Urethane Acrylate Oligomer Research Articles

Polyurethane Nanocomposites

This review describes the present state of science and technology of photopolymerizable (UV-curable) polyurethane (PU) nanocomposites which include nanosilica and organically-modified clay (organoclay). A number of documented improvements of properties of PU nanocomposites compared to the pristine PU are presented. Many data on the structure and properties of PU nanocomposites were obtained not only for UV-cured urethane acrylate oligomers, but also for nanocomposites produced in the dark reactions. These data are critically reviewed. There is an expectation in the field of dramatic improvement of properties of PU nanocomposites under low loading (1–5 wt%) of organoclay.

Synthesis and Photo-Polymerization of Poly(Alkyl Urethane) Acrylate Oligomers Using 2-Isocyanatoethyl Methacrylate for UV Curable Coating

The poly(alkyl urethane) acrylate oligomers (AUAOs) were obtained by the reaction of alkyl acrylate oligomers and 2-isocyanatoethyl acrylate. Synthesis of AUAOs were done with 2-mercaptoethanol (2-MEOH), alkyl (methyl, butyl, 2-ethylhexyl) acrylate, 2,2′-azobisisobutyronitrile (AIBN, initiator) and dibutyltin dilaurate as a catalyst. Then 2-MEOH was used for functional chain transfer agent. The oligomers were characterized by FT-IR, FT-NMR, rheometer, and DSC. Each oligomer was blended and photopolymerized by UV light, and their ball tack, adhesiveness, and thermal resistance were confirmed by ball tack tester and so on. Photo-polymerized AUAOs can be used for UV curable coatings, inks and adhesives.

Synthesis of a novel chelating ligand from pentane-2,4-dione and 3-aminopropyl[tris(trimethylsilyloxy)]silane. europium(III) and erbium(III) imino enolates

Acetylacetone reacts with 3-aminopropyl[tris(trimethylsilyloxy)]silane to give a mixture of the isomers 4-[3′-tris(trimethylsilyloxy)silylpropyl]iminopent-2-en-2-ol (90%) and 4-[3′-tris(trimethylsilyloxy)silylpropyl]aminopent-3-en-2-one (10%). According to 1H and 13C NMR data, both isomers exist in the cis-and trans-forms. Anhydrous europium(III) and erbium(III) tris{4-[3′-tris(trimethylsilyloxy)silylpropyl]iminopent-2-en-2-olates} were obtained from the mixture of the isomers and the corresponding propan-2-olates Eu(OPri)3 and Er(OPri)3. The resulting complexes are transparent air-stable liquids that are distillable in vacuo and well soluble in photopolymerizable polyorganosiloxane caoutchoucs and urethane acrylate oligomers. The volatility parameters of the europium(III) complex were studied.

Coating characteristics of electron beam cured Bisphenol A diglycidyl ether diacrylate-co-aliphatic urethane diacrylate resins

Abstract Electron beam (EB) was used to cure coatings of Bisphenol A diglycidyl ether diacrylate (BDGDA) containing varying proportions of aliphatic urethane diacrylate (AUA). The cured BDGDA-co-AUA polymer coatings were characterized by Fourier transformed infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel fraction and swelling estimation techniques. FTIR study showed that the coating formulations were completely cured at a dose of 420 kGy. The effect of AUA on the end use performance properties of BDGDA coating namely, abrasion resistance, specular gloss at 60° angle, tubular impact resistance, pencil hardness, pendulum hardness, scratch resistance, mar resistance, stain resistance, steam resistance and cigarette burn resistance was also investigated. It was observed that incorporation of urethane acrylate oligomer in the epoxy acrylate formulation improved abrasion resistance, gloss and impact resistance. However, scratch resistance, mar resistance and hardness of the BDGDA coatings decreased due to incorporation of AUA. All coating formulations exhibited excellent stains and steam resistance properties, but showed poor cigarette burn resistance.

