Room temperature‐curable VARTM epoxy resins: Promising alternative to vinyl ester resins

The objective of this investigation is to characterize various room temperature (RT)‐curable epoxies for vacuum‐assisted resin transfer molding (VARTM) of large structure manufacturing. Six epoxy candidate resins: X‐40, 780‐33, 780‐35, 8601/8602, 8602, 8603, and two vinyl ester resins (VE), 411‐350 and 411‐510A, are physically and thermochemically characterized. All the resins are cured at RT with extended period of time. The degree of cure for 24‐h RT‐cured samples ranges from 70 to 85% for epoxies and is comparable with the baseline VE systems (75%). After 1 year at RT, the degree of cure increases from 90 to 98%. Most of the epoxies show a single transition in dynamic mechanical analysis and differential scanning calorimetry. However, two heterogeneous transitions are observed for the VE systems. The glass transition temperature increases monotonically with exposure time, except X‐40, that rapidly achieves a plateau and remains constant. The degree of cure for the majority of the systems increases logarithmically with RT curing time with excellent fitting (R² varies from 0.92 to 1). Consistent with the increase in degree of cure, the storage modulus increases and (tan δ)_max decreases with time of exposure. A negative correlation between the curing temperature range and the total heat of reaction is observed among the epoxy systems. However, the VE systems show the reverse trend. RT curing epoxy resin (X‐40) shows promising overall result to VE system and can be a viable alternative to VE for VARTM processing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Effect of tertiary amines on yellowing of UV‐curable epoxide resins

The work reported demonstrates that the yellowness of UV‐curable epoxide resins can be improved by adding certain tertiary amines in appropriately determined amounts. According to the results of our experiments, 2.0 wt% benzoyl peroxide added to a resin effectively enhances the crosslinking density, and phenolic free radicals are produced during UV curing, which consequently induce yellowness via the reaction of oxygen and the free radicals. Imidazole (1‐amine) and tertiary amines, including 1,2‐dimethylimidazole (2‐amine), 2,4,6‐tris(dimethylaminomethyl)phenol (3‐amine), 1‐methylimidazole (4‐amine) and 2‐methylimidazole (5‐amine), were chosen to be added to resins, and their effects on UV conversion and yellowness were investigated. According to the experimental results, tertiary amines in the resin can provide a certain degree of improvement in yellowness index (ΔYI) and color parameter (ΔE*_ab) of the resin sample. Whatever the type of tertiary amine, it is found that the optimum content of amine in resin is 1.0 wt%. Also, among the studied amines, the 3‐amine exhibits the highest UV reactivity and the best efficiency for yellowness improvement with values of Δa*, Δb*, ΔYI and ΔE*_ab as low as ? 1.4, 6.23, 11.27 and 6.48, respectively. Copyright © 2007 Society of Chemical Industry     

Studies on UV‐stable silicone–epoxy resins

Silicone–epoxy resins were synthesized through hydrosilylation of 1,2‐epoxy‐4‐vinyl‐cyclohexane with 1,3,5,7‐tetramethycyclotetrasiloxane. The silicone–epoxy resins showed high reactivity in the presence of aluminum complex/silanol compound catalysts. Curing of the resins was effected at extremely low concentrations of the aluminum acetylacetonate/Ph₂Si(OH)₂ catalyst to give hard materials with optical clarity. For the silicone–epoxy resins containing Si? H bonds, Al(acac)₃ alone is effective for the curing. The cured silicone–epoxy resins showed excellent UV resistance. An improvement in the lifetime of UV‐LEDs was achieved using the silicone–epoxy compositions as encapsulant. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3954–3959, 2007     

Properties of nanocomposites based on maleate‐vinyl ether donor—acceptor UV‐curable systems

UV‐curable nanocomposites based on donor–acceptor crosslinking chemistry were prepared containing organically modified montmorillonites. The coatings were characterized for thermal, mechanical, and morphological properties. X‐ray diffraction and transmission electron microscopy showed that nanocomposites were formed in all samples. Results showed that an increase in the percentage of clay caused an increased modulus and glass‐transition temperature. It was also seen that tensile modulus showed dramatic improvement when compared with the unmodified polyester sample. Real time IR kinetic data showed that higher conversions were obtained at higher clay loadings. Pendulum hardness values and tensile modulus values showed different trends in properties depending on the combination of polymer matrix and organomodification. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Kinetic behavior of photo‐polymerization of UV‐curable resins with carboxylic acid and amino groups

