A novel UV‐curable epoxy acrylate resin containing arylene ether sulfone linkages: Preparation,characterization, and properties

UV‐curing processes are used in industrial applications because of their advantages such as high‐speed applications and solvent‐free formulations at ambient temperature. UV‐curable epoxy acrylate resins containing arylene ether sulfone linkages (EAAES) were synthesized through the condensation of bis(4‐chlorophenyl)sulphone and bisphenol‐A, followed by end‐caping of epichlorohydrin and subsequently acrylic acid. UV‐cured coatings were formulated with epoxy acrylates, reactive diluents such as pentaerythritol tri‐acrylate and pentaerythritol dia‐crylate and photoinitiator. Fourier transfer infrared, ¹H NMR, and thermal gravimetrical analysis were employed to investigate the structures and thermal properties of the EAs films. The introduction of EAAES into epoxy acrylate substantially improves its thermal properties and thermo‐oxidative stability at high temperatures. In addition, the acrylate containing arylene ether sulfone linkages can also improve pencil hardness and chemical and solvent resistance of the epoxy acrylate. The obtained UV‐curable epoxy acrylate containing arylene ether sulfone linkages is promising as oligomer for UV‐curable coatings, inks, and adhesives in some high‐tech regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41067.     

Amorphous polyamide coating resins from sugar-derived monomers

In this article, the synthesis of bio-based polyamides for powder coating applications and their evaluation in a solventborne coating system are reported. The M _n values of the resins were between 3000 and 4000 g mol^?1 and the resins displayed T _g values from 60 to 80°C. Both amine and carboxylic acid functionalities (total ~0.6 mmol g^?1) were introduced for curing purposes. The resins were cured with triglycidyl isocyanurate (TGIC) or N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide (Primid XL-552). The curing reaction was followed using rheology which indicated that TGIC achieved higher reaction rates and higher gel contents. The DSC analysis of the cured disks showed that all cured samples were amorphous as is desired for the targeted coating application. The resins required a curing temperature higher than 150°C. Aluminum panels were coated using a solventborne approach and the coatings were cured at 180°C during 1 h. Dewetting was observed on all panels. Network formation was adequate for an amine-functional resin cured with TGIC as indicated by solvent resistance testing. In conclusion, the developed bio-based polyamide resins are promising materials to be used as binder resins in powder coating applications.     

Preparation and characterization of soluble bismaleimide‐triazine resins based on asymmetric bismaleimide

A series of bismaleimide‐triazine resins (EBT) were prepared from 2‐(4′‐maleimido)phenyl‐2‐(4′‐maleimidophenoxyl)phenylbutane (EBA‐BMI) and 2,2‐bis(4‐cyanatophenyl)propane (BADCy). The resins show attractive processability with good solubility in low boiling point solvents and wide processing temperature windows. Introduction of diallylbisphenol A (DBA) can decrease the curing temperature of EBT resins that the curing exothermic peak temperature shifted from 291 to 237 °C as the content of DBA increased from 0 to 20%. The curing condition influenced the thermal properties of the cured EBT resins. The glass transition temperature increased as the curing temperature and curing time increased. The cured EBT resins show high glass transition temperature up to 352 °C, high thermal stability with 5% weight loss temperature over 405 °C, low coefficient of thermal expansion about 45 to 52 ppm/°C, and high storage modulus up to 2.6 GPa at 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44519.     

Photocrosslinked biobased phase change material for thermal energy storage

A series of novel photocrosslinked biobased shape‐stabilized phase change materials (PCMs) based on octadecanol, eicosanol and docosanol have been prepared by UV technique for the purpose of thermal energy storage applications. Epoxidized soybean oil was reacted with acrylic acid to form acrylated soybean oil (ASO). The structure and composition, cross‐section morphology, thermal stability performances and phase change behaviors of ASO and UV‐cured PCMs were examined by using Attenuated total reflection fourier transform infrared spectroscopy, thermogravimetric analysis system (TGA), scanning electron microscopy, and differential scanning calorimetry. The results indicate that the UV‐cured biobased PCMs possess perfect phase change properties and a suitable working temperature range. The heating process phase change enthalpy is measured between 30 and 68 J/g, and the freezing process phase change enthalpy is found between 18 and 70 J/g. The decomposition of UV‐cured PCMs started at 260 °C and reached a maximum of 430 °C. All the biobased UV‐cured PCMs improved latent heat storage capacity in comparison with the pristine ASO sample. With the obtained results we conclude that, these materials promise a great potential in thermal energy storage applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43757.     

