfacial adhesion of carbon fibers to vinyl ester resin using poly(arylene ether phosphine oxide) coatings as adhesion promoters

Poly(arylene ether phosphine oxide)s (PEPO) were prepared and utilized to coat carbon fibers to enhance the interfacial adhesion with vinyl ester resins. For comparison, poly(arylene ether sulfone) (PES), Udel^® P-1700, and Ultem^® 1000 were also used. The interfacial shear strength (IFSS) of thermoplastic polymer-coated fibers was measured via microbond pull-out tests. The interfacial adhesion between thermoplastics and as-received carbon fibers was also measured in order to investigate the adhesion mechanism. Thermoplastic polymer-coated fibers exhibited a higher IFSS than the as-received fibers with vinyl ester resin, and with thermoplastic polymers. PEPO-coated fibers showed the highest IFSS, followed by Udel^®, PES, and Ultem^®-coated fibers. The high IFSS obtained with PEPO coating could be attributed to the phosphine oxide moiety, which provided a strong interaction with functional groups in the vinyl ester resin and also on carbon fibers. A diffusion study revealed the formation of a clear interphase not only between PEPO and the vinyl ester resin, but also between Udel^® (PES or Ultem^®) and the vinyl ester resin, although the morphology of the two interphases differed greatly.     

Effect of solubility and miscibility on the adhesion behavior of polymer‐coated carbon fibers with vinyl ester resins

Interfacial shear strength (IFSS) of carbon fibers with vinyl ester resin was investigated as a function of the structure of the polymer coating on carbon fibers via microdroplet tests. For coating carbon fibers, high‐performance polymers such as poly(arylene ether phosphine oxide) (PEPO), Udel® P‐1700, and Ultem® 1000, water‐soluble poly(hydroxy ether ethanol amine) (PHEA), water‐dispersed carboxy‐modified poly(hydroxy ether) (C‐PHE), and water‐insoluble poly(hydroxy ether) (PHE) were utilized. Adhesion of polymers to carbon fibers was also evaluated and the failure surface of the fibers was analyzed by SEM to understand the adhesion mechanism. Diffusion between polymers and vinyl ester resins was investigated and the solubility parameters of the polymers were calculated, with the results being correlated to the IFSS. A highly enhanced IFSS was obtained with PEPO coating, while marginally improved IFSS resulted from PHE, Udel®, and C‐PHE coatings. However, PHEA and Ultem® coatings showed no improvement. Such results were attributed to the extent of solubility and/or miscibility of polymer coatings in vinyl ester resin, with better solubility and miscibility leading to a higher IFSS. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1042–1053, 2001     

Use of allyl‐functional benzoxazine monomers as replacement for styrene in vinyl ester resins

New vinyl ester systems are prepared using allyl‐functional benzoxazine monomers, 3‐allyl‐6‐methyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazine (pC‐ala) or bis(3‐allyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazin‐6‐yl)methane (BF‐ala), as reactive diluents for vinyl ester resins derived from an epoxy resin, diglycidyl ether of bisphenol A, instead of using styrene. Different initiators are used to investigate the copolymerization of allyl function from pC‐ala with vinyl function from vinyl ester resin prepolymer. The temperature dependence of viscosity is studied to demonstrate the retention of processability of the new vinyl ester resins. Dynamic mechanical and thermogravimetric analyses are used to investigate the dynamic mechanical properties and thermal stability of the new resins. Copyright © 2012 Society of Chemical Industry     

Vinyl ester resins, 3. Effect of ethyl methacrylate on thermal and mechanical properties

This paper describes the effect of ethyl methacrylate (EMA) on the thermal and mechanical properties of glass fibre-reinforced laminates of vinyl ester resins derived from diglycidyl ether of bisphenol-A and methacrylic acid. The thermal stability and the curing characteristic of the resins were investigated by thermogravimetric analysis and differential scanning calorimetry. The glass transition temperature of the laminates decreased with increase in EMA content. Dilution of vinyl ester resin with EMA resulted in a decrease in flexural strength and flexural modulus of the laminates.