To prepare UV-curable polyurethane-acrylate oligomer, NCO-terminated urethane prepolymers with trimethylolpropane, [TMP; 0 (0), 0.1 (0.021) and 0.2 (0.043) mole (mole fraction)] as crosslinkable tri-functional chain extender were end-capped with pentaerythritol triacrylate [PETA; 2.0 (0.400), 1.7 (0...
To prepare UV-curable polyurethane-acrylate oligomer, NCO-terminated urethane prepolymers with trimethylolpropane, [TMP; 0 (0), 0.1 (0.021) and 0.2 (0.043) mole (mole fraction)] as crosslinkable tri-functional chain extender were end-capped with pentaerythritol triacrylate [PETA; 2.0 (0.400), 1.7 (0.354) and 1.4 (0.304) mole (mole fraction)] with one hydroxyl group/three vinyl functionalities. The stable as-formulated UV-curable polyurethane-acrylates [stable mixtures of PETA-capped oligomer/reactive acrylic monomer diluents without/with heptadecafluorodecyl methacrylate (PFA; 0, 6 and 9 wt%)] were formed up to 0.2 (0.043) mole (mole fraction) of TMP content in the prepolymer, while homogeneous-mixing failed at 0.3 (0.068) mole (mole fraction), in which the crosslink density in NCO-terminated urethane prepolymer was too high to enable the formation of stable mixture. This study examined the effect of TMP/PETA molar ratio and heptadecafluorodecyl methacrylate (PFA) content (wt%) on the properties of UV-cured polyurethane-acrylates as marine antifouling coating materials. The properties of UV-cured polyurethane-acrylate were found to be significantly dependent on the crosslinkable TMP/PETA ratio and PFA content. With the increasing of the TMP and PFA contents, the contact angles increased, and consequently the surface tension decreased. The adhesion of algae/barnacles to PFA contained film samples were found to be sufficiently weak to allow their easy removal. These results suggest that the UV-cured samples containing PFA have strong potential as coating materials for antifouling applications.
To prepare UV-curable polyurethane-acrylate oligomer, NCO-terminated urethane prepolymers with trimethylolpropane, [TMP; 0 (0), 0.1 (0.021) and 0.2 (0.043) mole (mole fraction)] as crosslinkable tri-functional chain extender were end-capped with pentaerythritol triacrylate [PETA; 2.0 (0.400), 1.7 (0.354) and 1.4 (0.304) mole (mole fraction)] with one hydroxyl group/three vinyl functionalities. The stable as-formulated UV-curable polyurethane-acrylates [stable mixtures of PETA-capped oligomer/reactive acrylic monomer diluents without/with heptadecafluorodecyl methacrylate (PFA; 0, 6 and 9 wt%)] were formed up to 0.2 (0.043) mole (mole fraction) of TMP content in the prepolymer, while homogeneous-mixing failed at 0.3 (0.068) mole (mole fraction), in which the crosslink density in NCO-terminated urethane prepolymer was too high to enable the formation of stable mixture. This study examined the effect of TMP/PETA molar ratio and heptadecafluorodecyl methacrylate (PFA) content (wt%) on the properties of UV-cured polyurethane-acrylates as marine antifouling coating materials. The properties of UV-cured polyurethane-acrylate were found to be significantly dependent on the crosslinkable TMP/PETA ratio and PFA content. With the increasing of the TMP and PFA contents, the contact angles increased, and consequently the surface tension decreased. The adhesion of algae/barnacles to PFA contained film samples were found to be sufficiently weak to allow their easy removal. These results suggest that the UV-cured samples containing PFA have strong potential as coating materials for antifouling applications.
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문제 정의
However, studies on UV-curable polyurethane-acrylate containing chemical crosslinking component TMP and PETA and reactive diluents with fluorinated acrylic monomer PFA have not been issued. Thus, the aim of this study was to improve the surface antifouling properties and mechanical properties of crosslinked polyurethane-acrylate by introducing crosslinkable three vinyl groups contained PETA and internal crosslinkable TMP and fluorinated acrylic monomer PFA.
제안 방법
The UV-curable fluorinated urethane-acrylate mixtures were formulated from a viscous oligomer (40 wt%), diluents (60 wt%) and photoinitiator Irgacure 184 (2 wt% based on the prepolymer/diluents). A series of UV-curable fluorinated polyurethane acrylates mixture (prepolymer/diluents/photo-initiator) were formulated by adding the acrylate diluents [isobornyl acrylate (IBOA, 40 - 31 wt%)/ butyl acrylate (BA, 20 - 11 wt%), heptadecafluorodecyl methacrylate (PFA, 6 - 9 wt%), total diluents: 60 wt%] and photo-initiator Irgacure 184 (2 wt%) to the viscose urethane acrylate prepolymer (40 wt%) and mixing them at 45 ℃ for 3 h. Table 1 lists the sample designation and composition of the UV-curable fluorinated urethane-acrylate containing various contents of TMP, PETA and PFA.
