Preparation,mechanical properties and surface morphologies of waterborne fluorinated polyurethane-acrylate

A series of waterborne fluorinated polyurethane-acrylate (WFPUA) materials were prepared from polyester polyol (NJ-330), isophorone diisocyanate (IPDI), dimethylol propionic acid (DMPA) and different content of hexafluorobutyl acrylate (FA). The chemical structure was characterized with FT-IR, ¹H and ¹³C NMR; and the result confirmed that the FA monomer had been introduced into the chain of the WPUA polymer. The physical properties of WFPUA dispersions, mechanical properties and thermal properties of WFPUA films were measured. When the content of FA monomer was 3.0 wt.%, the film exhibited the highest tensile strength, hardness and excellent chemical resistance. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used for characterization of cross and surface sections of the WFPUA films to verify the results. The obtained WFPUA materials have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.     

Structure control, coating properties, and durability of fluorinated acrylic-based polymers

Fluorinated acrylates were employed for the synthesis of conventional, side-chain fluorinated, fully acrylic random copolymers, and of more unusual hybrid copolymers with vinyl ethers. The latter can feature alternating structure and peculiar material properties associated with fluorine or fluorinated groups substitution onto the polymer backbone. Improved efficacy and durability of the resulting coating, highly desirable for the consolidation and protection of highly valued works of art, was achieved through a systematic approach involving a detailed study of their photodegradation behavior, and extensive testing of protection efficacy upon application onto micro-and macroporous stone substrates of different chemical composition and morphology. Presented on behalf of FATIPEC (AITIVA) at the 78th Annual Meeting of the FSCT in Chicago, IL on October 16–20, 2000. Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, 56126 Pisa, Italy. Dipartimento di Chimica IFM, via Pietro Giuria 7, 10125 Torino, Italy. Piazza Leonardo da Vinci 32, 20133 Milano, Italy, Lucia.     

Preparation and properties of waterborne cationic fluorinated polyurethane

Waterborne cationic fluorinated polyurethane (WCFPU) micro-emulsion was prepared by the reaction of isophorone diisocyanate (IPDI), polytetramethyleneether glycol (PTMG1000), 1,4-butanediol (BDO), N-methyldiethanolamine (MDEA), trimethylolpropane (TMP) and perfluoroalkylethyl octanol (FEOH), and then the films of the WCFPU were prepared. The influence on the mechanical properties and water absorption of the films, such as the molar ratio of NCO to OH, the dosage of MDEA, TMP and FEOH, was investigated. Their structure, morphology and heat performance were characterized by fourier transform infared spectrometer (FT-IR), dynamic light scattering (DLS), transmission electron microscope (TEM), X-ray diffraction (XRD), differential scanning calorimeter (DSC) and thermogravimetry (TG). The results revealed that the best mechanical properties and water resistance could be obtained under the condition that NCO/OH molar ratio was 1.25, w(TMP) was 1.1%, w(MDEA) was 7.29% and w(FEOH) was 22.3%. In addition, WCFPU was endowed with low surface energy of its film and the membrane surfaces had excellent water and oil repellency. Furthermore, the thermal stability of the waterborne cationic fluorinated polyurethane increased with the incorporation of perfluoroalkyl chain. And XRD, DSC and TG showed that micro-crystallinity of polyurethane increased with the increase of FEOH, which was benefit to the micro-phase seperation.     

Structure and surface properties of a novel bulk-matte waterborne polyurethane coating composite

