Polyurethane coatings prepared from CNSL based polyols: Synthesis,characterization and properties

Conventional polyurethane chemistry based on polyol and isocyanate chemistry is widely used for many applications ranging from plastics to coatings, constructions, pharmaceuticals, foods, etc. The growing concern over depletion of petrochemical materials and their rising prices has led to search for environment friendly renewable materials. Cardanol derived from cashew nut shell liquid is one such renewable material which has reactive phenolic group and aliphatic double bond that could be tailor-made to produce novel functional materials for polymer and coating applications. This has previously been used for preparation of phenolics, epoxy resins and phenalkamine hardners. Diglycidyl ether of cardanol which is commercially available, is used as epoxy resin or modifier in epoxy formulations. In the present work, this was modified by simple one step ring opening reaction to produce polyols with different number of functionalities. The various polyols prepared were cured with polyisocyanate cross-linkers and applied on metallic substrates. The cured coatings were evaluated for physical, mechanical, chemical and thermal properties. The study conducted showed that the prepared polyols could be used as sole binder for coating formulation with overall excellent properties.     

马来海松酸类环氧树脂固化产物性能

本文研究了马来海松酸类环氧树脂与酸酐及芳香二胺类五种固化剂固化产物的耐热性能和机械性能,并详细讨论了固化后树脂的性能与环氧树脂、固化剂的化学结构及固化反应条件之间的关系。     

含有疏水化剂的水性环氧树脂的制备与性能

以聚丙二醇（PPG）和双酚A型环氧树脂为原料,使用特殊催化剂合成了水性环氧树脂涂料用疏水性剂基体,并在其中添加疏水性微粒子WS-12组成疏水化剂。使用该疏水化剂与水性环氧树脂、通用环氧树脂按一定比例混合调制成水性环氧涂料复合物,并研究和评价其固化物的力学性能及涂膜的相关性能。研究结果表明,当m（水性环氧树脂）：m（疏水化剂）：m（环氧树脂6002）=20：10：70时,树脂固化物及涂膜的力学与物理性能最佳。     

Aminimide as hardener/curing promotor for one part epoxy resin composition

Three kinds of aminimide compounds were examined as latent hardeners/promotors for epoxy resins. Since aminimides are thermolyzed to generate tertiary amine and isocyanate, the compounds are useful as polymerization initiators for the epoxy group as well as promotors for epoxy–acid anhydride reaction. The pot life was over 30 days at 40°C for a formulated one-part epoxy resin system. In comparison with epoxy resins cured with conventional hardeners, several interesting characteristics of the mechanical and electrical properties were observed. In particular, the epoxy resins cured by aminimides exhibited high tensile strength and high impact strength, which make them excellent curing agents for adhesive applications. The reasons for these unique properties are discussed.     

High-performance waterborne UV-curable polyurethane dispersion based on thiol–acrylate/thiol–epoxy hybrid networks

Synthesis, characterization, and film performance of waterborne thiol–acrylate/thiol–epoxy hybrid coatings are highlighted in this article. A dimer acid-modified epoxy (DME) polyol, containing both hydroxyl and epoxy functional groups, was prepared by reacting epoxy resin (EEW = 190 g/equi) with dimer fatty acid at 2:1 molar ratio. Further, a base UV-curable polyurethane acrylate dispersion (UV-PUD), with a pendant epoxy functional group, was prepared by reacting polyol (DME), isophorone diisocyanate, and dimethylol propionic acid and end-capped with hydroxyethyl methacrylate with subsequent dispersion in water. Prepared intermediates were characterized for the parameters relevant to the study by physical, spectroscopic, and chemical methods. UV-curable thiol–acrylate/thiol–epoxy hybrid coatings were prepared by blending UV-PUD with trimethylolpropane tris(3-mercaptopropionate) (TMPMP) at four different thiol ratios (0, 0.3, 0.6, and 1.0) with respect to acrylate/epoxy groups. Cured films of the hybrid coating were identified by FTIR spectroscopy. The impact of thiol ratio on film performance was evaluated in terms of mechanical, chemical, thermal, and coating properties. The gel content measurements confirm that the addition of TMPMP increased the double bond conversion along with the epoxy group. Evaluation of cured samples shows the significant improvement in storage modulus, glass transition temperature, tensile strength, and hardness with increase in thiol ratio. The cured films possessed excellent water and acid resistance (<4%) even after 28 days of immersion. Moreover, the notable improvement was alkali resistance of cured films, i.e., as thiol ratio was increased from 0 to 1, weight loss in alkaline environment deceased from 49.5 to 4.5% after 28 days. Better properties of the thiol–acrylate/thiol–epoxy hybrid films will allow it as a potential application in low-volatile high-performance coatings.     