Thermal properties and combustion behaviors of UV‐cured phosphate triacrylate/star poly(urethane acrylate) oligomer blends

AbstractA series of UV‐curable intumescent flame retardant resins was obtained by blending phosphate triacrylate (TAEP) in certain ratios with star poly(urethane acrylate) (SPUA) oligomer. The flammability of the cured films was characterized by limited oxygen index (LOI), UL 94, and the cone calorimeter. The results showed that the cured TAEP/SPUA samples greatly expanded while burning. A distinct synergistic effect was found between TAEP and SPUA. TAEP2 sample showed the highest LOI value (41) among all resins. The cone calorimeter results showed that the peak heat release rates and carbon monoxide yield decreased to the approximate level. The degradation was monitored by thermogravimetric analysis and real‐time Fourier transform infrared spectroscopy. A degradation mechanism is suggested in which the phosphate group in TAEP first degraded to form poly(phosphoric acid)s, which further catalyzed the degradation of the material to form char with emission of carbon dioxide and nitrogen volatiles from SPUA, leading to the formation of expanding char. The morphologic structures of crusts of the formed chars were observed by scanning electron microscopy, demonstrating the synergistic effect between TAEP and SPUA. Copyright © 2008 John Wiley & Sons, Ltd.

Effects of adding methacrylate monomers on viscosity and mechanical properties of experimental light-curing soft lining materials based on urethane (meth)acrylate oligomers.

We investigated the viscosity and mechanical properties of experimental light-curing soft lining materials based on six commercially available urethane (meth)acrylate oligomers. The viscosities of the six oligomers were 1.9, 20.6, 26.8, 144.0, 185.3, and 8803.4 Pa*s at 25 degrees C. Two monomers (ethyl- and butyl-methacrylate) were added at 20 wt% to these oligomers to decrease the viscosity, resulting in viscosity reductions of 0.2 to 13.6 Pa*s for the six oligomers. The mechanical properties (compressive modulus, Shore A hardness, and tensile strength) were measured after two times light-polymerization for 3 min. The addition of the monomers to the oligomers only slightly changed the mechanical properties, in contrast to the large viscosity changes. Based on these results, it appears that the addition of ethyl- or butyl-methacrylate monomers is useful for decreasing the viscosity of experimental light-curing soft lining materials without changing their mechanical properties.

Design of holographic polymer‐dispersed liquid crystals based on solubility parameters

AbstractBACKGROUND: A slight change of polymer structure leads to a significantly different solubility parameter (SP), which is related to incompatibility and interface anchoring energy between a polymer and a liquid crystal (LC).RESULTS: Holographic gratings in polymer‐dispersed liquid crystals have been fabricated based on various urethane acrylate oligomer sizes and type of reactive diluent at two LC loadings. A large SP gap, using N‐vinylpyrrolidone as reactive diluent, gave much faster saturation of diffraction efficiency at higher level, but the grating failed to operate. On the contrary, films having a small SP gap, using 2‐ethylhexyl acrylate, operated under 20 V with a response time of about 10 ms, although their saturation of diffraction efficiency was relatively low. The results were interpreted in terms of morphology (determined using scanning electron microscopy), anchoring energy and resin elasticity.CONCLUSION: Low driving voltage and high diffraction efficiency are obtained by controlling the SP gap between LC and polymer. Copyright © 2007 Society of Chemical Industry

Discussion of aqueous urethane acrylate oligomers with sulfoisophthalate on the antistatic hydrophilic finishing of different fabrics