Synthesis of novolac‐type phenolic resins using glucose as the substitute for formaldehyde

Novel Novolac type phenolic resins were prepared using glucose as the substitute for toxic formaldehyde (a carcinogenic chemical). The resins were synthesized with varying molar ratios of phenol to glucose, catalyzed by strong acid (such as sulfuric acid) at 120–150°C. Analysis of the resins using gel permeation chromatography (GPC) and proton nuclear magnetic resonance (¹H‐NMR) showed that they were broadly distributed oligomers derived from the Fridel‐Crafts condensation of phenol and glucose. Using hexamethylenetetramine (HMTA) as the curing agent, the phenol‐glucose resins could be thermally cured and exhibited exothermic peaks at 130–180°C, typical of thermosetting phenolic resins. The cured resins showed satisfactory thermal stability, e.g., they started to decompose at >280°C with residual carbon yields of above 58% at 600°C. Based on the thermal properties, phenol‐glucose resin with a molar ratio of 1 : 0.5 is promising as it could be cured at a lower temperature (147°C) and exhibited a satisfactorily good thermal stability: it started to decompose at >300°C with a residual carbon yield of >64% at 600°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Chemically stable polyphenylene ether microcapsules prepared using a facile method for the self‐healing of polymers

Chemically stable polyphenylene ether (PPO) microcapsules (MCs) filled with epoxy resins (PPO‐EP MCs) were prepared using low‐molecular‐weight PPO with vinyl end‐groups as shell wall and epoxy resins as core material using an oil‐in‐water emulsion solvent evaporation method. This method for synthesizing MCs with PPO shell walls is simple, convenient and novel, which can avoid the influence of processing parameters on the chemical stability of the epoxy resin core material. The resulting PPO‐EP MCs exhibit good chemical stability below 255 °C mainly owing to the absence of a polymerization catalyst of the epoxy resins. The initial thermal decomposition temperature of the MCs is about 275 °C. The MCs were embedded in a 4,4′‐bismaleimidodiphenylmethane/O,O′‐diallylbisphenol A (BMI/BA) thermosetting resin system. When processed at high temperature (up to 220 °C), the microencapsulated epoxy resins could be released from the fractured MCs to matrix crack surfaces and bond the crack surfaces. An amount of 8 wt% MCs restored 91 and 112% of the original fracture toughness of the BMI/BA matrix when heated at 220 °C/2 h and 80 °C/1 h + 220 °C/2 h, respectively. The MCs only slightly decreased the thermal property of the matrix. © 2016 Society of Chemical Industry     

Synthesis of silicone–acrylic resins and their applications to superweatherable coatings

Silicone–acrylic resins were synthesized to prepare superweatherable paints for building materials. The raw materials used were n‐butyl acrylate, methyl methacrylate, and n‐butyl methacrylate as acrylic monomers and 3‐methacryloxypropyltrimethoxysilane (MPTS) as a silicone monomer reactive with the acrylic monomers. Acrylic copolymers were synthesized such that their glass‐transition temperatures were adjusted to 30°C and their MPTS contents were varied to 10, 20, and 30 wt %. As the content of silicone and MPTS increased, average molecular weight and viscosity increased, and thermal stability at high temperatures improved. When we tested the properties of coatings by blending the synthesized silicone–acrylic resins with a white pigment, adhesion was superior with various substrates, and their properties were suitable on the whole. Weatherability was tested by an outdoor exposure test with a weather‐ometer and an accelerated weathering tester, and their results showed that silicone–acrylic resin composed of 30 wt % MPTS was a superweatherable coating. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1614–1623, 2001     

Effects of small molecular weight silicon‐containing acrylate on kinetics,morphologies, and properties of free‐radical/cationic hybrid UV‐cured coatings

