氟代聚丙烯酸酯无皂乳液整理剂的防水防油性能研究

本文采用无皂乳液聚合法,以全氟烷基酯（FEA）为功能单体,制备了一种氟代聚丙烯酸酯无皂乳液整理剂,并对其乳液颗粒粒径大小及分布和高分子溶液表面活性进行了研究。通过对棉织物进行防水防油整理应用实验,详细考察了该织物整理剂的使用质量百分数和烘焙温度对防水防油性能的影响,并测试了其他应用性能。结果表明,通过该防水防油剂处理的织物有优异的防水防油性能,处理后的织物表面动态防水性可达90分,防油性可达5级,对水的接触角可达142.5°,对石蜡油的接触角可达126?,并且有良好的耐水洗性和常规应用性能。     

Improved shale hydration inhibition with combination of gelatin and KCl or EPTAC,an environmentally friendly inhibitor for water-based drilling fluids

An effective and environmentally friendly shale hydration inhibitor is essential to develop high-performance water-based drilling fluid with good environmental properties. For this purpose, and to minimize shale hydration under satisfactory environmental profit, composites of gelatin and inorganic salt (KCl) or organic salt (2, 3-epoxypropyl-trimethylammonium chloride, EPTAC) were prepared as environmentally friendly shale inhibitors to perfect the inhibitive effect. The inhibitive properties of the composites were evaluated by comparison with pure gelatin and common inhibitors. Results suggested that when 2.0 wt % gelatin and 1.0 wt % salt were combined, the composites reduced the swelling height of montmorillonite (Mt) to <1.70 mm, improved shale recovery to 80% at 150 °C and inhibited 16.0 wt % Mt mud-making, thereby displaying excellent inhibition performance. Moreover, the gelatin composite with EPTAC seemed to perform better synergistic inhibition than that with KCl. The underlying inhibitive mechanisms were also investigated by measuring interlayer space through X-ray diffraction, observing aggregation through electron microscopy, comparing hydrophobic modification degree by water contact angle measurement, and determining the zeta potential and water activity. The gelatin composites presented lower water activity and effectively prevented water from invading Mt. In these composites, gelatin mainly adsorbed on the surface of Mt particles, encapsulated Mt particles, and improved their hydrophobic property to a certain degree, whereas the salts entered the interlayer, expelled water, and decreased the interlayer space. Consequently, the combinations of gelatin and KCl or EPTAC had an excellent effect on inhibiting shale hydration. This study can also provide new insights into the design of totally environmentally friendly additives for water-based drilling fluid. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47585.     

Synthesis of photo-crosslinked hybrid fluoropolymer and its application as releasing coating for silicone pressure-sensitive adhesives

In this study, a novel photo-crosslinked polymer composite was made from NCO-terminated fluoropolymers by the incorporation of functionalized graphene through the in situ polymerization method. This polymer composite can be photoinduced to form a network under UV radiation without photoinitiators, displaying an excellent transmittance (T% > 90% at 550 nm), a high thermostability with a glass transition temperature (T _g < −15 °C), and a 10% weight loss temperature (410 °C). With UV radiation, the hybrid coating exhibited a controlled releasing force between 100 and 500 g/25 mm for silicone PSAs, which was an important breakthrough in the heavy-releasing industry. Their aging releasing performance and residual adhesion force were satisfactory. More importantly, antistatic agents are not needed any more before the coating of this novel releasing agent. In addition, the coating possessed good hydrophobicity with a contact angle of 110° and great resistance to solvents. These metrics indicate that incorporating functionalized graphene as curable points into composites can greatly improve the performance of fluoropolymer properties. The obtained polymers have potential applications in the releasing and protective industry. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48322.     

Robust,fluorine-free and superhydrophobic composite melamine sponge modified with dual silanized SiO_2 microspheres for oil–water separation

Massive oily wastewater discharged from industrial production and human daily life have been an urgent environmental and ecological challenge. Superhydrophobic materials have attracted tremendous attention due to their unique properties and potential applications in the treatment of wastewater. In this study, a novel superhydrophobic/superoleophilic composite melamine sponge modified with dual silanized Si O_2 microspheres was fabricated simply by a two-step sol–gel method using vinyltriethoxysilane and hexadecyltrimethoxysilane as functional agent, which exhibited a water contact angle of 153.2° and a water sliding contact angle of 4.8°. Furthermore, the composite sponge showed the excellent oil adsorption performance and the compressive elasticity reaching up to 130 g·g~(-1) of dichloromethane and 33.1 k Pa of compressive stress. It was worth noting that the composite sponge presented the excellent separation efficiency(up to 99.5%) in the processes of continuous oil/water separation. The robust superhydrophobic composite melamine sponge provided the possibility with the practical application for oil–water separation.     

