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.     

UV‐curable sol–gel based protective hybrid coatings

UV‐curable, novel, fluorinated polyether ether ketone urethane acrylate oligomer (FPEEKUA) has been synthesized and used as corrosion‐protector in sol–gel hybrid coatings for metallic substrates. Incorporation of FPEEKUA and sol–gel in the formulations improved coatings’ physical properties such as gel content, hardness, adhesion, gloss, flexibility, and contact angle. Due to strong interaction between acrylate and highly crosslinked structures, mechanical properties improved drastically with homogenously dispersed structures throughout the organic matrix, while water uptake values decreased and thermal stability and char yields increased. Highest contact angle values were measured up to 94° with shinny coatings. The results are important for two reasons. First, polyether ether ketone (PEEK) immiscibility problem are overcome by using reactive oligomer and benefitted from high performance properties of poly(arylene ether ketones) (PAEK)s in hybride coating applications. Second, Coatings combine the advantages of sol–gel with poly(arylene ether ketone urethane acrylate) (PAEKUA) oligomer and they can be used as barrier coatings in metal corrosion protection. Performance tests in corrosive mediums at room temperature of chlorine solution (bleach) for 24 h and also in a 10 wt% HCl solution for 92 h produced promising results for use in corrosion mitigation applications in highly corrosive downstream oil and gas industry. POLYM. ENG. SCI., 59:E146–E154, 2019. © 2018 Society of Plastics Engineers     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Synthesis and ultraviolet‐curing behaviors of vinyl ether functionalized polyurethane oligomers

The vinyl ether functionalized oligomer is one of the most basic components of vinyl ether functionalized materials for cationic UV‐curable coatings. In this study, three types of vinyl ether functionalized polyurethane oligomers (i.e., polyether, polyester, and polydimethylsiloxane) were synthesized with diisocyanate, diol, and hydroxyethyl vinyl ether. These oligomers were characterized by IR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The effect of the raw material ratio on the oligomer, UV‐curing behaviors, and thermal properties of these oligomers were investigated. The UV‐curing behavior was analyzed by real‐time Fourier transform infrared spectroscopy. The vinyl ether terminated polyester urethane oligomer exhibited better UV curing, with a higher final conversion and maximum UV‐curing rates. In addition, the light intensity was enhanced for oligomers with better UV‐curing properties. Research on these vinyl ether functionalized oligomers is essential to the development and applications of cationic vinyl ethers systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40501.     

Pendant crosslinked poly(aryl ether sulfone) copolymers sulfonated on backbone for proton exchange membranes

A series of sulfonated poly(aryl ether sulfone) copolymers containing phenyl pendant groups with sulfonic acid groups on the backbone were synthesized through condensation polymerization. The degree of sulfonation (DS) of the copolymers was controlled by changing the feed ratios of sulfonated to unsulfonated monomers. Post‐crosslink reactions are carried out with 4,4′‐thiodibenzoic acid (TDA) as a crosslinker and the carboxylic acid groups in TDA can undergo Friedel–Craft acylation with the phenyls pendent rings in sulfonated poly(arylene ether sulfone)s copolymers to prepare polymer electrolyte membranes for fuel cell applications. The chemical structures of crosslinked and uncrosslinked sulfonated poly(arylene ether sulfone)s copolymers (SPSFs and CSPSFs) were characterized by FTIR, ¹H NMR spectra. The thermal and mechanical properties of the membranes were characterized by thermogravimetric analysis and stress–strain test. The dependence of water uptake, methanol permeability, proton conductivity, and selectivity on DS was studied. Transmission electron microscopic observations revealed that SPSFs and CSPSFs membranes form well‐defined microphase separated structures. POLYM. ENG. SCI., 54:2013–2022, 2014. © 2013 Society of Plastics Engineers     

