高憎水性含氟丙烯酸树脂及其涂料的制备

以甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸羟乙酯以及两种不同氟链段长度的丙烯酸酯单体,先通过自由基聚合,再用一种氟碳改性剂对其进行化学改性,制得了一种高憎水性的含氟丙烯酸树脂。利用红外光谱、接触角仪、原子力显微镜、X射线光电子能谱仪等对树脂和涂层性能进行了表征。研究表明:氟碳改性剂的加入可明显降低涂层表面能,增大涂层接触角,但当加入量大于1.8%时,继续增加氟碳改性剂用量对接触角影响不大。     

含氟硅丙烯酸酯核壳乳液及涂膜表面性能

在可聚合阴离子乳化剂体系下,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主要单体,甲基丙烯酸十二氟庚酯(DFMA)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为功能单体,采用半连续种子乳液聚合法合成了含氟硅丙烯酸酯核壳乳液。考察了DFMA和KH-570用量对乳液聚合过程和乳胶膜表面疏水性能的影响,并对乳胶膜的表面自由能进行了估算。采用傅里叶红外光谱(FT-IR)、差示扫描量热仪(DSC)、热重(TG)、接触角(CA)及X射线光电子能谱(XPS)对氟硅丙乳液及乳胶膜进行了表征。研究结果表明,氟硅单体有效地参与了聚合,乳胶膜中氟硅元素呈梯度分布,当氟硅丙乳液中DFMA和KH-570用量分别为16%和5%（质量分数）时,涂膜-空气界面与去离子水的接触角为110.6°,涂膜的表面能低至15.4 mN·m^-1,其疏水性和耐热性有较大幅度提高。     

Coating performance and characteristics for UV-curable aliphatic urethane acrylate coatings containing norrish type I photoinitiators

The purpose of this study was to investigate the influence of several Norrish I (α-cleavage) type photoinitiators and UV dose on the curing behavior and coating performance of UV-curable aliphatic urethane acrylate coatings. UV-curable coatings were cured under a high-pressure mercury lamp. The curing behavior and coating performance of the UV-curable coatings that were cured using 2-hydroxy-2-methyl-1-phenyl-propan-1-one or 1-hydroxy-cyclohexyl-phenyl-ketone were superior to those of the UV-curable coatings cured using bis (2,4,6-trimethylben-zoyl)-phenylphosphine oxide or diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide, when the UV-curable coating was cured in air. Current address: Electronic Chemical Materials R&D Center, CHEIL Industries Inc.     

Modification of Epoxy Resin with a Phosphorus,Nitrogen, and Fluorine Containing Polymer to Improve the Flame Retardant and Hydrophobic Properties

Targeting high‐effective modification of flame retardant epoxy resin, elements including phosphorus, nitrogen, and fluorine are simultaneously incorporated into a polymer named as PFNP. A certain amount of amino groups are preserved on PFNP chains to participate in the curing of epoxy resin. The reactive groups and segments contain 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) endowed PFNP with good compatibility in epoxy resin. The proper addition of PFNP improves the mechanical property and T_g values of epoxy resins. The limiting oxygen index values of EP/PFNP increases while the peak heat release rate, heat release capacity, and total heat release values reduce after introduction of PFNP. Samples with contents of PFNP higher than 5 wt% reach UL‐94 V‐0 rating without dripping. Notably, the migration effect of trifluoromethyl (CF₃) groups not only increases the water contact angles, but also reduces the dielectric constants of epoxy resins.     

Preparation and surface properties of core‐shell polyacrylate latex containing fluorine and silicon in the shell

The core‐shell polyacrylate latex particles containing fluorine and silicon in the shell were successfully synthesized by a seed emulsion polymerization, using methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, dodecafluoroheptyl methacrylate (DFMA), and γ‐(methacryloxy) propyltrimethoxy silane (KH‐570) as functional monomers. The influence of the amount of fluorine and silicon monomers on the emulsion polymerization process and the surface properties of the latex films were discussed, and the surface free energy of latex films were estimated using two different theoretical models. The emulsion and its films were characterized by particle size distribution (PSD) analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹⁹F‐NMR) spectrometry, contact angle (CA) and X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. The results indicate that the average particle size of the latex particles is about 160 nm and the PSD is narrow, the synthesized latex particles exist with core‐shell structure, and a gradient distribution of fluorine and silicon exist in the latex films. In addition, both the hydrophobicity and thermal stability of the latex films are greatly improved because of the enrichment of fluorine and silicon at the film‐air interface, and the surface free energy is as low as 15.4 mN/m, which is comparable to that of polytetrafluoroethylene (PTFE). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Blocked polyisocyanates containing fluorine atoms as crosslinking agents for polyurethane powder coatings