Preparation of hydrophilic woven fabrics: Surface modification of poly(ethylene terephthalate) by grafting of poly(vinyl alcohol) and poly(vinyl alcohol)-g-(N-vinyl-2-pyrrolidone)

One of the most industrially important synthetic textile materials, woven poly(ethylene terephthalate) (PET) fabrics, have limitations in the usage of casual apparel applications due to their unwanted hydrophobicity. For that reason, in this study, to impart permanent hydrophilicity to the PET fabrics, hydrophilic poly(vinyl alcohol) (PVA) and a PVA-based copolymer were introduced to the alkaline hydrolysis pretreated PET surface by graft copolymerization for the first time. The graft modification of PET fabric surface was performed with an industrial-adaptable approach. The synthesis of a novel PVA-g-(N-vinyl-2-pyrrolidone) copolymer was achieved by the introduction of glycidyl methacrylate monomer to the PVA backbone. The structure of the copolymer was evidenced by attenuated total reflection–Fourier transform infrared spectroscopy and ¹H-NMR techniques. The introduction of PVA and copolymer structures with desired functional groups to the PET fabric surface was confirmed with the X-ray photoelectron spectroscopy technique. It was obtained that the contact angle–wetting time of PET fabric (145° and 98 s) could be dropped to 37° and 0.1 s and 64° and 0.7 s after PVA and copolymer grafting, respectively. This suggests that the graft-modified PET fabrics may find the potential of use in the textile applications as the alternative hydrophilic materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48584.     

Optimization of amphiphobic structural surface thickness in relation to its functionality on stainless steel plates

Fluorine‐based amphiphobic coatings have been widely used in commercial textiles to provide water‐ and oil‐repelling abilities. However, few reports from the literature survey have discussed the surface structural effects of the coated substrate on amphiphobicity. In this research, various thickness amphiphobic coatings based on mixed epoxy, tetraethylorthosilicate, and a particular alkoxysilane with fluorinated side chains (F‐silane) were deposited on Grade 420 stainless steel plates. Film amphiphobicity is characterized by measuring the water and oil contact angles of the coating. Film morphology is examined using atomic force microscopy. The deposited films free of F‐silane are thinner than 150 nm. The films become thick at high F‐silane volume percentage with the surface cavities, ridges, and granules being masked out. On the addition of F‐silane, the water contact angle of the deposited films increases up to 105° and then reaches a plateau of ～ 107° with increasing F‐silane. In contrast, the oil contact angle increases up to 60° at first and then slowly declines with the F‐silane concentration. The total drop of oil contact angle by ～ 20° was attributed to the masking out of surface features on film thickening. This indicates that the surface oleophobicity depends on surface structures. Therefore, improving surface amphiphobicity correlates with creating more refined multiscale surface structures during the industrial manufacturing process of steel plate, prior to surface modification by F‐silane. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41003.     

Star-shaped silicon-containing arylacetylene resin based on a one-pot synthesis using zinc powder catalysis with improved processing and thermal properties

Herein, reporting a simple, sustainable, and cost-effective chemical synthesis of a star-shaped silicon-containing arylacetylene (SSA) resin via a one-pot process using zinc powder as a catalyst. The as-prepared viscous liquid resins exhibited moderate rheological behavior. The thermal curing temperature was determined to be 203 °C using differential scanning calorimetry, which is much lower than that reported for polyimide and phthalonitrile (>300 °C), indicating the SSA resins are suitable for processing at a lower temperature. Thermogravimetric analysis also revealed the excellent thermal stability and extremely high carbon residue of the cured SSA resin (the temperature at 5% mass loss and residual yield at 800 °C under N₂ were 654 °C and 93%, respectively). The results showed the excellent processability and thermal stability of SSA resin. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48248.     