Photo‐polymerization behaviors of bisphenol‐A epoxy diacrylate (EPA) and six kinds of EPA‐derived resins containing different amounts of carboxylic acid, urethane, amide, and imide groups were studied by a photo differential scanning calorimetry. The dark polymerization was performed and pseudo‐steady state assumption of growing radicals was made to obtain the kinetic constants for propagation, bimolecular termination, monomolecular termination, and the concentration of growing radicals of different resins as a function of extent of reaction. Compared with EPA, it was found that the rate of polymerization and kinetic constants of the six resins were relatively small because the mobility of reacting species in resins was restricted by carboxylic acid, urethane, amide, and imide groups. Finally, three different photo‐initiators were used to initiate the polymerization, and their kinetic behaviors were compared. The effect of tertiary amine group of photo‐initiator on the rate of polymerization of resins having carboxylic acid group and the initiator efficiency were discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Preparation and thermal and thermo‐oxidative stability of vinylidene chloride‐co‐vinyl chloride copolymer/synthetic hectorite nanocomposites

Poly(vinylidene chloride‐co‐vinylchloride)/organically modified hectorite (VDC‐VC/SPN) nanocomposites were prepared by melt blending VDC‐VC copolymer with SPN in the presence of dioctyl phthalate, which acted as a plasticizer. As a result, the exfoliated structure was found in the VDC‐VC/SPN nanocomposites. In nitrogen atmosphere, VDC‐VC/SPN nanocomposites exhibited a single‐step thermal degradation. The thermal stability of VDC‐VC/SPN nanocomposites is significantly influenced by the SPN, which was modified with long alkyl ternary ammonium salt. In air atmosphere, VDC‐VC/SPN nanocomposites revealed a two‐step thermo‐oxidative degradation behavior. At the first degradation stage, the weight loss pattern is similar to that of VDC‐VC composites in nitrogen, in which the thermo‐oxidative stability of VDC‐VC/SPN nanocomposites is affected by the ternary ammonium salt and oxygen rather than its morphology. At the second degradation stage, both the enhanced thermo‐oxidative stability and the flame‐retardation ability of VDC‐VC composites are strongly and closely related to the morphology of nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci ,2009     

Effect of process conditions on the properties of surface‐modified organic pigments encapsulated by UV‐curable resins

Aqueous dispersions of nanoscale organic pigments were successfully prepared via ball milling and ultrasonication. The dispersed organic pigments were encapsulated into UV‐curable resins via a mini‐emulsion technique. Critical factors that affected the dispersion and encapsulation stability were investigated. The encapsulated organic pigments were characterised with transmission electron microscopy, thermogravimetric analyses, Fourier Transform‐infrared spectra and zeta potential. The results clarified that the type of dispersing agent plays an important role in achieving maximal dispersion stability. Encapsulated organic pigments showed greater dispersion stability, and better wettability than the original pigments. Polyester tetra‐acrylate oligomer can stabilise the mini‐emulsion from diffusion degradation and inhibit phase separation with time. 1,6‐Hexandiol dimethacrylate was the monomer of choice for ink‐jet printing inks. Furthermore, it was found that monomer/oligomer and pigment/resin ratios were more influential and needed to be optimised. Thermal analysis, ultracentrifuge sedimentation and morphologies provided supporting evidence for the encapsulation of organic pigments into UV‐curable resins.     

Preparation and characterization of UV‐curable ZnO/polymer nanocomposite films

A series of novel nano‐ZnO/polymer composite films with different ZnO contents was prepared through incorporation of pre‐made colloidal ZnO particles into monomer mixtures of urethane‐methacrylate oligomer and 2‐hydroxyethyl methacrylate, followed by ultraviolet (UV) radiation‐initiated polymerization. The colloidal ZnO nanoparticles with a diameter of 3–5 nm were synthesized from zinc acetate and lithium hydroxide in ethanol via a wet chemical method. In order to stabilize and immobilize the ZnO particles into the polymer matrix, the ZnO nanoparticles were further capped using 3‐(trimethoxysilyl)propyl methacrylate. Thermogravimetric analyses show that the ZnO nanoparticles were successfully incorporated into the polymer matrix and these ZnO/polymer composites have a good thermal stability. Transmission electron microscopy studies indicate the ZnO nanoparticles were uniformly dispersed in the polymer and they remained at the original size (3–5 nm) before immobilization. All nanocomposite films with ZnO particle contents from 1 to 15 wt% show good transparency in the visible region and luminescent properties. In addition, composite films with high ZnO content (>7 wt%) are able to absorb UV irradiation below 350 nm, indicating that these composite films exhibit good UV screening effects. Copyright © 2006 Society of Chemical Industry     