Using alicyclic diisocyanates (HDI, TMDI, IPDI, H₁₂MDI), aliphatic unfluorinated and fluorinated alcohols, dibutyltin dilaurate as well as triethylamine as catalysts, blocked polyisocyanate crosslinkers for powder lacquers were synthesized. The chemical structure of these compounds was characterized by means of IR, ¹H‐NMR, ¹³C‐NMR, and ¹⁹F‐NMR spectroscopy. Their molecular weight distribution parameters were determined by gel permeation chromatography. These blocked polyisocyanates were used for the production of powder lacquer compositions and coatings. The three‐dimensional surface topography and surface chemical structure of the resulting powder lacquers were investigated by means of confocal microscope and ATR FT‐IR. The values of surface roughness parameters were calculated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

船舶用低表面能防污涂料的性能研究

以一种有机硅弹性体作基料,制备了低表面能船舶防污涂料,研究了该涂料在不同温度条件下的复涂间隔、与环氧树脂涂料的配套性和防污性能。结果表明,有机硅弹性体漆与环氧防锈漆之间的复涂间隔非常窄,在环氧底漆上喷涂有机硅弹性体时必须严格控制复涂时间;有机硅弹性体漆在高温高湿下,可更好的快速固化;该涂料可以有效防止海洋生物的生长繁殖,且不释放任何重金属有害物质。     

Conducting fluorine doped tin dioxide (FTO) coatings by ultrasonic spray pyrolysis for heating applications

Fluorine doped tin dioxide (FTO) coatings were deposited on AISI 304 stainless steel (SS) substrates using ultrasonic spray pyrolysis (USP) technique. Four different candidate insulating intermediate layers of TiO₂, MgO, Al₂O₃ and SiO₂ were selected and coated on AISI 304 SS using USP and investigated in order to overcome dielectric breakdown of FTO layer due to conductive nature of stainless steel substrate under the applied voltage. After the optimization of the process parameters for the depositions, only TiO₂ layer was successfully deposited while other oxides did not form continuous films on AISI-304 SS surface despite the efforts. SEM analysis, supported by back-scatter imaging, revealed thickness values of the layers for FTO and TiO₂, individually. Heating performances of the samples with varying sheet resistance values were examined under different applied voltages. Heating experiments showed that 300 °C can be reached with 10 V of applied voltage without occurrence of an electrical breakdown of FTO coating having 160 nm thickness with TiO₂ intermediate layer of 660 nm. 28.6% efficiency for the conversion of electrical energy into heat was calculated for FTO coating while bare stainless steel showed only 7.3% efficiency. Later, the heating experiments were repetitively conducted and the samples were tested under high relative humid environment to determine their resistance against moist conditions.     

Fluorinated polyacrylates containing amino side chains for the surface modification of waterborne epoxy resin

Fluorinated polyacrylates containing amino side chains (FACAs) were synthesized to improve the water repellency of waterborne epoxy resin. First, FACA was prepared by a two-step process. Then, a phase-inversion emulsion technique, taking FACA as the reactive surface additives, was employed to prepare waterborne epoxy resin. The effect of the fluorinated content and the length of the fluorine side chain on the surface, thermal, and bulk properties of the waterborne epoxy resin were investigated. It was observed that moderate increase of the fluorinated content or the length of the fluorine side chain improved the contact angle and thermal properties while the mechanical property was not deteriorated. A small amount of fluoride (0.07 wt %) in the EA-F1/3-1 sample can dramatically increase the water contact angle from 72.63° to 95.31° due to the strong tendency of the macromonomers to migrate toward the outmost layer, resulting in enrichment of fluorine atoms on the surface. X-ray photoelectron spectroscopy results revealed that for a given weight of the two macromonomers, F atomic concentration of the copolymer modified by longer fluorinated side chains was higher than that modified by short fluorinated side chains. From the present investigation, FACA successfully improved the surface property of waterborne epoxy resin and showed a prominent potential application in large-scale industrialization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47091.     