4)-F9. In this study, the chemical reactions between the functional groups were checked by monitoring the disappearance of the reactive functional groups present on the monomers and prepolymer. The capping reaction of the NCO-terminated urethane prepolymer with PETA was confirmed by the disappearance of NCO peak at 2270 cm-1.
In this study, the rigid bulky cycloalkyl group contained monomer isobornyl acrylate (IBOA) to raise toughness/rigidity, longalkyl chain group contained acrylic monomer butyl acrylate (BA) to raise flexibility/hydrophobicity, long perfluoroalkyl group contained monomer perfluoroalkyl acrylate (PFA) to expand surface tension, three vinyl groups/one hydroxyl group contained PETA as an end capping agent as well as a crosslinking/multibranching agent for acrylate monomer, and TMP as an internal cross-linker for PU hard segment, are used in this study. This study focused on the effects of TMP/PETA molar ratio and PFA content on the properties such as mechanical properties, thermal properties, contact angle, surface tension and antifouling property of UV-cured polyurethane acrylates with a fixed urethane oligomer content (40 wt%) to find the optimum composition for outstanding antifouling materials.
In this study, the rigid bulky cycloalkyl group contained monomer isobornyl acrylate (IBOA) to raise toughness/rigidity, longalkyl chain group contained acrylic monomer butyl acrylate (BA) to raise flexibility/hydrophobicity, long perfluoroalkyl group contained monomer perfluoroalkyl acrylate (PFA) to expand surface tension, three vinyl groups/one hydroxyl group contained PETA as an end capping agent as well as a crosslinking/multibranching agent for acrylate monomer, and TMP as an internal cross-linker for PU hard segment, are used in this study. This study focused on the effects of TMP/PETA molar ratio and PFA content on the properties such as mechanical properties, thermal properties, contact angle, surface tension and antifouling property of UV-cured polyurethane acrylates with a fixed urethane oligomer content (40 wt%) to find the optimum composition for outstanding antifouling materials.
However, their adhesion to ship hulls was sufficiently weak to allow their easy removal by water jets or simply by the friction of sea water in the case of fast ships. To overcome the problem of lack of adhesion of these materials to ship hulls, UV-curable crosslinkable polyurethane-acrylates containing fluorine component, whose adhesion to ship hulls was strong enough, was synthesized in this study. However, studies on UV-curable polyurethane-acrylate containing chemical crosslinking component TMP and PETA and reactive diluents with fluorinated acrylic monomer PFA have not been issued.
Field tests in seawater were performed from September 2015 (78 days) located at Dadaepo in Busan, Korea. The film samples that were mounted onto the PVC supports were immersed into the seawater at depths of about 1 m below the surface.
The testing liquids used were water (L1) and methylene iodide (L2), and their γ L1d , γ L1p ,γ L2d , and γ L2p were 21.8, 51.9, 1.3 and 49.5 mN m-1, respectively [36].
이론/모형
H12MDI was dropped slowly into the flask, and the reaction mixture was allowed to react at 85 ℃ until the theoretical NCO content was reached. The change in NCO value during the reaction was determined using the standard dibutylamine back-titration method (ASTM D 1638). The reaction mixture of the NCO-terminated urethane prepolymer was cooled to 45 ℃, and PETA was added dropwise.
The gel content of UV-cured film samples was determined by the Soxhlet extraction method using toluene/DMF for 24 h. The gel contents of the UV-cured film samples were determined from the difference in dry weight before and after the extraction experiment.
The tensile properties were measured at room temperature using a universal testing machine (Instron, USA) with a 5582 system according to ASTM D 638. A cross-head speed of 10 mm min-1 was used throughout these investigations to determine the ultimate tensile strength, modulus, and elongation at break for all samples.
성능/효과
Table 1 lists the sample designation, composition and viscosity of UV-curable polyurethane acrylates [polyurethane-acrylate prepolymer (40 wt%)/diluents (60 wt%)/photoinitiator Irgacure 184 (2 wt%)]. In this study, the UV-curable polyurethaneacrylate had a fixed weight ratio of polyurethane-acrylate prepolymer (oligomer)/diluents (40/60 wt%), whereas the compositions of TMP/PETA and BA/PFA were changed. The as-formulated UV-curable polyurethane acrylate containing up to 0.
The gel content (%) is a measure of curing and crosslinking of the UV-curable coating materials. It was found that the gel content of all UV-cured film samples was near 100%, indicating that the UV-cured film samples prepared in this study had a very high molecular weight (crosslink-like structure). The difference of effect of PETA/TMP/PFA contents on the gel content was negligible.
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