Preparation of melamine–formaldehyde resin grafted by (3-aminopropyl) triethoxysilane for high-performance hydrophobic materials

Aiming at meeting the specific market demands and expanding the downstream application of melamine–formaldehyde (MF) resins, a series of (3-aminopropyl) triethoxysilane (APTES) grafted MF (MF-Si) resins were synthesized via an effective method that minimized the hydrolysis of APTES and overcame the polarity discrepancy of APTES with MF resin matrix. The structure of MF-Si resins was characterized by FTIR spectroscopy, Raman spectroscopy, ¹H nuclear magnetic resonance (NMR), and solid state ¹³C NMR. It was found that APTES moieties in MF-Si materials afforded increased hydrophobicity, water resistance, and the thermal stability was not affected. With the increasing amount of APTES, the water contact angle of MF-Si films increased from 70.56 to 105.92°and the surface free energy decreased from 46.8 to 23.5 mN/m. The temperature of maximum weight loss rate (T_dmax) of MF-Si materials decreased slightly from 371.15 to 353.70 °C and the ultimate residual weight of MF-Si materials increased from 12.51 to 30.04% at 800 °C under N₂. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48664.     

N-羟乙基全氟辛酰胺甲基丙烯酸酯聚合物的合成及性能研究

以全氟辛酸为起始原料合成N 羟乙基全氟辛酰胺甲基丙烯酸酯 ,再经均聚得到溶剂型的有机氟织物整理剂。均聚物对水和二碘甲烷的接触角分别为 98 4°和 80 5° ,计算得到其表面自由能为 0 0 185J/m2 。处理后的各类织物憎水性达 10～ 11级 ,憎油性达 4～ 5级     

Modification of a fluorine–silicone acrylic resin with a free‐radical‐catching agent

Several kinds of free‐radical‐catching fluorine–silicone acrylic resins with different contents of 2,2,6,6‐tetramethyl‐4‐piperidyl methacrylate (TMPM) were synthesized by solution copolymerization. The chemical structures and properties of the resins were characterized and followed the performances of their respective coatings. The results demonstrate that these kinds of resins showed a high ability to produce nitroxide. The coatings had good thermal stability and hydrophobicity with water contact angles over 100°. Moreover, the weather resistance showed a great improvement for the synergetic protection by bonded TMPM, organic fluorine, and silicone. By aging tests, the modified coatings still maintained excellent mechanical properties with an impact strength and flexibility of 400 N cm and 2 mm, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46385.     

Synthesis and characterization of poly(methyl methacrylate)/polysiloxane composites and their coating properties

A series of poly(methyl methacrylate) (PMMA)/polysiloxane composites and their coatings were prepared as designed. A copolymer (PMMAVTEOS) containing methyl methacrylate (MMA) and vinyltriethoxysilane (VTEOS) was prepared by free radical polymerization and then condensed with methyl triethoxysilane (MTES) to fabricate PMMA/polysiloxane composites; their corresponding coatings were obtained via a curing process in an oven (at 75 °C). The polymers were characterized by gel permeation chromatography and Fourier transform infrared spectroscopy. The surface property, hardness, water contact angle, thermal stability, and optical property of the coatings were investigated by scanning electron microscopy, pencil hardness testing, water contact angle testing, thermogravimetric analysis, and ultraviolet–visible spectroscopy, respectively. The results showed that, after addition of MMA, the pencil hardness of the coatings was reduced from 6H to 2H and the thermal stability decreased from 365 to 314 °C. However, it increased the flexibility and adhesion properties (the water contact angle increased from 94.7° to 102.1°). The transparent PMMA/polysiloxane coatings showed excellent scratch resistance, a smooth surface, high thermal stability, and a strong adhesion property. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46358.     

Atmospheric air-plasma treatments of polyester textile structures

The effects of atmospheric air-plasma treatments on woven and non-woven polyester (PET) textile structures were studied by surface analysis methods: wettability and capillarity methods, as well as atomic force microscopy/lateral force microscopy (AFM/LFM). The water contact angle on plasma-treated PET decreased from 80° to 50–40°, indicating an increase in the surface energy of PET fibres due to a change in the fiber surface chemical nature, which was confirmed by a higher fiber friction force measured by the LFM. The extent of water contact angle decrease, as well as the wash fastness of the treatment varied with the structure of the textile. Indeed the more porous the textile structure is (such as a non-woven), the fewer are the chain scissions of the PET at the fiber surface, during the plasma treatment. Thus, the level of surface oxidation and the weak boundary layers formation depend not only on plasma treatment parameters but also on the textile structure.     