低表面能涂层在飞机防除冰领域的研究进展与应用

阐述了飞机防除冰的重要性及通常采用的防除冰方法,简要介绍了疏水型低表面能涂层在飞机防除冰领域的辅助作用及该类涂层的疏水机理和分类,评述了几类含氟低表面能树脂在疏水涂料领域的研究进展以及该类涂层在飞机蒙皮和防除冰领域的应用。     

A novel fluorinated polymeric product for photoreversibly switchable hydrophobic surface

A new chemical product, that is, photoreversibly switchable hydrophobic surface coating, was synthesized by atom transfer radical polymerization and graft‐from method based on molecular design. Focusing on the strategy of new product development from the chemical product engineering perspective, the product characterization, switching mechanism analysis, performance evaluation, and model interpretation were carried out to confirm the new product manufacture and to ensure the product application with a following aging test. The results show that the product enables surfaces to have reversibly switchable wettability and excellent stability after a month‐long test with eight irradiation cycles. Additionally, the wetting behavior of silicon surface can be tuned between hydrophilicity and hydrophobicity based on blank sample using the surface engineering technique (decorated with functional film and surface roughening). The product presented here can be utilized for constructing a hydrophobic surface with photo‐induced controllable wettability in moisture‐resistance, and it also offers a new technique for the manipulation of liquids in microfluidic devices. © 2014 American Institute of Chemical Engineers AIChE J 60: 4211–4221, 2014     

一种粘接性能优异的含氟聚合物粘合剂

研究以一种含氟聚合物为主体材料制备用于聚四氯乙烯粘接的粘合剂,探讨了固化剂和金属氧化物对该粘合剂粘接性能的影响,分析了表面改性剂的改性作用,并考察了用于不锈钢粘接的情况。     

氟碳驱菌涂料用于斜板(管)沉淀池中的实验研究

论证了氟碳材料在斜板（管）沉淀池当中应用的可行性，将氟碳涂料涂到斜板（管）上，利用氟碳涂料具有很低的表面能而对细菌具有驱赶作用，来解决斜板（管）沉淀池中由于结生物膜而带来的问题；提出可以将氟碳材料加入到斜板（管）的制作材料当中，来减小微生物对斜板（管）的附着作用。并在污水处理系统的曝气池中进行了挂板实验，实验证明生活污水处理可以用涂氟碳材料的斜板（管）沉淀池，以提高斜板（管）沉淀池的效率。     

Vapor‐based polymer coatings for potential biomedical applications

Over the last decade, biology and biotechnology have witnessed an extraordinary development spanning genomics, proteomics, and metabolics. This progress was so rapid and definite that it not only changed the face of modern biology, but indeed altered the way day‐to‐day business is done in biology and related fields. This scientific advancement came with a need for concurrent technological advances. In this context, the ability to interface sophisticated devices with relevant biological microenvironments has emerged as a critical challenge. Already, novel biomaterials are on the horizon that promise to fulfill the rigid criteria of being both biocompatible under the conditions of a versatile range of biological applications and compatible with the increasing demands for miniaturization, integration, and throughput of future device architectures. As currently employed solvent‐based polymer coatings are increasingly reaching their limits, a range of unconventional materials, such as vapor‐based polymer coatings, are discussed as attractive alternatives. One of the main features of vapor‐based polyreactions is their versatility in synthesizing both simple and complex polymers with relative ease and at generally low temperatures. The advantages of the chemical vapor deposition (CVD) technique also include control of the composition and architecture of the resulting materials, high accuracy, solvent‐free environments, excellent adhesion, and the ability to accommodate custom‐tailored surface modifications. For further illustration, selected examples of polymer‐based surface engineering approaches using vapor‐based polyreactions are discussed in this review. For instance, reactive coating technology uses CVD polymerization to deposit a wide range of chemically functionalized polymer coatings on various substrate materials. Its simplicity in providing chemically reactive groups and its applicability to three‐dimensional geometries (e.g. for microfluidics) enables exact tailoring of surface properties and the preparation of biologically relevant microenvironments. CVD‐based reactive coatings are compatible with soft lithographic processes allowing for patterning of proteins, DNA, cytokines, and mammalian cells. Copyright © 2006 Society of Chemical Industry     

New method for preparation of hydrophobic interaction chromatographic stationary phases based on polymer-grafted silica and their chromatographic properties