This paper reports on a novel self-matte or bulk-matte waterborne polyurethane coating composite with inherently extremely low gloss. The coating composite was comprised of a siloxane-containing waterborne polyurethane (SPU) resin and a crosslinked waterborne polyurethane (CPU) resin. The CPU resin was mainly responsible for fabricating the micro-rough surface of the film, which was achieved by a crosslinking reaction between the waterborne polyurethane and bisphenol A-type epoxy E-44 resin. The SPU resin was used to improve the comprehensive properties of the film, which was ascribed to the addition of silane coupling agent KH792. Compared with traditional matte coatings, this coating composite made it possible to avoid high loadings of matting agent and to arrive at highly flexible low-gloss finishes. Gloss levels of as low as a few tenths of a percent, even at high incidence angles, have been achieved with zero loading of extraneous dulling agent. The chemical structures of the SPU and CPU resins were characterized by FTIR-ATR and NMR spectra. The micro-rough topographies and surface rough degrees of the SPU, CPU and their 50%/50% composite films were measured by SEM and MSP, respectively. The particle sizes and particle morphologies of the SPU and CPU resins were imaged by TEM. Finally, the comprehensive properties of the SPU, CPU and their 50%/50% composite resins were evaluated, including the water contact angle, film transparency, tensile strength and storage stability.     

Effects of morphology and surface treatment of inorganic pigments on waterborne coating properties

Inorganic pigments in aqueous coatings are investigated using atomic force microscopy and microprobe analysers. The first method characterises the topography at a very high resolution. The findings obtained using the second method reveal the distribution of the pigment in the paint film. Taking selected titanium dioxide and iron oxide pigments, the effects of particle morphology as well as inorganic and organic surface treatment on the dispersibility and flocculation stability are shown. These two phenomena are factors in gloss, hazing, hiding power, tinting strength and viscosity – key quality parameters in waterborne coatings.     

Effect of crosslinking on the surface free energy and surface reorganization of waterborne fluorinated polyurethane

To endow waterborne fluorinated polyurethanes (WFPUs), films with stable lower surface free energy and lower surface reorganization after the films contacted with water, a series of crosslinked WFPUs (CWFPUs) emulsions were prepared by adjusting the content of aziridine (AZ). The effect of crosslinking on the surface free energy, glass-transition temperature (T _g), water absorption, and surface composition of dry/hydrated WFPUs and CWFPUs films were studied by CAs test, dynamic mechanical analysis, water absorption measurements, and X-ray photoelectron spectroscopy. When the fluorine content was 0.5%, the surface free energy of the CWFPUs films modified by 0.4% AZ content (CWFPU-6-0.5-CK0.4) reached to the lowest value of 15.76 mN m⁻¹ which almost equaled to the surface free energy (15.45 mN m⁻¹) of the dry uncrosslinked films (WFPU-6-0.5). With the increasing of AZ content, the T _{g, hard} of hard segments of the CWFPUs films increased and the water absorption of the CWFPUs films decreased, which suggested the formation of the crosslinked network structures. The studies of the surface elements and groups composition of dry/hydrated WFPUs and CWFPUs both confirmed that the surface reorganization and the migration of fluorinated side chains were restricted by the crosslinked network structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47167.     

新型水基涂料及其膜的性能

1　前言近年来 ,紫外固化水基涂料由于可减少空气污染 ,降低火灾危险 ,改善现场健康条件 ,提高安全性 ,尤其是以水作为紫外固化体系稀释剂 ,降低了有毒气体对环境的污染 ,解决了粘度控制和活性稀释剂影响固化膜性能之间的矛盾 ,而且易于清洗 ,因而得到广泛的工业应用。有 2种水基体系 :含外加表面活性剂的乳液或胶体分散液和水溶性或水分散型含亲水性基团的树脂体系。前者制备时通常加入表面活性剂 ,有助于形成稳定的乳液。但外加的表面活性剂影响最终产品的性能 ,即留在紫外固化膜中的表面活性剂使涂层具有水敏性。后一种体系不用加入表面…     

Surface and bulk properties of waterborne polyurethane modified with fluorinated siloxane

Two series of polyester and polyether waterborne polyurethanes (WPUs) modified with poly[(3,3,3‐trifluoropropyl)methylsiloxane] (PTFPMS) were synthesized by prepolymerization method and the effect of PTFPMS on surface and bulk properties were investigated by a variety of experimental methods. FTIR and DSC results showed that the polyester WPU has better compatibility between soft segments and hard segments than polyether WPU in bulk and the degree of phase separation increased in polyester WPU but decreased in polyether WPU with increasing PTFPMS. ARXPS analysis revealed the migration of PTFPMS to WPU surface and the migration ability of Si element was better than F element. AFM images demonstrated that the surface of WPU films became rougher as PTFPMS content increased. The enrichment of PTFPMS with low surface energy and roughened surface imparted good hydrophobicity and oleophobicity to WPU films and polyether WPU has better surface properties compared with polyester WPU. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46473.     