Superhydrophobic films of UV‐curable fluorinated epoxy acrylate resins

Photopolymerization processes are often used in industrial applications because of their solvent‐free formulations and various advantages over conventional thermal processes. Fluorinated monomers and oligomers yield coatings of great interest because of the peculiar characteristics of fluorine atoms: these coatings show hydrophobicity, chemical stability, weathering resistance, etc. Novel UV‐curable fluorinated epoxy acrylate oligomers were synthesized from 1H,1H‐perfluorohexan‐1‐ol, 1,6‐hexamethylene diisocyanate (HDI) and epoxy acrylate (EA). The HDI plays the role of a spacer group in the side chain between the EA backbone chain and the fluorinated segment. This new spacer containing a urethane moiety with long alkyl groups can exhibit a self‐organization effect through the formation of strong hydrogen bonding. This resulted in a stiffening of the whole HDI urethane–perfluoalkyl chain to form nanostructure surface segregation. The designed fluorinated EA with fluoroalkyl (C₅F₁₁) units in the side chain exhibited a contact angle of about 151°, which is in the superhydrophobic range. Copyright © 2010 Society of Chemical Industry     

Influence of a long‐side‐chain‐containing reactive diluent on the structure and mechanical properties of UV‐cured films

The dimethacrylate reactive diluent (HEMA‐DDSA), a long‐side‐chain‐containing reactive diluent, was prepared by reacting 2‐dodecen‐1‐ylsuccinic anhydride with two equivalents of hydroxyethyl methacrylate. Its structure was characterized by IR and ¹H NMR spectroscopy. This new diluent was added into the formulation of UV‐curable epoxy acrylate networks. Results show that the formulation with the addition of HEMA‐DDSA has massively reduced viscosity and shows several attractive properties of epoxy acrylate oligomers. The mechanical resistance of the films is dramatically enhanced with the incorporation of long alkyl groups derived from HEMA‐DDSA, the plastic deformation zone expands, thus decreasing the inner stress of the polymer structure. Moreover, the cured coatings have a higher glass transition temperature as the percentage of HEMA‐DDSA is increased up to 5 wt%. Due to the excellent integrated performance of the polymeric films, HEMA‐DDSA proved to be an effective reactive diluent, which is of potential interest for applications in high performance materials. © 2016 Society of Chemical Industry     

UV‐curable coatings with nano‐TiO2

Nano‐TiO₂ particles were first milled into butyl acetate or trimethylolpropane triacrylate (TMPTA) to obtain TSB and TST slurries, then embedded into epoxy acrylate to obtain UV‐curable coating. The influence of nano‐TiO₂ particles on the photopolymerization kinetics, tack free time, thermal and optical properties of UV‐curable coatings was investigated. It was found that TST‐based coating had a decreasing but TSB‐based coating had an increasing UV cured rate in comparison with the pristine epoxy acrylate. Nevertheless, the TST‐based coating occupied shorter tack free time, good thermal property and UV absorbance than their corresponding TSB‐based coating. POLYM. ENG. SCI. 46:1402–1410, 2006. © 2006 Society of Plastics Engineers.     

Effect of hyperbranched acrylates on UV‐curable soy‐based biorenewable coatings

Utilization of biorenewable components in UV‐curable coating formulations is both economically and environmentally beneficial, particularly when compared to their petrochemical‐based counterparts. To produce UV‐curable coatings of high biorenewable content with enhanced performance, acrylated epoxidized soybean oil (ASBO) was combined with biorenewable reactive diluent tetrahydrofufuryl acrylate, adhesion promoters, photoinitiator and hyperbranched acrylates (HBAs) as synthetic tougheners. The HBAs were found to impart high functionality and low viscosity, thus increasing crosslinking in the coating network and improving mechanical and thermal properties such as film hardness, adhesion, solvent resistance, impact resistance, tensile modulus and toughness, glass transition temperature and thermal stability. Real‐time Fourier transform infrared spectroscopy showed decreased acrylate conversion when compared with a reference formulation without HBAs, which was attributed to earlier coating network vitrification during UV irradiation. ASBO‐based coatings were also thermally annealed to allow further reaction of unreacted components in the vitrified network. As a result, coating properties were further improved. Overall, the addition of HBAs as synthetic tougheners to UV‐curable ASBO‐based biorenewable coating systems was shown to greatly improve the corresponding coating properties. Copyright © 2010 Society of Chemical Industry     

Synthesis and properties of poly(arylene ether)s based on 3‐pentadecyl 4,4'‐biphenol