Recent developments in two-pack water-based epoxy coatings

In recent years new curing agent technology has been developed which allows water-based curing agents to be introduced into high performance coating, these are classified according to the type of epoxy resin used. Type I utilises low molecular weight, liquid epoxy resins and Type II pre-formed dispersions of higher molecular weight solid epoxy resins. The chemical composition of the binder of water-borne epoxy coatings plays a critical role in their performance properties, hence some of the structural properties of the amine hardeners will be reviewed. New curing agents will be discussed which demonstrate the versatility these products can offer to the coating formulator. Performance data of clear coats and anti-corrosive primers confirm the applicability of the new systems for the long term protection of steel and concrete surfaces.     

Synthesis of bio-based epoxy resin from gallic acid with various epoxy equivalent weights and its effects on coating properties

The bio-based epoxy resins for coating application were synthesized from gallic acid (GA) in various molar ratios with epichlorohydrin (ECH). The reaction was carried out in the presence of sodium hydroxide (NaOH) and phase-transfer catalyst tetrabutylammonium bromide. The reaction progress rate at various molar ratios as 1:8, 1:12, and 1:16 with respect to time was monitored by calculating the epoxy content. The epoxy content value increases in the product as the molar ratio of GA to ECH increases. Epoxy equivalent weight of products was evaluated by physiochemical method and structure illustrated by Fourier transform infrared and ¹H-nuclear magnetic resonance spectroscopy. This bio-based epoxy resin was cured with polyamide hardener, and the coating properties such as mechanical, chemical, and solvent resistance were studied. The cured films have been evaluated for glass transition temperature (T _g) and thermal behavior by a differential scanning calorimeter and thermogravimetric analysis, respectively. The bio-based epoxy coatings show interesting mechanical, chemical, and thermal properties as compared to the conventional epoxy resin. The gel and water absorption of polyamide-cured coatings has also been evaluated.     

Two-component aqueous epoxy binders free of volatile organic content (VOC)

Water-borne two-pack coatings based on a novel epoxy resin emulsion, cross-linked with three different amine group containing curing agents, are discussed. The aqueous binders developed at the Research Laboratory at Dow Deutschland Inc. are free of volatile organic content. The epoxy resin emulsion has a low MFFT (minimum film formation temperature) and is hence capable of forming a continuous film at low temperatures and good emulsifying properties. The interaction is discussed between the epoxy emulsion, pigments and hardeners which are in aqueous solution, emulsion or hydrophobic (non-aqueous) form. Some of the described systems will gain interest in a wide range of applications because of their excellent properties, including adhesion to various substrates, resistance to chemicals, solvents and water, hardness and toughness. The predicted major applications for such systems include concrete, plastic and wood coatings, and anti-corrosive systems for steel and other metals.     

Preparation and characterization of thermally stable epoxy-titanate coatings

Epoxy-polyamide coatings are used to protect metallic substrates in corrosive atmosphere. Thermal stability of the coating can be improved by the addition of inorganic cross-linking agent. Epoxy resin is incorporated with small percentage of silicone resin and cured with two types of hardeners such as polyamide and butyl titanate. The physical properties, heat resistance properties and electrochemical impedance behaviour of these coatings on steel in 0.5 M NaCl solution have been studied. The result implies that the heat resistant character of the titanate-cured coating is increased from 260 to 370 °C. The impedance study has shown that the coating resistance exerted by both the systems is in the range of 10⁵ Ω cm² after 6 days of immersion in 0.5 M NaCl. FTIR and Raman spectroscopy analysis confirm the presence of titanate linkage in the cured polymer coating. Thermal stability data indicate that the epoxy silicone resin cured with titanate hardener possesses higher thermal stability than that cured by polyamide hardener.     