A series of UV‐curable, silicon‐containing mixtures were prepared by adding different micro amounts of small molecular weight silicon‐containing acrylate KH570 to an interpenetrating polymer network system composed of cycloaliphatic polyurethane acrylate, trimethylolpropane triacrylate, cycloaliphatic epoxy resin, free‐radical photoinitiator Irgacure 754 and cationic photoinitiator Irgacure 250 with a weight ratio of 15 : 15 : 65 : 1 : 4. Hybrid coatings with different addition amounts of KH570 (0.2, 0.6, 1.0 wt %) were cured from the mixtures by UV‐initiated free‐radical/cationic dual curing technique. Final reactant conversions and photopolymerization rates of the hybrid UV‐cured coatings were improved with the increase of KH570 content, as evaluated by conversion profiles. The morphologies and microstructures were characterized by scanning electron micro‐scopic, atomic force micrographic, and fourier transform infrared spectrophotometer measurements. Thermal, mechanical, and surface properties of the hybrid UV‐cured coatings were investigated. The increase in KH570 content caused a decrease in mechanical properties besides the breaking elongation. Thermo‐gravimetric analysis revealed that the incorporation of silicon into cross‐linked network structure resulted in high thermal stability. The surface properties of hybrid UV‐cured coatings, such as hardness, contact angle, flexibility, and glossiness were also examined. It is found that transparent hybrid coating with the addition of 1.0 wt % KH570 exhibited a relatively higher contact angle as a direct result of a relatively higher hydrophobic surface. These researches showed that micro amounts of small molecular weight silicon‐containing acrylate could greatly influence the morphologies of liquid nitrogen quenching cross sections and properties of hybrid UV‐cured coatings and could be used to modify UV‐cured coatings for some superior properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40655.     

Flame-retardant Elvacite acrylic resin/clay nanocomposites

Flame-retardant Elvacite acrylic resin/Cloisite 6A nanocomposites were prepared via direct melt intercalation. Transmission electron microscopy micrographs showed that 75% of the clay platelets were completely exfoliated. This high degree of exfoliation resulted in a large improvement in thermal stability and UV absorption properties without sacrificing optical clarity. Cone calorimetry tests clearly showed that the heat release rate was far lower and more gradual in the nanocomposites than in pure resins. Thermal gravimetric analysis measurements showed that the thermal stability of nanocomposites was enhanced by almost 50°C (at 50 wt% loss) when the samples were thermally degraded under nitrogen. These results are consistent with a dramatic increase in the specific heat of the nanocomposites as verified by high precision differential scanning calorimetry measurements. Additionally, Fourier transform infrared spectroscopy results indicated that the introduction of clay did not change the chemical structure of acrylic resins.     

Bis[4‐(4‐maleimidephen‐oxy)phenyl]propane/N,N‐4,4′‐bismaleimidodiphenylmethyene blend modified with diallyl bisphenol A

In this article, 2,2′‐bis[4‐(4‐maleimidephen‐oxy)phenyl)]propane (BMPP) resin and N,N‐4,4′‐bismaleimidodiphenylmethyene (BDM) resin blends were modified by diallyl bisphenol A (DABPA). The effects of the mole concentration of BMPP on mechanical properties, fracture toughness, and heat resistance of the modified resins were investigated. Scanning electron microscopy was used to study the microstructure of the fractured modified resins. The introduction of BMPP resin improves the fracture toughness and impact strength of the cured resins, whose thermal stabilities are hardly affected. Dynamic mechanical analysis shows that the modified resins can maintain good mechanical properties at 270.0°C, and their glass transition temperatures (T_g) are above 280.0°C. When the mole ratio of BDM : BMPP is 2 : 1(Code 3), the cured resin performs excellent thermal stability and mechanical property. Its T_g is 298°C, and the Charpy impact strength is 20.46 KJ/m². The plane strain critical stress intensity factor (K_IC) is 1.21 MPa·m^0.5 and the plane strain critical strain energy release rate (G_IC) is 295.64 J/m². Compared with that of BDM/DABPA system, the K_IC and G_IC values of Code 3 are improved by 34.07% and 68.10%, respectively, which show that the modified resin presented good fracture toughness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40395.     

A novel flame retardant UV‐curable vinyl ester resin monomer based on industrial dipentene: Preparation,characterization, and properties

A novel bio‐based and flame‐retardant UV‐curable vinyl ester resin (VER) monomer named Diglycidyl ester of maleinized dipentene modified with dibutyphosphate and methacrylic anhydride (MDDMD) was synthesized from industrial dipentene via Diels‐Alder reaction, glycidylation, epoxy ring‐opening reaction, and esterification. Its chemical structures were characterized by Fourier transform infrared (FTIR) analysis and proton nuclear magnetic resonance (¹H‐NMR). In order to improve its flexibility, we prepared a series of copolymers under UV light radiation by mixing it with certain proportions of poly(ethylene glycol) dimethacrylate‐200 (PEGDMA‐200) which contained flexible groups. Their tensile property, curing degrees (CD), hardness, limiting oxygen index (LOI), dynamic mechanical thermal properties, and thermostability were all investigated. The cured mixed resins have a relatively high tensile strength of 10.05 MPa and curing degrees up to 92.5%. Both hardness (range: 50 to 23 HD) and LOI (range: 22.8% to 24.4%) of cured resins are improved with the increase of MDDMD content. Dynamic mechanical analysis (DMA) shows that their glass transition temperatures rise with the increase of MDDMD content. Thermogravimetric analysis (TGA) shows that the thermal stability of cured resins is enhanced with the increase of PEGDMA‐200 content, as the main thermal initial decomposition temperatures are all above 260 °C and char yield at 800 °C are above 18.10%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44084.     