A new biphenol, 3‐pentadecyl 4,4′‐biphenol, was synthesized starting from 3‐pentadecylphenol and was polycondensed with 4,4′‐difluorobenzophenone, 1,3‐bis(4‐fluorobenzoyl)benzene and bis(4‐fluorophenyl)sulfone to obtain poly(arylene ether)s with biphenylene linkages in the backbone and pendent pentadecyl chains. Inherent viscosities and number‐average molecular weights (M_n) of the poly(arylene ether)s were in the range 0.50 ? 0.81 dL g^?1 and 2.2 × 10⁴ ? 8.3 × 10⁴, respectively. Detailed NMR spectroscopic studies of the poly(arylene ether)s indicated the presence of constitutional isomerism which existed because of the non‐symmetrical structure of 3‐pentadecyl 4,4′‐biphenol. The poly(arylene ether)s readily dissolved in common organic solvents such as dichloromethane, chloroform and tetrahydrofuran and could be cast into tough, transparent and flexible films from their chloroform solutions. The poly(arylene ether)s exhibited T_g values in the range 35–60 °C which are lower than that of reference poly(arylene ether)s without pentadecyl chains. The 10% decomposition temperatures (T₁₀) of the poly(arylene ether)s were in the range 410–455 °C indicating their good thermal stability. A gas permeation study of poly(ether sulfone) containing pendent pentadecyl chains revealed a moderate increase in permeability for helium, hydrogen and oxygen. However, there was a large increase in permeability for carbon dioxide which could be attributed to the internal plasticization effect of pendent pentadecyl chains. © 2016 Society of Chemical Industry     

Preparation and characterization of hybrid thiol‐ene/epoxy UV–thermal dual‐cured systems

Hybrid thiol‐ene/epoxy coatings were prepared by combining thiol‐ene photo‐curable formulations with epoxy monomers, through a dual UV–thermal curing process. An increase in glass transition temperature and in storage modulus was observed for the hybrid thiol‐ene/epoxy coatings when compared with the pristine thiol‐ene UV‐cured system. Also, the bisphenol A moieties introduced into the hybrid networks during the dual‐curing process induced an increase in thermal stability of the cured materials. It has been demonstrated that the addition of epoxy monomer to the thiol‐ene photo‐curable system is a good strategy to follow in order to improve the final properties of thiol‐ene‐based coatings leading to a wide range of possible applications for the hybrid materials. Copyright © 2010 Society of Chemical Industry     

A new intumescent flame retardant containing phosphorus and nitrogen: Preparation,thermal properties and application to UV curable coating

A novel intumescent flame retardant piperazine-N,N′-bis(acryloxyethylaryl-phosphoramidate) (N-PBAAP) containing phosphorus and nitrogen used for UV curable coating was synthesized and characterized by Fourier transform infrared spectrometry (FTIR), ¹H and ³¹P nuclear magnetic resonances (NMRs). The thermal degradation and volatilized products of the N-PBAAP cured film were monitored by real time Fourier transform infrared (RT-FTIR) and thermal gravimetric-Fourier transform infrared (TG-FTIR) technique, respectively. Scanning electron microscopy (SEM) was employed to investigate the surface morphology of the residual char. And possible mechanism for the thermal degradation of N-PBAAP film was proposed. To investigate the flame retardancy of N-PBAAP in UV curable coatings, a series of UV curable intumescent flame retardant resins were obtained by blending N-PBAAP with EA (epoxy acrylate oligomer) in different ratios. The flammability and thermal properties of the cured films were studied by Microscale Combustion Calorimeter (MCC) and thermogravimetric analysis (TGA). In MCC test, the peak heat release rates (pHRRs) of the blends were all lowered by the addition of N-PBAAP comparing with the pure EA. And TG results revealed that N-PBAAP can greatly enhance the char residues of EA films at high temperature region.     