Fabrication of durable hydrophobic cellulose surface from silane‐functionalized silica hydrosol via electrochemically assisted deposition

Durable excellent hydrophobic surface on cellulose substrate was fabricated from the silica hydrosol functionalized with silane chemicals by a facile electrochemically assisted deposition technique. The silica hydrosol was synthesized using tetraethoxysilane (TEOS) as the precursor and sodium dodecylbenzene (SDBS) as the emulsifier under acidic conditions. The hydrophobic silane modifiers including octyltriethoxysiliane (OTES), dodecyltriethoxysiliane (DTES) and isooctyltriethoxysiliane (iso‐OTES) and the silane‐coupling agent γ‐mercaptopropyltriethoxysilane (MPTES) were used to dope the silica hydrosol for preparing durable hydrophobic cellulose surface. The cellulose surface modified with silane modifier iso‐OTES exhibited the best hydrophobicity with water contact angle of 162.3 ± 0.5° due to its non‐polar and hydrolytically stable of ? Si(C₈H₁₇) groups. The addition of silane‐coupling agent MPTES containing the ? SH group led to good durability of hydrophobicity with water contact angle of 130.0 ± 1.2° after 20 washing times. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42733.     

Abrasion resistant semitransparent self-cleaning coatings based on porous silica microspheres and polydimethylsiloxane

Transparent, abrasion-resistant and superhydrophobic coatings have attracted considerable interest owing to their great advantages in applications. In this work, a semitransparent abrasion-resistant superhydrophobic coating was attained via depositing suspensions of porous silica microspheres and polydimethylsiloxane, followed by calcining and fluorating process. Herein, the porous silica microspheres were fabricated through a template method. Consequently, the coating exhibited a water contact angle of 153°, a hexane contact angle of 100° and an average optical transparency of 78%. Significantly, the coating displayed a robust resistance against sandpaper abrasion and knife-scratch. Furthermore, the coating also exhibited excellent self-cleaning performance even after it was contaminated by oil.     

Microcapsules on Woven and Non-woven Materials

Abstract

Properties of textiles can be improved or changed by applying a special finishing, which contains microcapsules and contributes to an antimicrobial, deodorising, medicinal or insect repelling effect. For the impregnation of woven and non-woven textiles, the compatibility of microcapsules with various water-based additives was tested: (1) water suspensions of binders based on latex (styrene-butadiene, polyvinylacetate, acrylate) with anionic and/or non-ionic emulsifiers, (2) binders based on solutions of water-soluble polymers (polyvinyl alcohol, carboxymethyl cellulose, modified starch, xanthanes), (3) finishing media based on urea- and melamine-forinaldehyde resins and dimethylolethylene urea. The suspension of microcapsules can be mixed with the above binders in all ratios. To determine the optimum conditions for the preparation of finishing formulations with microencapsulated ingredients, the coating system, the target effect of finishing, the textile properties and the target properties of the final product have to be defined.     

全氟烷基侧链改性阳离子水性聚氨酯的制备与应用研究

以异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃二醇(PTMG1000)、1,4-丁二醇(BDO)、N-甲基二乙醇胺(MDEA)、三羟甲基丙烷(TMP)等为主要原料,通过全氟乙基辛醇(FEOH)封端改性,制备了含全氟烷基侧链的阳离子含氟水性聚氨酯乳液。通过红外光谱(FTIR)、热重分析(TG)对其结构与膜性能进行了表征,并且将其作为纸张防水防油剂用于表面施胶,对处理后纸张表面的水和液体石蜡接触角及纤维形态进行了研究。结果表明,聚氨酯分子链中的全氟烷基成膜时产生了较大取向作用,含氟基团向空气/聚合物界面伸展,有明显的"趋表"现象,这有利于形成低能表面,对聚合物内部分子形成了很好的保护作用,使涂膜具有较高的耐热降解性能。当表面施胶质量分数为0.3%时,纸张即可达到优异的防水防油效果,水接触角达到134.7°,液体石蜡接触角达到119.2°。     