功能型环氧树脂基防腐涂层的研究进展

环氧树脂涂层因其优异的耐蚀性能、对金属表面良好的附着力而在金属防腐领域得到广泛应用。但涂层固化过程中会形成缺陷和孔洞，腐蚀介质可以直接接触到金属表面。为了开发出具有优良耐久性的防腐涂层，研究人员使用不同的方法和材料制备了多种环氧树脂防腐涂层。该文综述了纳米粒子改性环氧防腐涂层、超疏水型环氧防腐涂层、自修复型环氧防腐涂层、导电聚合物改性环氧防腐涂层及生物基材料改性环氧防腐涂层的制备及性能。但这5种防腐涂层各有局限性，未来应该探究出新的环氧防腐涂层，在提升涂层防腐性能的同时，兼顾其他性能，使环氧树脂基防腐涂层朝着功能化、智能化的方向发展。     

The influence of the molecular structure on the chemical resistivity of solventless and high-solid epoxy resins

The chemical resistance of solventless and high-solid epoxy compositions has been studied. The compositions have been cured at normal temperature and the chemical resistivity has been studied as a function of various resin types, solvent types and hardener types. The chemical resistance increases slightly with increasing epoxy equivalent weight. This is especially pronounced for this type of dependence relative to low molecular weight organic acids. The resistance of diluents to hydrolysis is more important than the reactivity of the diluent used. Also the capacity to swell plays an important role for a given solvent and resin system. The highest resistances have been determined for styrene as a reactive diluent and for 1,1-diphenylethane as the non-reactive diluent. The differences due to polyamine hardeners are decreased with the use of epoxy resin of higher epoxy equivalent weight.     

固化剂对环氧玻璃鳞片涂层性能的影响

以双酚A环氧树脂(E20)为主要成膜物,层片状玻璃鳞片和云母氧化铁为主要填料,辅助以铝粉、氧化铁红颜料,以及各种助剂和溶剂,再分别加入固化剂脂肪族胺加成物、聚酰胺TY-650,制得高固体分厚浆型环氧玻璃鳞片涂料。通过常规的力学性能(涂层的硬度、耐冲击性、柔韧性、附着力等)和耐腐蚀性测试,对比了不同固化剂对环氧玻璃鳞片涂层性能的影响。研究结果表明,脂肪族胺加成物与环氧树脂交联固化的玻璃鳞片涂层的硬度、附着力以及交流阻抗值都较高,具有良好的综合性能,加入铝粉对基体可起到阴极保护作用。     

Polyamidoamines based on castor oil-styrene co-oligomer/triethylenetetramine as curing agents in high-performance epoxy coatings

Polyamidoamines (PAMAMs) based on castor oil-styrene co-oligomer and triethylenetetramine (TETA) or benzylated TETA were synthesized and diluted with an amide-like diluent (EFA). The intermediates and products structures were characterized using FT-IR, ¹H NMR, gel permeation chromatography, and scanning electron microscopy. The diluted PAMAMs types were used as the curing agents of the epoxy resin to produce the modified coatings. The mechanical, chemical, and visual properties of the epoxy coatings obtained by commercial hardeners compared to the modified coatings. The modified coatings were transparent, and had humidity resistance higher than the commercial coatings, at 15°C and 80% relative humidity. The modified coatings were obtained with the lowest surface defects and improved mechanical properties such as Izod impact resistance, tensile strength, and the pull-off adhesion (3.3–4.8 kJ m⁻², 42.2–54.5 MPa and 3.0–3.5 MPa) relative to the commercial coatings (1.1–3.0 kJ m⁻², 28.7–39.9 MPa and 1.4–2.1 MPa), respectively. Moreover, in spite of the commercial coatings, the modified coatings were cost-effective and showed the behaviors of appropriate self-healing and chemical resistance.     