A novel type of Si‐containing acrylic resins: Synthesis,characterization, and film properties

A novel type of Si‐containing acrylic resins was prepared by two steps and investigated their usage as surface coatings materials. At first a reactive polysiloxane intermediate Z‐6018 was reacted with 2‐hydroxyethyl methacrylate (HEMA) in toluene at 110°C under N₂ atmosphere. After the condensation reaction was stopped, reacted with different acrylic ester monomers such as ethyl acrylate (EA) and methyl methacrylate (MMA) at different mole ratio (1/3 and 1/4) by the free radical addition polymerization. Structures of Si‐containing acrylic resins were characterized by Fourier Transform Infrared Spectrometer (FTIR) and thermal properties of these resins were investigated by thermogravimetric analysis and differential scanning calorimetry DSC techniques. Surface coating properties of the films prepared from these resin were also determined. The results showed that all films are flexible, glossy or semi gloss and have excellent drying and adhesion properties. All films also exhibit abrasion resistances moderately. Water resistance of the films was generally modified by cured in oven and alkaline resistance of the films prepared from resins containing ethyl acrylate units are excellent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Photopolymerization and thermal behavior of phosphate diacrylate and triacrylate used as reactive‐type flame‐retardant monomers in ultraviolet‐curable resins

Tri(acryloyloxyethyl)phosphate (TAEP) and di(acryloyloxyethyl)ethyl phosphate (DAEEP) were used as reactive‐type flame‐retardant monomers along with commercial epoxy acrylate and polyurethane acrylate oligomers in ultraviolet (UV)‐curable resins. The concentrations of the monomers were varied from 17 to 50 wt %. The addition of the monomers greatly reduced the viscosity of the oligomers and increased the photopolymerization rates of the resins. The flame retardancy and thermal degradation behavior of the UV‐cured films were investigated with the limiting oxygen index (LOI) and thermogravimetric analysis. The results showed that the thermal stability at high temperatures greater than 400°C and the LOI values of the UV‐cured resins, especially those containing epoxy acrylate, were largely improved by the addition of the monomers. The dynamic mechanical thermal properties of the UV‐cured films were also measured. The results showed that the crosslink density increased along with the concentrations of the monomers. However, the glass‐transition temperature decreased with an increasing concentration of DAEEP because of the reduction in the rigidity of the cured films, whereas the glass‐transition temperature increased with the concentration of TAEP because of the higher crosslink density of the cured films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 185–194, 2005     

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.     

Methacrylate/acrylate terminated derivatives of diglycidyl hexahydrophthalate: Synthesis,structural, and thermal characterization

Mono‐ or di(meth)acrylate‐terminated derivatives of diglycidyl hexahydrophthalate (ER) were prepared by reacting 1 : 1 or 1 : 2M ratio of ER and methacrylic acid or acrylic acid. These vinyl ester (VE) resins were characterized by determining epoxy equivalent weight, acid number, and molecular weight by gel permeation chromatography. Structural characterization was done by FTIR and ¹H NMR spectroscopy. In the ¹H NMR spectra of acrylate‐terminated VE resins, three proton resonance signals were observed in the region 5.8–6.4 ppm due to vinyl group while in methacrylate‐terminated VE resins only two proton resonance signals due to vinylidene protons were observed at 5.6–6.1 ppm. The Brookfield viscosity (room temperature (25 ± 2)°C) of these resins diluted with varying amounts of MMA was determined at 20 rpm. Curing behavior was monitored by determination of gel time and differential scanning calorimetry. An exothermic transition was observed in the DSC scans in the temperature range of (81–150)°C. Isothermal curing of MMA‐diluted VE resins containing AIBN as an initiator was done at 60°C for 2 h in N₂ atmosphere, and then heating for another 2 h in static air atmosphere. Thermal stability of isothermally cured resins in N₂ atmosphere was evaluated by thermogravimetric analysis. All cured resins decomposed above 310°C in single step. Thermal stability of the cured resins having acrylate end caps was marginally higher than the resins having methacrylate end groups. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Improvement in mechanical properties and thermal stability of solvent‐based pressure‐sensitive adhesives based on triazine heterocyclic monomer