AbstractIn this study, PEG(SE) containing sulfonic acid group was produced by transesterification of dimethyl 5‐sulfoisophthalate sodium salt (SIP) with PEG. The reactive urethane acrylate oligomers were synthesized by using SE as soft segment, isophorone diisocyanate (IPDI) as hard segment, and hydroxyethyl methacrylate (HEMA) as blocking agent. Their solution properties and thermal properties were investigated. Dipping process was carried out on polyethylene terephthalate (PET) fabric, polyamide (nylon) fabric, and cotton fabric for hydrophilic finishing and the effects of processing condition on the fixation behavior and hydrophilic property of treated fabric have been discussed. The conclusions are as follows: the particle size of oligomer solutions are about 45–90 μm, surface tension of solutions are below 43 dyn/cm, and they have smaller contact angle than water. The particle size, particle variance, and streaming current reading decreased, but the surface tension and contact angle enhanced upon increasing PEG molecular weight. The melting point of oligomer is 38°C–52°C and the glass transition point is −18°C to −25°C. In comparison with the fabric finishing, the add‐on of PET fabric is the highest, followed by nylon, then cotton. The durability of treated cotton fabric is the highest, followed by PET, then nylon. The hydrophilicity is most stable for nylon fabric with PEG molecular weight of 2,000, and cotton and PET fabric with molecular weight of 1,000. POLYM. COMPOS., 29:45–57, 2008. © 2007 Society of Plastics Engineers

Novel binder system for ultraviolet‐curable coatings based on tobacco seed (Nicotiana rustica) oil derivatives as a renewable resource

AbstractSeveral coatings have been developed to reduce volatile organic component emissions, such as water‐borne coatings, high‐solid coatings, powder coatings, and radiation‐curable coatings. Ultraviolet‐curable coatings are one such boon to paint industries, not only reducing volatile organic components but also increasing productivity. Most polymers industrially produced nowadays are based on petroleum, which is a limited resource. Developing new procedures for making polymers based on natural renewable resources is a resounding theme for this decade and the future also. In response to both these needs, we have investigated the use of tobacco seed (Nicotiana rustica) oil in the synthesis of radiation‐curable coatings. In this work, the alcoholysis of oil in various ratios with polyhydroxyl compounds was performed to prepare novel polyols, and these different polyols were reacted further with excess polyisocyanate to produce isocyanate‐terminated prepolymers. The prepolymer were further reacted with hydroxyethyl methacrylate to produce urethane acrylate oligomers. The radiation‐curable coating compositions were than prepared by the mixing of these oligomers with different reactive diluents, photoinitiators, and activators. These coating compositions were studied for their various physical and film characteristics, and certain coating compositions from tobacco seed oil were found to show very excellent overall coating properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

SYNTHESIS AND CHARACTERIZATION OF POLYURETHANE ACRYLATES FOR UV CURABLE COATING AGENTS

The single hydroxyl-terminated urethane acrylate oligomers were synthesized from 2-mercaptoethanol (2-MEOH), alkyl (methyl, butyl, and 2-ethylhexyl) acrylate, and 2,2-azobisisobutyronitrile (AIBN, initiator), with dibutyltin dilaurate (DBTDL) as a catalyst. 2-MEOH was used as a functional chain transfer agent. Poly(alkyl urethane) acrylate oligomers were obtained by the reaction of single hydroxyl-terminated polyalkyl acrylates and 2-isocyanatoethyl acrylate. They were characterized by NMR, FT-IR spectroscopy, rheometer, and DSC. Because poly(alkyl urethane) acrylate oligomers have lower Tg and viscosity than hydroxyl-terminated polyalkyl acrylate oligomers (HTPAO) non-containing urethane groups, they can be used for ultraviolet (UV) curable coatings, inks, and adhesives.