水性环氧硅溶胶复合防腐涂料的制备及其性能

以水性环氧树脂乳液和水性硅溶胶作为成膜基料,添加防锈颜填料,制备了一种有机-无机水性复合防腐涂料。研究了防腐涂料的腐蚀速率以及水性硅溶胶用量对涂层在不同腐蚀介质中的耐蚀性,及其表干时间、实干时间、硬度、附着力和耐盐雾性的影响,通过电化学方法确定了涂层的最佳厚度。结果表明:当防闪锈剂添加量为1%(w)、颜基比为20%(w)、水性硅溶胶的质量占水性环氧树脂质量的15%、漆膜厚度为180μm时,所制复合水性防腐涂料具备良好的耐水、耐碱、耐盐雾性。     

Oligomeric fluorinated additives as surface modifiers for solid polymers

Successful modification of the surface properties of solid polymers was obtained by the adsorption of appropriate partially fluorinated oligomers at polymer/air and polymer/substrate inter faces during the formation of these interfaces. These additives, in concentrations of 0.25 percent, effectively lowered the critical surface tension of wetting, γ_c, of such polymers as polystyrene, poly(methylmethacrylate), and poly(vinylidene chloride) copolymers by as much as 26 dyn/cm. The obtained low γ_c values of 14 dyn/cm correspond to surfaces containing closely packed CF₃ and CF₂ groups. Adhesion of additive-containing polymer films to various substrates was demonstrated to be a function of additive diffusion to the polymer/substrate interface, its subsequent adsorption and molecular orientation at that interface, and the surface energy of the substrate. The fluorinated additive molecules also have the advantage of being sufficiently mobile in the solidified polymer to reach and repair the interfaces.     

水性铝基金属微粉涂层的性能研究

介绍了水性铝基金属微粉涂层的工艺配方和工艺流程,对涂层的外观、厚度、附着强度、孔隙率和耐蚀性进行了研究。结果表明,涂层外观呈银白色,表面均匀、平整;涂层与基体的结合力良好,平均厚度为18μm,具有较高的致密性,无孔隙分布;完整的涂层经480 h的中性盐雾试验后,不起雾,不生锈,表现出较好的耐蚀性,达到国家标准中的三级水平。     

Novel, water-based fluorinated polymers with excellent antigraffiti properties

In this article we describe novel, water-based, crosslinkable fluorinated polymers that form coatings with excellent antigraffiti properties. The synthesis of the binders and the surface and bulk properties of their coatings are discussed. The surface properties of these coatings are characterized in terms of their surface-free energy, as calculated from static contact angle measurements. The distribution of the fluorine atoms throughout the coating is measured by X-ray photoelectron spectroscopy (XPS). The bulk properties are studied by determining the crosslink density through dynamic mechanical thermal analysis (DMTA), and the effect of the crosslinking conditions on the crosslink density and the antigraffiti properties is discussed. The results indicate that a combined action of surface and bulk properties gives these coatings their excellent antigraffiti properties. The applicability of these polymers as protective coatings for metal and concrete surfaces are demonstrated. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL     

水性涂料印花黏合剂的合成与性能研究

以丙烯酸异辛酯(2-EHA)、丙烯酸丁酯(BA)、丙烯酸乙酯(EA)、丙烯腈(AN)和丙烯酸(AA)为主要原料,以反应性阴/非离子型乳化剂(HS-10/OP-10)为复合乳化剂、Dow Corning-346为有机硅助剂和甲基丙烯酸缩水甘油酯(GMA)为交联剂,采用半连续滴加预乳液的乳液聚合方法,制备了水性丙烯酸酯类涂料印花黏合剂。探讨了单体、乳化剂和交联剂等对黏合剂性能的影响,并采用红外光谱(FT-IR)法鉴别出国外同类产品中所用助剂的品种及含量。研究结果表明:当m(HS-10)∶m(OP-10)=2.2∶1、w(GMA)=3%、w(BA)=40%、w(2-EHA)=20%、w(EA)=14%、w(AA)=3%、w(AN)=20%和w(Dow Corning-346)=3%时,相应涂料印花黏合剂的综合性能与国外同类产品相当。     