UV‐curable,oxetane‐toughened epoxy‐siloxane coatings for marine fouling‐release coating applications

BACKGROUND: UV‐curable coatings are promising candidates for environmentally friendly marine fouling‐release coatings. Cationic UV‐curable epoxy‐siloxane release coatings show good release performance but suffer from poor coating mechanical properties. A difunctional oxetane monomer, DOX, was co‐photopolymerized with an epoxy‐siloxane oligomer at loading levels from 10 to 40 wt% to obtain toughened fouling‐release coatings. RESULTS: The DOX‐toughened coatings showed enhanced cationic photopolymerization activity, solvent resistance and modulus. DOX‐toughened coatings (10 and 20 wt%) exhibited higher impact resistance. The DOX‐toughened coatings showed no leachate toxicity and the coatings were hydrophobic and non‐toxic to biofilm growth when analyzed with marine bacteria and algae. In general, 10 and 20 wt% DOX‐toughened coatings exhibited better marine bacteria and algae fouling‐release performance among the DOX‐toughened coatings. Pseudo‐barnacle shear release stress for the DOX‐toughened coatings increased with increasing DOX content. Live barnacle reattachment assay showed that 10 and 20 wt% DOX‐toughened coatings had comparable barnacle removal stress to commercial silicone reference coatings. CONCLUSIONS: DOX‐toughened (10 and 20 wt%) UV‐curable epoxy‐siloxane coatings exhibited enhanced mechanical properties and better overall marine fouling‐release performance among the toughened UV‐curable release coatings studied. Copyright © 2008 Society of Chemical Industry     

Synthesis of Poly(arylene ether ketone)s containing Unsymmetrical Pyridyl Ether Linkages

Summary New high molecular weight poly(arylene ether ketone)s were prepared from pyridine containing unsymmetrical dichloro monomers. Incorporation of unsymmetrical pyridyl ether linkages instead of phenylene ether linkages reduces the high crystallinity of parent poly(arylene ether ketone)s and provides enhanced solubility. Replacement of a single atom in the repeating units of polymers can efficiently change the physical properties of the resulting polymers. The pyridyl ether containing poly(arylene ether ketone)s showed outstanding thermal stability (T_d5>470 °C).     

Copolymers of poly(arylene sulfide sulfone)/poly(ether sulfone): Synthesis,structure, and rheology properties

In order to overcome the poor flowability of poly(arylene sulfide sulfone) (PASS), we introduced ether bonds into the polymer main chain. A series poly(arylene ether sulfide sulfone) copolymers (PAESS) containing different proportion of ether bonds were synthesized with 4,4′‐dichlorodiphenyl sulfone (DCDPS), sodium sulfide (Na₂S·xH₂O), and 4,4′‐dihydroxydiphenyl ether (DHDPE). The copolymers were characterized by Fourier transform infrared (FTIR), ¹H‐nuclear magnetic resonance (NMR), differential scanning calorimetry, dynamic mechanical analysis (DMA), and rheometer. The results of FTIR and ¹H‐NMR indicate the copolymers are synthesized successfully. PAESS were found to have excellent thermal properties with glass transition temperature (T_g) of 175.7–219.1 °C and 5% weight lost temperature were all above 420 °C. The tensile and DMA test indicates that these resultant copolymers have good mechanical properties with tensile strength of 60 MPa and storage modulus of 1.5 GPa. From the results of rheology properties testing, we found that the melt stability and melt flowability of PASS were improved distinctly from 25,470 Pa s down to 355 Pa s with the incorporation of ether bonds. That will be quite beneficial to the processing of PASS, especially for the thermoforming of precision products. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46534.     

Compatibilization and property characterization of polycarbonate/polyurethane polymeric alloys

Semi‐crystalline dendritic poly(ether‐amide)s were synthesized by modifying hydroxyl end‐groups of dendritic poly(ether‐amide) with aromatic urethane acrylate and octadetyl isocyanate. The ratio of these modifiers can adjust the final properties of products to fulfill the requirements of UV‐curable powder coatings. These UV‐curable semi‐crystalline dendritic poly(ether‐amide)s have a T_g in the range of 41–45°C and a T_m of around 120°C. Their thermal behavior and semi‐crystalline properties were studied by DSC and XRD. The photopolymerization kinetics was investigated by Photo‐DSC. The residual unsaturation, thermal stability, and hardness of the UV‐cured films were also studied. The obtained results show that these semi‐crystalline dentritic poly(ether‐amide)s may be used as prepolymers in UV‐curable powder coating systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 287–291, 2003     