Reciclagem de vidro laminado: utilização dos vidros de baixa granulometria como carga abrasiva na formulação de vernizes de alto tráfego para pisos de madeira

O vidro laminado, especialmente o proveniente dos pára-brisas, é de difícil reciclagem após sua utilização, sobretudo o resíduo de vidro constituído de partículas pequenas (com baixa granulometria). O vidro muito fino se caracteriza como um resíduo, uma vez que não pode ser recuperado na indústria vidreira, pois nos grandes fornos de fusão de vidro evita-se a utilização deste material para impedir que ocorra o fenômeno de arraste de pó pela chaminé, bem como a deposição de vidro fundido nas paredes internas do forno e do regenerador[1]. Neste estudo duas granulometrias de vidro foram utilizadas - malha 200 e 325 mesh - na formulação de vernizes baseados num oligômero uretano-acrilado e usado para pintura e proteção de pisos de madeira. A cura desses vernizes foi por meio de radiação ultravioleta. Os resultados encontrados mostraram que a resistência à abrasão do verniz com a adição de vidro fino aumentou significativamente.

A study on UV-curable coatings for HD-DVD: Primer and top coats

This study relates to the development of coatings for optical discs in high-density digital versatile disc systems (HD-DVD or blue lay disk) that use a high numerical aperture of 0.85 at 405 nm wavelength and have a protective top layer over a primer layer for protection against damage and dust. Ultraviolet-curable raw materials of two acrylic monofunctional monomers ( isobornylacrylate, IBA and tetrahydrofurfurylacrylate, THFA) and two kinds of urethaneacrylate oligomers (OUMD and OUME) have been easily mixed with photoinitiators. Curing rate of these materials was characterized by FT-IR. In case of top coats, VTES (vinyltriethoxysilane) and acrylic acid were added to enhance the abrasion resistance. These two kinds of UV-curable resinous materials having no solvent were synthesized and investigated as means for making a blue ray disk having good optical and mechanical properties. In addition, dynamic characteristics including reflectivity, fluctuation of RF signal and noise level were also investigated.

Enhancement of Physico-mechanical Properties of Plywood Surface with Urethane Acrylate (M-1200) by UV Curing Method

Several UV-curable formulations containing urethane acrylate (M-1200) oligomer with a trifunctional monomer, trimethylol propane triacrylate (TMPTA), and photoinitiator Irgcure-369 were developed to improve the surface of plywood. Thin polymer films were prepared on glass plate with these formulated solutions and finally applied on polished plywood surface to modify the surface, and both were cured under UV-radiation. The properties of UV-cured thin films were studied as a function of UV-radiation intensities. Pendulum hardness (PH) and gel content were found to increase with the increase of TMPTA concentration up to a certain level and with further increase of monomer concentration the physical properties were decreased. The polymer-coated surface yielded enhanced physico-mechanical properties compared to that of unmodified surface.

Structure‐property relations in UV‐curable urethane acrylate oligomers

AbstractFour 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, Tg'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… Pn… 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

A study on UV-curable adhesives for optical pick-up: II. Silane coupling agent effect

Ultraviolet curable optical pick-up adhesive composites composed of acrylic and methacrylic mono-, bi- and trifunctional monomers and two kinds of urethaneacrylate oligomers have been easily prepared. In this paper, we studied the influence of various silane coupling agents to enhance the adhesion property in thermal and humid conditions by acting as both inorganic surface and organic polymer modifiers. Among them, vinyltriethoysilane (VTES) provides good adhesion effects on acrylate binder as well as silica surface. VTES added adhesives were studied by the real time FT-IR. The reliability of adhesives was explained by thermal-mechanical analysis (TMA) and then durability was tested by water boiling test. These UV-adhesives were successfully applied and settled in CD and DVD optical pick-up bodies in commercial application.

A study on UV-curable adhesives for optical pick-up: I. Photo-initiator effects

Ultraviolet curable optical pick-up adhesive composites composed of acrylic and methacrylic mono-, bi- and trifunctional monomers and two kinds of urethaneacrylate oligomers has been easily prepared by dual planetary mixer. And various fillers, thixotropic agents, antiemission and rheological additives were also used. The free radical photo-initiated polymerization reaction followed with various photo-initiators and its physical and mechanical properties were tested within 30 s of UV-irradiation. In this paper, we studied the influence of the photo-initiators and their mixtures on the polymerization rate of the adhesive compositions were studied. From these results, the mixture Irgacure 184 and Irgacure 819 provides synergic effects of surface and through curing. UV-adhesives of two types were well applied and settled in CD and DVD optical pick-up body at the reliability evaluation of Samsung Electronics’ production lines.