Epoxy acrylate UV/PU dual‐cured wood coatings

For improving the finishing performances of complicated three‐dimensional coated wood products (e.g., furniture) with some shadow zones in the absence of ultraviolet (UV) light, resulting in incomplete curing of UV coatings, the aim of this study was to investigate the characteristics and effects of curing process on the properties of epoxy acrylate UV/PU dual‐cured resin for wood coatings when compared with traditional UV and polyurethane (PU) coatings. The epoxy acrylate oligomer was synthesized for providing a double bond of acryloyl group and a secondary hydroxyl group. The UV/PU dual‐cured coating was formulated with epoxy acrylate resin/tripropylene glycol diacrylate (TPGDA) monomer by the weight ratio of 80/20, 3% dosage of benzil dimethyl ketal as a photoinitiator, and the NCO/OH mole ratio of 1.0. The aromatic polymeric diphenylmethane diisocyanate was used as a hardener. The films of the dual‐cured coating, obtained from UV‐cured or room temperature‐cured process, showed an excellent tensile strength, elongation at break, impact resistance, and lightfastness when compared with traditional UV and PU coatings; especially, the adhesion of UV/PU dual‐cured coating by UV‐cured process was better than that of traditional UV coating. It can therefore be concluded that the epoxy acrylate oligomer‐based dual‐cured coating could readily be used for complicated wood products finishing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development and characterization of silicone/phosphorus modified epoxy materials and their application as anticorrosion and antifouling coatings

Epoxy resin is chosen for our present study owing to its exceptional combination of properties such as easy processing, high safety, excellent solvent and chemical resistance, toughness, low shrinkage on cure, good electrical, mechanical and corrosion resistance with excellent adhesion to many substrates. This versatility in formulation made epoxy resins widely applied for surface coatings, adhesives, laminates, composites, potting, painting materials, encapsulant for semiconductor and insulating material for electric devices. There are numerous paint/coating systems based on epoxy resin available for corrosion and fouling prevention. They however are not completely satisfactory in field applications, where high corrosion, fouling and flame resistance are required. The demand for epoxy resin as corrosion/fouling resistant coatings is restricted mainly due to its inferior characteristics like poor impact strength, high rigidity, and moisture absorbing nature besides inadequate flame retardant properties. It is for this reason that silicones and phosphorus-based compounds are used as modifier in this work by intercrosslinking network mechanism (ICN) to obtain epoxy resin with desired properties ideally suitable for field applications for preventing corrosion and fouling with flame retardantancy. The present work involves the development of solvent free silicone/phosphorus modified epoxy coating systems, since solvent free coating systems are widely used for numerous applications due to their lower cost per unit film thickness, freedom from fire and pollution hazard and ability to provide better performance. For the development of coating systems, epoxy resin (X) serves as base material, hydroxyl terminated polydimethylsiloxane (HTPDMS) as modifier, γ-aminopropyltriethoxysilane (γ-APS) as crosslinking agent and dibutyltindilaurate (DBTDL) as catalyst. Polyamidoamine (A), aromatic amine adducts (B) and phosphorus-containing diamine (C) were used as curing agents. The study also describes the evaluation of corrosion resistant behaviour of unmodified epoxy and siliconized epoxy coatings by potentiodynamic polarization method, electrochemical impedance spectroscopy (EIS), salt-spray and antifouling tests. The results are discussed.     