Production of superhydrophobic polymer fibers with embedded particles using the electrospinning technique

Superhydrophobic materials are currently used for their water‐repelling, self‐cleaning and anti‐fouling properties but are also potentially attractive to prevent snow or ice accumulation on exposed structures. Using the electrospinning technique, polymer mats made of polystyrene and poly[tetrafluoroethylene‐co‐(vinylidene fluoride)‐co‐propylene] (PTVFP) were prepared. They were found to show highly hydrophobic properties, water contact angle (CA) between 130 and 150°, when a dual fiber–bead microstructure was observed. Superhydrophobicity, CA > 150°, was reached when PTVFP mats were electrospun from a polymer solution containing dispersed polytetrafluoroethylene (PTFE) nanoparticles. Using atomic force microscopy imaging, protruding nanosized asperities on fiber and bead surfaces were observed and this structure led to superhydrophobic properties. Materials prepared from a high‐viscosity PTVFP/ethyl acetate solution with PTFE particles, 200 nm diameter and 8% (w/w), showed an 11.2% improvement in hydrophobicity, CA = 161°, compared to the materials obtained from a particle‐free polymer solution (CA = 143°). Copyright © 2007 Society of Chemical Industry     

Gel based on modified chitosan for oil spill cleanup

A method has been developed for obtaining a polymer porous gel and coating based on nontoxic and environmentally friendly components: chitosan, citral, and glutaraldehyde. The chemical structure and morphology of the polymer gel were investigated by infrared spectroscopy and scanning electron microscopy, respectively. The contact angles were determined using a goniometer, and the water and oil absorption of the gel were determined by the gravimetric method based on changes in the gel mass. Measurement of the contact angle θ of transmission oil and water drops on the coating surface showed the hydrophobic nature of the coating (θ = 90° for water and θ = 0° for oil). Study of the sorption properties of the resulting gel showed high sorption capacity with respect to transmission oil (9.05 kg/kg) and low sorption capacity with respect to water (2.46 kg/kg). It was found that after oil desorption from the loaded aerogel, it can be reused. The potential possibility of recycling the spent gel through its biodegradation in the soil was shown. Because of the excellent sorption capacity, high porosity, low density, and soil degradability, the developed gel has a great potential for application in the field of environmental purification from oil pollution.     

HDI trimer based fluorine containing urethane methacrylates for hydrophobic photocured coatings

In this work, hexamethylene diisocyanate (HDI) trimer based two urethane methacrylates were synthesized by reacting 2-hydroxyethyl methacrylate (HEMA) and a fluoroalcohol with HDI trimer. Due to the high viscosity of the fluorinated methacrylates, they were applied onto glass substrates after mixing with tripropylene glycol diacrylate (TPGDA). The performance of the fluorinated resins were compared to a fluorine free HDI trimer based trimethacrylate. The TPGDA diluted formulations were better in terms of surface wettability than the neat resins. TPGDA diluted fluorinated resins exhibited a water contact angle of 109°± 2. All coatings exhibited high surface hardness (4H and 5H) and good adhesion.     

One-step fabrication of superhydrophobic P(VDF-co-HFP) nanofibre membranes using electrospinning technique

In this study, superhydrophobic electrospun P(VDF-co-HFP) membranes were fabricated in a one-step electrospinning process. The effects of the key parameters of electrospinning (solution concentration, electrical potential, flow rate, and solvent) on the surface roughness, fiber formation, and hydrophobicity of the membranes were evaluated using Taguchi method. A 4 × 3 orthogonal array was utilized, and the results indicated that the solvent played the critical role in producing the superhydrophobic nanofibre membranes. It was demonstrated that it is possible to produce superhydrophobic membranes with P(VDF-co-HFP) without additional functionalisation and fillers. The highest water contact angle and the lowest contact angle hysteresis obtained were 156° and 5°, respectively, and the roughness values varied from 0.15 to 5.74 μm for the produced P(VDF-co-HFP) nanofibre membranes. The surface superhydrophobicity of the membranes was attributed to the specific structures consisting of a combination of beads and nanofibres. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48817.