Morphology of rubber‐modified vinyl ester resins cured at different temperatures

The morphologies of styrene (St) crosslinked divinylester resins (DVER) modified with elastomers were analyzed. The primary focus of this study was on the effect of the molecular weight of the resins, the reactivity of the elastomeric modifiers, and the temperature of curing. All of these variables have a strong influence on both the miscibility and the viscosity of the system, affecting the phase‐separation process that takes place in the unreacted and the reacting mixture. The selected liquid rubbers were carboxyl‐terminated poly(butadiene‐co‐acrylonitrile) (CTBN), a common toughening agent for epoxy resins, and an almost unreactive rubber with the DVER; and St comonomers and vinyl‐terminated poly(butadiene‐co‐acrylonitrile (VTBN), a reactive rubber. Different morphologies potentially appear in these systems: structures formed by DVER–St nodules surrounded by elastomer and spanning the whole sample; dual cocontinuous micron‐size domains formed by elastomer‐rich or resin‐rich domains; and a continuous DVER–St‐rich phase with included complex nodular domains. These microstructures can be varied by just changing the nature and concentration of the elastomer, the molecular weight of the resin, or the curing temperature. The appearance of these morphologies is discussed as a function of the above variables. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 274–283, 2003     

Synthesis and kinetic studies of UV‐curable urethane‐acrylates

The UV‐curable urethane‐acrylates based on 2‐hydroxyethyl methacrylate (HEMA)‐terminated polyurethane (PU) for lithographic and coating applications are investigated in this study. Series of PU prepolymers were made from 4,4‐diphenyl methane diisocyanate (MDI), poly(propylene oxide) glycol (PPG 400), poly(butylene adipate)glycol (PBA 500), or poly(tetramethylene oxide) glycol (PTMO 1000) and are terminated with HEMA. The 2,2‐azobisisobutyronitrile (AIBN) was used as a UV‐initiator under air atmosphere. The curing kinetics of HEMA‐terminated PU film were studied. The curing analysis, using FTIR and reaction kinetics, indicate the reaction rate equation correlates well with the film thickness [T], initiator concentration [I], unreacted double bond concentration [C?C], and exposed energy [E] of the reaction system. The kinetic rate equation for the UV‐curable reaction can be written as © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3162–3166, 2004     

Preparation and properties of UV‐curable fluorinated polyurethane acrylates containing crosslinkable vinyl methacrylate for antifouling coatings

To obtain highly effective antifouling coatings, a series of UV‐curable polyurethane acrylates containing diluents [heptadecafluorodecyl methacrylate (PFA, 6 wt %)/isobornyl acrylate (IBOA, 34 wt %)/methyl methacrylate (MMA, 20‐5 wt %)/vinyl methacrylate (VMA, 0–15 wt %)] were prepared. This study examined the effect of bulky MMA (20‐5 wt %)/crosslinkable VMA (0–15 wt %) weight ratio on the properties of the UV‐curable polyurethane acrylates. The fluorine concentration in UV‐cured film surface increased with increasing VMA content up to 9 wt % and then decreased. The T_gα, transparency, elasticity, and mechanical properties of the UV‐cured film samples increased with increasing VMA content. The water/methylene iodide contact angles and surface tension of samples increased from 107/79 to 121/91° and decreased from 17.8 to 12.7 mN/m with increasing VMA content up to 9 wt % and then decreased/increased, respectively. From these results, it was found that the optimum VMA content was 9 wt % to obtain a high‐performance antifouling coating. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42168.     

Use of allyl‐functional benzoxazine monomers as replacement for styrene in vinyl ester resins

New vinyl ester systems are prepared using allyl‐functional benzoxazine monomers, 3‐allyl‐6‐methyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazine (pC‐ala) or bis(3‐allyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazin‐6‐yl)methane (BF‐ala), as reactive diluents for vinyl ester resins derived from an epoxy resin, diglycidyl ether of bisphenol A, instead of using styrene. Different initiators are used to investigate the copolymerization of allyl function from pC‐ala with vinyl function from vinyl ester resin prepolymer. The temperature dependence of viscosity is studied to demonstrate the retention of processability of the new vinyl ester resins. Dynamic mechanical and thermogravimetric analyses are used to investigate the dynamic mechanical properties and thermal stability of the new resins. Copyright © 2012 Society of Chemical Industry     

UV‐curable positive photoresists for screen printing plate

One of the most interesting application areas of screen printing is the production of microelectronic devices. Although negative photoresists are commonly used for the screen printing plate, their resolution limit is about 30 µm. A higher resolution of resist patterns on the screen plate is essential for microelectronic device applications. This paper describes the novel design of a UV‐curable positive photoresist and its application to the screen printing plate. Positive patterns on the screen plate were obtained by conventional photolithography using a photomask and 365 nm light and the patterns were exposed to 254 nm light to enhance the mechanical strength of the resist patterns. It was essential to use photoacid generators sensitive to 365 nm and photoradical generators sensitive to 254 nm. A screen printing plate, which enabled the formation of 6 µm wide conductive lines, was developed. © 2016 Society of Chemical Industry     

Preparation and characterization of UV‐curable organic/inorganic hybrid composites for NIR cutoff and antistatic coatings