Effect of chemical structure and shear force on the morphology and properties of jet printed black micropatterns using imide epoxy binders

Epoxy and epoxy acrylates with phthalimide groups on the main chain or pendent side chain were synthesized and used as binders for solvent‐free UV‐curable inks. Effects of chemical structures on the solubilities of binders in monomers, together with the influences of shear force and ink compositions on the morphology and nanoindentation properties of the microstripes were studied. PIK1 inks containing BAPSBD epoxy with phthalimide groups on the main chain showed shear‐thinning behaviors and pigment aggregation problems. Variations of the shear stress at different positions of the dispenser led to PIK1 microstripes with rough central regions and smoother edges. AMPDP acrylate with pendent phthalimide side chain afforded not only good solubility in monomers but also good thermal and mechanical properties after curing. Stripes prepared by the PIK2 ink containing AMPDP exhibited straight edge and smooth surface. Considering the solubility and compatibility in inks, together with properties of cured stripe, binders with pendent phthalimide groups are better candidate as UV‐curable ink compositions than those with main chain phthalimide groups. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

紫外光固化环氧丙烯酸酯的研究进展

环氧丙烯酸酯树脂是紫外光(UV)固化领域中用量最大的一类光固化树脂,具有粘接强度大、硬度高及耐化学药品性等优点,但也存在黏度较大、韧性较差等问题。为了提高环氧丙烯酸酯的综合性能,有必要对其进行改性。介绍了环氧丙烯酸酯的合成基本原理及主要合成条件对树脂的影响,综述了国内外近期对环氧丙烯酸酯改性的主要方法及研究进展,指出了目前环氧丙烯酸酯在涂料中应用存在的主要问题,为今后对环氧丙烯酸酯性能的进一步改进提供了参考。     

Synthesis and properties of novel fluorinated poly(arylene ether)s

Dibromomethylene‐containing monomer with a tetrafluorobenzene central unit was synthesized using 2,3,5,6‐tetrafluoro‐1,4‐bis(4‐methylphenoxy)benzene as a starting material. This approach enabled preparation of several fluorinated poly(arylene ether)s containing isomeric fragments, with or without allyl or acetyl side groups, which were prepared by interaction of the synthesized tetrafluorobenzene‐based monomer with various types of hydroxyl‐substituted diphenyl ethers. The structure of the synthesized compounds was determined using Fourier transform infrared, ¹H NMR and ¹⁹ F NMR spectroscopy techniques. Most of the resulting polyethers were soluble in chlorinated, ether‐type or polar amide solvents. The molecular weight, mechanical and thermal properties of the synthesized fluorinated poly(arylene ether)s were studied depending on the inherent isomery of macromolecular chains and the nature of functional groups. Some ways of functionalization of the prepared fluorinated polyethers with epoxy and triethoxysilyl groups were proposed. © 2015 Society of Chemical Industry     

Preparation and evaluation of epoxy methacrylate UV‐curable coatings containing phthalazinone

Epoxy methacrylate resin (EMA) UV‐curable coatings exhibit high reactivity, low viscosity and excellent chemical resistance in environmentally friendly coatings. A novel EMA containing phthalazinone moieties for high temperature resistant UV‐curable coatings was synthesized. The formulations were cured with hexanediol diacrylate (HDDA) and trimethylol propane triacrylate (TMPTA) as reactive diluents promoted by a photoinitiator, and then interpenetrating polymer networks were generated. The mechanical, chemical and thermal properties of the clear coatings were characterized using Chinese National Standard methods (GB). EMA was used with UV radiation curing in combination with 6.7 wt% of HDDA and 13.4 wt% of TMPTA, and the properties of the cured films were as follows: pencil hardness of 5 H, 30% NaOH resistance for 30 days, 15% HCl resistance for 10 days, 3% NaCl resistance for 30 days and 5% weight loss temperature of 300.5 °C. EMA UV‐curable coatings containing phthalazinone exhibit excellent chemical and thermal stability, and could be potential candidates for UV‐curable zero volatile organic compound coatings applied in the fields of salt spray corrosion, strong radiation and high‐temperature resistance. Copyright © 2009 Society of Chemical Industry