水性炭系电热涂料的制备及性能研究

以水性丙烯酸树脂为粘结剂,石墨为主要导电填料,配入其他导电填料制备了水性炭系电热涂料。研究了水性丙烯酸树脂添加量、溶剂水的用量、固化温度和导电填料种类对涂层电热性能的影响,并测试了最佳条件所得涂层的使用性能。结果显示,水性丙烯酸树脂与石墨的质量比为5∶5时,涂层在80 V的电压下通电5 min,表面温度可达95°C。溶剂水的添加量宜23%~27%,涂层固化温度宜50°C左右。在所选炭黑、煅后焦、无烟煤、三氧化二铝、二氧化硅和碳化硅这6种填料中,石墨与炭黑复合后所得涂层电热性能最好。当m(水性丙烯酸树脂)∶m(石墨)∶m(炭黑)=5∶4∶1时,40 V电压时涂层表面温度可迅速达到100°C以上,且耐水性、耐热性、硬度和附着力均满足使用要求。     

The colloidal properties of alkaline‐soluble waterborne polymers

Waterborne polymer dispersions are widely used in coatings and graphic arts markets as environmentally friendly and more sustainable alternatives to solvent borne binders. Traditionally, waterborne (meth)acrylic dispersions are prepared by emulsion polymerization using low molar mass surfactants as a key ingredient to control particle size. However, these surfactants can have a negative influence on the performance of coatings such as reduced water resistance and adhesion. To mitigate the negative effects of surfactants, polymer latexes have been developed that employ alkaline‐soluble polymers as the sole stabilizer for a subsequent emulsion polymerization step. In this way surfactant‐free polymer dispersions are obtained. Despite the high commercial impact and relevance of this technology, fundamental studies regarding the physicochemical properties of the alkaline‐soluble polymers are lacking. In this article, the synthesis and colloidal properties of alkaline‐soluble waterborne methacrylic copolymers are reported. The dissolution behavior and colloidal properties of these alkaline‐soluble polymers were studied as function of molar mass, acid content, and pH. The dissolving polymer particles were characterized using static and dynamic light scattering, static and dynamic surface tension measurements, and cryogenic‐transmission electron microscopy analysis. It is concluded that the dissolution mechanism of alkaline‐soluble polymers follows a gradual process. As the pH increases deprotonation of the carboxylic acid groups swells the particle enhancing the further swelling with water. At a certain amount of base, the particles disintegrate into small polymer aggregates while the most water‐soluble polymer chains are dissolved in the water phase. An important learning is that part of the alkaline‐soluble polymer resides in very small particles (<5 nm). The formation of these polymer particles below 5 nm was not reported previously and offers a new insight into the dissolution mechanism of alkaline soluble polymers. The most important parameter steering this process is the acid value of the polymer, while the molar mass plays a modest role. The understanding gained in this study can be used to further advance alkaline‐soluble polymers as stabilizer in surfactant‐free emulsion polymerization technology, improving the performance of a wide range of industrially relevant coatings. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46168.     