In this study, UV‐curable organic/inorganic hybrid composite coatings with near infrared (NIR) cutoff and antistatic properties were prepared by high‐shear mixing of two kinds of polymer matrices and coated on plastic and glass substrates by the doctor‐blade method. This study also investigated the morphology, stability, optical properties, electrical resistivity, and durability of the UV‐cured composite coats. It was found that the composite coatings were very stable under centrifugation. Moreover, the films with transmittance of above 80% in a visible light region (400–800 nm) and of ～ 40% to 50% in the NIR region (1000–1600 nm) showed low haze of 6.9%, electrical resistivity of around 2.3 × 10⁷ Ω/square. Thus, excellent adhesion, scratch, and weathering durability can be produced on polycarbonate substrate at room temperature. The experimental results reveal that UV‐curable organic/inorganic hybrid composites can be used effectively to fabricate films with NIR cutoff as well as antistatic properties, indicating a high potential for practical application in architectural, automotives, and optoelectronics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

UV‐curable nanocomposites containing zirconium vinylphosphonate or zirconia

UV‐cured nanocomposite films were prepared from acrylic monomer and two types of nanomaterial: zirconium vinylphosphonate and zirconia, in the presence of a photoinitiator. The films were characterized by FTIR, SEM, and AFM. FTIR spectra showed the disappearance of band assigned to the CC group both of monomer and zirconium vinylphosphonate by polymerization and the presence of the phosphonate group in polymer. The influence of zirconium vinylphosphonate and zirconia content on thermooxidative degradation of polymeric films was studied by thermogravimetry. SEM and AFM images showed that nanomaterials are dispersed in polymer matrix with no macroscopic phase separation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure‐property relations in UV‐curable urethane acrylate oligomers

Four urethane acrylate oligomers were synthesized by a reaction of an excess of isophorone diisocyanate (D) with polypropylene glycol Acclaim 4200N (P) with a subsequent reaction of nonreacted D with a hydroxy acrylate Tone M100 (A). The latter has a common name caprolactone acrylate. Oligomers were prepared by different ways of addition of P to D or D to P and at different ratio of [D]/[P]. The fifth oligomer ADA was prepared as an individual compound. Viscosities, GPC traces, T_g's of oligomers were taken alongside with other physical properties of cured oligomers. It was demonstrated that oligomers with P consist of ADPDA, ADA, and of a chain‐extended product A… P_n… A, which has two or more Ps in a molecule. Additive contributions of these three components essentially determine properties of the liquid and cured oligomers. Structure‐property relations of urethane acrylate oligomers are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99:489–494, 2006     

Preparation and properties of UV‐curable fluorinated polyurethane acrylates

A series of UV‐curable polyurethane acrylates (PUA0, FPUA3, FPUA6, FPUA 9 FPUA12, FPUA15, where the numbers indicate the wt % of perfluoroalkyl acrylate), were prepared from a reactive oligomer [4,4 ?‐dicyclohexymethanediisocyanate(H12MDI)/ poly(tetramethylene glycol)(PTMG)/2‐hydroxyethyl methacrylate (HEMA): 2/1/2 molar ratio, prepolymer:40 wt %] and diluents [methyl methacrylate (MMA, 20 wt %)/ isobornyl acrylate (IBOA, 40–25 wt %)/heptadecafluorodecyl methacrylate (PFA, 0–15 wt), total diluents: 60 wt %]. This study examined the effect of PFA/IBOA weight ratio on the properties of the UV‐curable polyurethane acrylates for antifouling coating materials. The as‐prepared UV‐curable coating material containing a 15 wt % PFA content in diluents (MMA/IBOA/PFA) form a heterogeneous mixture, indicating that a PFA content of approximately 15 wt % was beyond the limit of the dilution capacity of diluents for the oligomer. In the wavelength range of 400–800 nm, the UV‐cured PUA0 film sample was quite transparent (transmittance%: near 100%). On the other hand, the transmittance% of the FPUA film sample decreased markedly with increasing PFA content. XPS showed that the film‐air surface of the UV‐cured polyurethane acrylate film had a higher fluorine content than the film‐glass dish interface. As the PFA content increased from 0 to 12 wt %, the surface tension of the UV‐cured urethane acrylates decreased from 26.8 to 15.6 mN/m, whereas the water/methylene iodide contact angles of the film–air surface increased from 90.1/63.6° to 120.9/87.1°. These results suggest that the UV‐curable polyurethane acrylates containing a PFA content up to 12 wt % have strong potential as fouling‐release coating materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40603.     

氯乙烯-异丁基乙烯基醚共聚树脂生产技术概述

介绍了国内外氯乙烯-异丁基乙烯基醚共聚树脂的生产技术现状,详细地比较了国内微悬浮法和乳液法两种工业生产技术的优缺点。