A new “grafting to” method for the preparation of polymer-grafted silica hydrophobic interaction (HIC) packings was used in following steps. Firstly, 3-mercaptopropyltrimethoxysilane was bonded on silica to obtain SH-group modified silica. Secondly, glycidylmethacrylate (GMA) was coated on the surface of SH-silica to obtain polymer-grafted epoxide-silica. Finally, the polymer-grafted epoxide-silica was dispersed in polyethylene glycol of dioxane solution to produce HIC stationary phase. The prepared HIC packings have advantages for biopolymer separation, high column efficiency and good resolution for proteins. The dynamic protein loading capacity of the synthesized packings was 36.0 mg/g. Six proteins were fast separated in less than 12.0 minutes using the synthesized HIC stationary phases. Then the stationary phase was evaluated in detail to determine the effects of pH of mobile phase, concentration of ammonium sulfate and the temperature on the retention of proteins. The thermodynamic parameters of these proteins are consistent with the entropically driven nature of hydrophobic interactions, The HIC column was used for purification of trypsin from a crude extract solution with only one step. The purity of the purified trypsin was more than 95%. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Antimicrobial coatings based on hydantoin‐containing polymer networks for textiles

An advanced method with an initiator pretreatment was developed for the coating of nylon/cotton fabrics with the hydantoin‐containing monomer 3‐allyl‐5,5‐dimethylhydantoin and two water‐soluble crosslinkers N,N′‐methylene bisacrylamide and poly(ethylene glycol) 200 diacrylate. The formulations were applied to textiles by either batch coating or dip coating. In the dip‐coating process, the influence of individual parameters on the fabric modification was investigated and evaluated. After treatment with chlorine, the hydantoin structure was transformed into antimicrobial active N‐halamines. The modified fabrics exhibited potent antibacterial properties against Staphylococcus aureus and Escherichia coli. Our method, based on an initiator pretreatment and water‐soluble crosslinkers, outperformed current technologies in the degree of fabric modification. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

有机硅低表面能/自抛光海洋防污涂料的制备

采用接枝共聚的方法,即环氧和丙烯酸反应,环氧开环的同时生成带有羟基的丙烯酸单体,加入引发剂结合另外2种丙烯酸单体,在催化剂的作用下接入有机硅,制得有机硅环氧丙烯酸树脂。讨论了环氧树脂的用量对涂膜性能的影响、涂料的水解特性,并进行了实海挂板实验。结果表明:当环氧的用量为10%时,制备的防污涂料与水的接触角达到133°,附着力1级;有机硅/环氧改性丙烯酸树脂制得的防污涂料在海水中能够稳定地水解,兼具低表面能和自抛光的特性,实海挂板实验结果表明,涂料具有良好的防污性能。     

Synthesis and characterization of novel polyurethanes based on fluorine‐containing polyphosphazene

Fluorine‐containing poly[bis‐(2,2,3,3,4,4,5,5‐octafluoro‐1‐pentanol)_1.6 (4‐hydroxybutaneoxy)_0.4 phosphazene] (OFHBP) was synthesized and characterized by Fourier transform infrared (FTIR) spectra, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The obtained OFHBP was used as a cross‐linker to prepare a series of novel polyurethanes (PUPFs). The composition of the PUPFs was confirmed by FTIR and elemental analysis (EA). The crystalline structure and microstructure of the PUPFs were examined by X‐ray diffraction (XRD) and atomic force microscopy (AFM). The thermal and tensile properties of the PUPFs were characterized by differential scanning calorimetry (DSC) and tensile testing. In addition, the surface energy of the PUPFs was also evaluated by contact angle measurements (CA). The results showed that glass transition temperature of the PUPF‐4 was decreased by 15°C, elongation at break was improved by 61% and a 41% decrease in surface energy in comparison with conventional polyurethane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of prepolyurethane on the performances of poly(acrylates‐co‐urethane) copolymer

Poly(acrylates‐co‐urethane) copolymers were synthesized by the polymerization of acrylates and 2‐hydroxyethyl acrylate terminated polyurethane (prepolyurethane) at room temperature. The polymerization was initiated by the radicals, which were produced by the oxidation of tri‐n‐butylborane (TBB) from the mixing of TBB/hexamethylene diamine complex and diisocyanate decomplexer. The effects of prepolyurethane on the performances of copolymers were discussed. The results indicated that the damping property and flexibility of copolymers were obviously higher than that of pure polyacrylates. Dynamic mechanical analysis and transmission electron microscope results showed that PU was dispersed in polyacrylates phase very well. The copolymers were found to bond well to low surface energy materials because of introduction of PU. The lap shearing strength of copolymer bonding polypropylene or polyethylene both had the trend of first increase followed by decrease with the prepolyurethane content increase. The copolymers as adhesives were also shown to have a long working life and be suitable for utilization at low temperature especially at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

改性有机硅低表面能防污涂料用树脂的合成

综述了改性有机硅防污涂料用树脂的合成原理及主要合成类型，并讨论了新方法新工艺在改性有机硅树脂合成中的应用情况以及今后的研究发展方向。