含氟丙烯酸酯改性聚氨酯乳液的研究进展

对国内外含氟丙烯酸酯改性聚氨酯乳液（FPUA）中的氟化丙烯酸酯/聚氨酯链段结构的合成方式及工艺进行了较为全面的论述,介绍了含氟丙烯酸酯改性水性聚氨酯的优异性能及其应用领域。指出了含氟丙烯酸酯改性水性聚氨酯当今研究的热点和今后发展方向。     

水性聚氨酯的改性及水性聚氨酯涂料

介绍了几种水性聚氨酯的改性技术,并对水性聚氨酯涂料的配制及其应用作了相关概述。     

Preparation and surface characteristics of low-temperature curing fluorinated cathodic electrodeposition coating

Fluorinated cationic cathodic electrodepositing (CED) resins were synthesized by copolymerization of several acrylic monomers including Zonyl. Water dispersible cationic blocked-diisocyanate (denoted as TId) was also synthesized from isophorone diisocyanate (IPDI), cationic triethanolamine (TEOA), and dimethylpyrazole as the cross-linker for the low temperature curing at 90–120 °C. The emulsion stability of the cationic fluorinated CED resin was improved by ionization of the cross-linker TId, showing a mean particle diameter of 140–150 nm and a narrow distribution. 0.5 wt% of curing catalyst dibutyltin dilaurate (DBTL) was enough to accelerate the curing reaction and the gel content of the TId cured fluorinated CED film was higher than 90 wt% after being cured at 130 °C for 40 min. The contact angle and XPS spectrum of the CED film demonstrated that the surface enrichment of C–F₂ and C–F₃ groups effectively reduced the surface tension of the fluorinated CED coating and its surface tension γ_sv is even lower than 15 mN m⁻¹ for PTFE. The preheating of the CED film above T_g but below curing temperature promoted this surface enrichment of the fluorinated groups. Thermal fragmentation of the fluorinated side chains in the CED resins was successfully avoided due to using TId for low temperature curing.     

Synthesis and properties of UV-curable waterborne unsaturated polyester for wood coating

UV-curable waterborne unsaturated polyesters for wood coatings were prepared. The effects of different polyols and acids on the properties of the UV-curable waterborne unsaturated polyesters were investigated. Several different unsaturated polyester prepolymers were prepared from three different polyols [ethylene glycol (EG), diethylene glycol (DEG), and propylene glycol (PG)] and three different acids [tetrahydrophthalic anhydride (THPAn), terephthalic acid (TPA), and trimellic anhydride (TMAn)]. UV-curable coating materials were formulated from the prepolymers and 2-hydroxy-2-methylphenyolpropane-1-one as a photoinitiator with distilled water as a diluent. Trimethylolpropane diallyl ether was used as an air inhibitor of cure. The dynamic mechanical studies showed the properties of those unsaturated polyesters were well correlated with their glass transition temperature behaviors. It was found that the unsaturated polyester prepared with 60/40 (mol %) TMAn/THPAn and the equimolar mixture of EG, DEG, and PG showed balanced coating properties such as good tensile properties and weatherability, as well as proper viscosity (ca. 2500 cps) when using distilled water as a diluent. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 695–708, 1998     

氟硅烷改性水性丙烯酸二级分散体的制备与涂层性能

将1,1,3,3-四甲基-1,3-二乙烯硅氮烷(DVDZ)和甲基丙烯酸六氟丁酯(EINECS)进行Micheal加成反应,合成2,2,3,4,4,4-六氟丁基-3-(二(二甲基(乙烯基)硅基)氨基)-2-甲基丙酸酯(DVE)功能有机氟硅单体,与甲基丙烯酸甲酯(MMA)、甲基丙烯酸羟乙酯(HEMA)等单体混合,以偶氮二异丁腈(AIBN)为引发剂,异丙醇(IPA)为溶剂,合成氟硅烷改性水性丙烯酸二级分散体。然后,将其与异氰酸酯固化剂混合,制备了双组分水性聚氨酯(2K-WPU)涂膜。通过FTIR、1HNMR、TG、SEM、XPS对DVE和2K-WPU进行表征和检测,结果表明:随着DVE质量分数的增加,丙烯酸二级分散体的粒径增大,黏度降低,涂膜的耐水性增强,铅笔硬度和附着力减弱。当DVE质量分数为6%时,吸水率为8.2%,接触角为91.5?,热失重10%和50%时的温度分别为220.9和438.5℃,涂膜耐热、耐水和耐酸碱等性能均有提升。