UV-curable hyperbranched urethane acrylate oligomers containing soybean fatty acids

Urethane acrylate resins based on partially modified aliphatic hyperbranched polyesters (HBP) have been synthesized. HBP of the second and the third generation were synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylol propane. The modification of certain amount of OH end-groups was carried out with soybean fatty acids. The urethane acrylates with different degrees of acrylation have been obtained by reaction of partially modified HBP and different amounts of NCO adduct which had been previously obtained by reaction of equimolar amounts of isophorone diisocyanate and 2-hydroxyethyl acrylate. The synthesized samples were characterized by FT-IR, 1H and 13C NMR and GPC. The rheological properties of uncured samples and mechanical and thermal properties of UV cured urethane acrylates diluted with 20 wt.% hexanediol diacrylate were examined. The modification of OH end-groups with soybean fatty acids causes a rapid decrease in viscosity of HBP. The examined properties of urethane acrylates depend on the degree of acrylation. After irradiating, the additional cross-linking, which is caused by reaction of double bonds from unsaturated fatty acids, has also important effect on the properties of cured samples.

Synthesis and Properties of Urethane Acrylate Oligomers: Direct versus Reverse Addition

Common urethane acrylate oligomers can be synthesized by one of two modes of addition. A polyol can be terminated on each end with diisocyanate and then capped with a hydroxy functional acrylate, direct addition, or a diisocyanate can first be reacted with a hydroxy functional acrylate, and that product can be used to terminate a polyol, reverse addition. This paper demonstrates how the mode of addition of the same reagents essentially changes the viscosity and molecular weight of the synthesized urethane acrylate oligomer.

가교형 폴리우레탄기 겔 폴리머 전해질의 합성과 전기화학적 특성

Urethane acrylate oligomer was synthesized and used in a gel polymer electrolyte (GPE) and then its electrochemical performances were evaluated. <TEX>$LiCoO_2/GPE/graphite$</TEX> cells were prepared and their performances depending on discharge currents and temperatures were evaluated. The precursor containing <TEX>$5 vol\%$</TEX> curable mixture had a low viscosity relatively. ionic conductivity of the gel polymer electrolyte at room temperature and <TEX>$-20^{\circ}C$</TEX> was ca. <TEX>$5.9\times10^{-3}S{\cdot}cm^{-1}\;and\;1.4times10^{-3}S{\cdot}cm^{-1}$</TEX>, respectively. GPE showed good electrochemical stability up to potential of 4.5V vs. <TEX>RLi/Li^+.\;LiCoO_2/GPE/graphite$</TEX> cell showed a good high-rate and low-temperature performance.

Influence of Coadditives on Physical and Mechanical Properties of Jute Fabrics Improved by UV-Cured Coating with Urethane Acrylate

Twelve different formulations were developed with aliphatic backbone-based urethane acrylate oligomer (Ebecry-264) in combination with a number of monomers like N-vinyl pyrrolidone (NVP), tripropylene glycol diacrylate (TPGDA), plasticizer, diallyl phthalate (DP), and antibubling agent methyl ethyl ketone (MEK), along with a photoinitiator Irgacure 184. Some additives and coadditives, such as calcium carbonate, urea, copper, and acrylamide, were incorporated into these formulations to study their effects on the physical and mechanical properties of pendulum hardness, gel content, and tensile strength and elongation at break of the films produced under UV radiation with these formulated solutions. These formulations were applied on jute fabrics (Hessian cloth) and cured under UV radiation. The improvement of various physicomechanical properties, such as tensile strength, elongation at break, and water resistivity of the treated jute fabrics was determined. The best formulation was evaluated.