A heat‐resistance monomer denoted as triazine heterocyclic compound (TGIC‐AA) was synthesized and applied into improving the thermal stability of solvent‐based acrylic pressure sensitive adhesives (PSAs) through copolymerization. The modified acrylic PSAs tapes possessed longer holding time at temperature up to 150°C and no large areas of residues could be seen when peeled off on the substrate while the temperature of test was cooled down to room temperature. The thermal stability could be significantly enhanced in PSAs as the content of triazine heterocyclic compounds increased due to the extensive crosslinking networks. This indicated a worthy method to prepared heat resistant acrylic PSAs. An obvious reduction in peel adhesion occurred at the content of crosslinkers range 5 wt %‐7 wt %, while beyond 7 wt % adhesion failure occurred. The influences of crosslinking density on the molecular weight, glass transition temperature and viscosity, etc. for PSAs were also studied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43281.     

Allyl ether‐modified unsaturated polyesters for UV/air dual‐curable coatings. I: Synthesis and characterization of the oligomers and their cured films

Allyl ether (AE)‐modified unsaturated polyester oligomers were synthesized from polyethylene glycol (PEG), maleic anhydride (MAH), and trimethylolpropane mono allyl ether (TMPAE), and characterized by Fourier transform infrared (FTIR) spectra. The UV/air dual‐curable coatings were prepared from the oligomers using vinyl ether (VE) as a reactive diluent. FTIR spectra showed that C?C bonds in the coating composition had polymerized partially after cured by UV or air. The investigation of rheological behavior of the dual curable composition suggested that all the systems belonged to pseudoplastic fluid, and the increasing allyloxy content in oligomer resulted in a higher viscosity. Differential scanning calorimetry (DSC) analysis showed that the increasing TMPAE‐PEG molar ratio resulted in lower T_g, and all samples had the same glass transition temperature irrespective of the type of curing. The results of TGA for cured films indicated that UV‐cured film had better thermal stability than the air‐cured one. The air‐cured film showed superior pencil hardness, impact strength, and flexibility to the UV‐cured counterpart. However, the air‐cured film had poor adhesion and electric resistance properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2765–2770, 2004     

Synthesis and characterization of UV‐curable acrylic resin containing fluorine groups

A novel fluorine‐containing acrylic resin, 4‐trifluoromethylphenyl glycerol dimethacrylate (TPGD), was synthesized and the structure was characterized by FTIR, ¹³C NMR, ¹H NMR, and ¹⁹F NMR spectroscopy. The conversion of cure reaction, thermal stability, glass transition temperature (T_g), and electrical properties of the TPGD acrylic resin cured with UV radiation were investigated. The thermal stability and T_g of the UV‐cured specimens show a maximum value at 1 wt% photoinitiator, due to the formation of advanced network structures. The cured specimens had a relatively low dielectric constant, attributed to the decreased deformation polarizability of segment motion in the fluorine‐containing resin. Copyright © 2004 Society of Chemical Industry     

电子束固化木器清漆的制备及性能研究

电子束（ EB）固化技术作为一种重要的辐射固化技术,其固化的清漆涂层性能在许多方面优于紫外（ UV）光固化清漆涂层。本研究通过选取不同类型的商品化丙烯酸树脂及活性稀释剂配制木器涂料配方,分别利用电子束（ EB）和紫外光（ UV）对其进行固化,然后对固化后的涂层进行基本性能、热性能和机械性能的表征。研究结果表明： EB固化速度快,固化膜具有较高的铅笔硬度和附着力,而且树脂种类和单体结构的不同会对电子束固化涂层的热性能及机械性能产生影响。     

High glass transition temperature bismaleimide‐triazine resins based on soluble amorphous bismaleimide monomer

A novel bismaleimide (DOPO‐BMI) with unsymmetrical chemical structure and DOPO pendant group has been prepared. The particular molecular structure makes DOPO‐BMI show an intrinsic amorphous state with a T_g about 135°C and excellent solubility in most organic solvents, which is beneficial to the processability of bismaleimide composite materials. A series of bismaleimide‐triazine (BT) resins have been prepared based on DOPO‐BMI and 2,2‐bis(4‐cyanatophenyl)propane at various weight ratios. The prepared BT resins show outstanding solubility in organic solvent and low viscosity about 10–671 mPa s at 180°C. The cured BT resins exhibit high glass transition temperature (T_g) over 316°C. As the weight ratio of DOPO‐BMI increases to 80% (BT80), the T_g can rise to 369°C (tan δ). The cured BT resins also show good thermal stability with the 5% weight loss temperature over 400°C under both nitrogen and air atmosphere. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42882.