耐热,耐油防腐涂料的研制

研制成耐热、耐油防腐涂料。该涂料是以生漆为主要原料,经改性,拼入多种颜填料配制而成,解决了热油介质下热交换器的防腐。阐述了漆酚甲醛树脂和环氧有机钛改性漆酚甲醛树脂的制法,以及涂料的配制。列举了该涂料的物理机械性能和耐化学品性能指标。讨论了影响涂层性能的因素。     

Thermo-mechanical properties of rosin-modified o-cresol novolac epoxy thermosets comprising rosin-based imidoamine curing agents

Rosin-modified o-cresol novolac epoxy resin (AEOCN) was synthesized by condensation of rosin acid with o-cresol formaldehyde novolac resin (AOCN). The AEOCN resin was further epoxidized using epichlorohydrin and sodium hydroxide. Rosin-based imidoamine curing agents (IAMDK, IASDK, and IAEDK) were also prepared by reacting dimaleopimaryl ketone (DMPK), a dimerized rosin product with aromatic diamines. The chemical structures of all synthesized products were confirmed by FTIR, ¹H-NMR, ¹³C-NMR, and DEPT-135° spectroscopic techniques. The curing process of rosin-modified epoxy cured with imidoamine crosslinkers was studied using differential scanning calorimetry (DSC) and the results were compared to o-cresol novolac epoxy resin (EOCN) and some previously reported commercial-based systems. The thermal and mechanical properties of the cured epoxy thermosets were determined using a thermogravimetric analyzer (TGA) and a universal testing machine (UTM), respectively. The chemical resistance analysis was carried out by immersing cured epoxy coated panels in 1M NaOH, 1MHCl, and 1M NaCl solutions. The results were evaluated in terms of % weight loss method and the morphological changes that appeared due to chemical exposure were also investigated via scanning electron microscopy (SEM). This study presents the economical synthetic approach towards high-performance bio-based epoxy coating materials impending to replace some of the petrochemical compounds in coating industries.     

Novel isocyanate-free self-curable cathodically depositable epoxy coatings: Influence of epoxy groups on coating properties

Novel self-curable cathodically depositable coatings were developed from glycidyl functional epoxy ester-acrylic graft co-polymer (EEAG) without using any external crosslinking agents. The EEAG-amine adducts (EEAGAs) were prepared by reacting EEAG with varying amount of diethanolamine (DEoA) which are neutralized with acid and dispersed in deionised water to give stable dispersion for cathodic electrodeposition (CED) coatings. The dispersions were cathodically electrodeposited on phosphated steel panels and thermally cured to give uniform coating. The coatings were evaluated for different mechanical, chemical and corrosion resistance properties. The coatings were evaluated for their thermal properties using thermo gravimetric analysis (TGA). The final properties of the coatings were found to be affected by the amount of amine reacted with epoxy. The coating films showed good overall performance properties for their use in coating industry.     

Synthesis of acid anhydride-modified flexible epoxy resins and enhancement of impact resistance in the epoxy composites

Epoxy resins are key materials used in various applications, including coatings, adhesives, and composites. Tougheners, such as nanoparticles, soft polymers, elastomeric polyurethanes, and core/shell particles, have been widely applied to compensate for the brittleness of the epoxy matrix and to enhance the impact resistance. Modifying epoxy resin by reacting it with a flexible component is one of the representative methods to overcome the weakness of cured epoxy polymers upon impact. For introducing flexible parts, we synthesized three types of epoxy-modified resins by reacting acid anhydride with glycidol, followed by reaction with bisphenol [F, S, or J] glycidyl ether to produce flexible modified epoxy resins. Mechanical tests, such as flexural strength and impact resistance tests, were performed by adding various amounts of the synthesized resin to the epoxy composites. The results of these tests suggest that the modified resins were effective in improving the toughness of the epoxy matrix.     

Computer simulation of structure and properties of crosslinked polymers: application to epoxy resins

In this work, a methodology has been developed for construction of atomistic models of crosslinked polymer networks. The methodology has been applied to low molecular weight water soluble epoxy resins crosslinked with different curing agents that are being considered for use as a primer coating on steel. The simulations allowed the crosslink density and the amount of free crosslinking sites in the coatings to be predicted. Shrinkage of the resin upon curing was reproduced by the simulation. In addition, the barrier properties of the model coatings were estimated. The interface between an inorganic substrate and cured epoxy resin has been constructed and the strength and molecular mechanisms of adhesion have been revealed. The developed methodology has a potential to significantly impact on the design and development of new coatings with improved barrier and adhesion properties.