• Elastomers and Composites
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• v.57 no.3
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• pp.100-106
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• 2022

Waterborne polyurethane-acrylate(WPUA) dispersions were prepared by surfactant-free emulsion polymerization in a two-step process. In the first step, polytetrahydrofuran, isophorone diisocyanate, dimethylol proponic acid, and 2-hydroxyethyl methacrylate were used to synthesize a vinyl-terminated polyurethane prepolymer. In the second step, styrene, methyl methacrylate, butyl acrylate, and different multi-functional crosslinkers were copolymerized. 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate were used as the crosslinkers, and their effect on the mechanical and thermal properties of WPUA was investigated. Overall, as the number of functional groups of the cross-linker increased, the gel fraction improved to 79.26%, the particle size increased from 75.9 nm to 148.7 nm, and the tensile strength was improved from 5.86 MPa to 12.40 MPa. In thermal properties, the glass transition temperature and decomposition temperature increased by 9.9℃ and 18℃, respectively. The chemical structures of the WPUA dispersions were characterized by Fourier-transform infrared spectroscopy. The synthesized WPUA has high potential for applications such as coatings, leather coatings, adhesives, and wood finishing.

• Corrosion Science and Technology
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• v.12 no.1
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• pp.27-33
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• 2013

According to its merits about high curing speed and low emission of volatile organic compounds, UV curable inorganic-organic coating technology has been developed as an alternative for toxic and carcinogenic chromate-based treatments for years. It is consistently observed that ultra-thin films offer excellent corrosion protection as well as paint adhesion to metals. Based on the tetra-ethylorthosilicate(TEOS) and methacryloxypropyl trimethoxysilane(MPTMS), inorganic sol was synthesized and formed hybrid networks with UV curable acrylic monomer, 6-hexanediol diacrylate(HDDA), trimethylolpropane triacrylate(TMPTA), pentaerylthritol triacrylate(PETA). Several methods were used to test their properties such as salt spray test, potentiodynamic measurement, tape peel test, etc. It was shown that anti-corrosive property and stability of storage were affected by the molecular ratios of inorganic and organic compounds. It was not only the stability of storage, but had a excellent anti-corrosive, paint adhesive, and anti-solvent properties in a final molar ratios of 0.6/0.04/0.86/0.005 (TEOS/MPTMS/Acetone/HNO3) and 0.08/0.106/0.081/0.02 (TMPTA/HDDA/PETA/photo initiator).

• Applied Chemistry for Engineering
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• v.26 no.4
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• pp.439-444
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• 2015

Several attempts to design the best-available thermosetting road markings by using MMA to improve the durability and retroreflectivity are presented in this paper. In order to improve field applicability, the components of main materials were designed by means of reducing the hardening time lower than eight minutes. The optimum mixing ratio of thermosetting road marking was TSRM-6 composed of 15.6 wt% of MMA monomer ($Tg=105^{\circ}C$), 6.0 wt% of PMMA (MW = 70,000, $Tg=60^{\circ}C$) and 1.2 wt% of TMPTA (MW = 338, $Tg=27^{\circ}C$). Also the homogeneous mixing of all components was necessary. The use of ceramic glass beads with an optimized TSRM-6 exhibited excellent performance by achieving retroreflectivity coefficients of 431, 354 and $172mcd{\cdot}m^{-2}{\cdot}lux^{-1}$ for dry, wet and rainy test condition, respectively at two hundred thousand cycles.

• Journal of the Korean Applied Science and Technology
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• v.22 no.3
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• pp.257-269
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• 2005

This study was focused on the maximization of flame-retardancy of polyesters by a synergism of simultaneously introduced chlorine and phosphorus into polymer chains of modified polyesters. To prepare modified polyesters, reaction intermediates, TD-adduct (prepared from trimethylolpropane /2,4-dichlorobenzoic acid (2,4-DCBA)) and TMBO (prepared from tetramethlene bis (orthophosphate)), were prepared first, then condensation polymerization of the prepared intermediates, adipic acid, and 1,4-butanediol were carried out. In the condensation polymerization, the content of phosphorus was fixed to be 2wt%, and the content of 2,4-DCBA that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as ABTTs. The prepared intermediates and modified polyesters were characterized with FT-IR, NMR, GPC, and TGA analysis. Average molecular weight and polydipersity index of the preparation of ABTTs were decreased with increasing 2,4-DCBA content because of the incease in hydroxyl group that retards reaction. We found that the thermal stability of the prepared ABTTs increased with chlorine content at high temperatures.

• Journal of the Korean Applied Science and Technology
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• v.24 no.4
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• pp.319-331
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• 2007

The aim of this study is to enhance the flame retardancy by the synergism effect of phosphorus and bromine groups. The flame-retardant polyurethane coatings containing phosphorus and bromine compounds were synthesized. After synthesizing the intermediate products of tetramethylene bis(orthophosphate) (TBOP) and trimethylolpropane/2,3-dibromopropionic acid (2,3-DBP) [2,3-DBP-adduct], the condensation polymerization was performed with four different monomers of two intermediate products, 1,4-butanediol, and adipic acid to obtain four-components copolymer. In the condensation polymerization, the content of phosphorus was fixed to be 2wt%, and the content of 2,3-DBP that provides bromine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing phosphorus and bromine as DTBA-10C, -20C, -30C. Average molecular weight and polydispersity index of the preparation of DTBAs were decreased with increasing 2,3-DBP content because of increase of hydroxyl group that retards reaction. We found that the thermal stability of the prepared DTBAs increased with bromine content at high temperature.

• Polymer(Korea)
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• v.26 no.2
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• pp.200-208
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• 2002

Two-component polyurethane flame-retardant coatings were prepared by blending trichloro lactone modified polyesters (TAPTS) and isocyanate, Desmodur IL. Polycondensation reaction of trichlorobenzoic acid (TBA) as a flame-retardant component, and adipic acid with trimethylolpropane, polycaprolactone 0201, and 1,4-butanediol gave the corresponding TAPTs. The content of TBA was adjusted from 10 to 30 wt% in our experiment. It was found that various properties of these new flame-retardant coatings were comparable to other non-flame-retardant coatings. We also carried out three different tests for the measurement of flammability of flame -retardant coatings. The results of vertical burning test for the coatings containing more than 20 wt% of TBA were determined as 'no burn'. The results of flammability test for the coatings with 20 and 30 wt% of TBA contents indicated the limiting oxygen index (LOI) values of 25% and 27% respectively, which implied relatively good flame retardancy. They also showed the char length of 3.6-5.2 cm according to $45^{\circ}$ Meckel burner test, which can be classified as the first grade flame-retardant coatings.

• Polymer(Korea)
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• v.24 no.1
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• pp.72-81
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• 2000

Benzoic acid polyester/lactone polyol were synthesized by polycaprolactone 0201 as diol, trimethylolpropane as triol, adipic acid as dibasic acid, and benzoic acid as monobasic acid. Polyisocyanate prepolymer Desmodur N-100 of HDI-biuret type was used in this study. Two-component polyurethane coatings were prepared by blending benzoic acid polyester/polycaprolactone, polyisocyanate, wetting/dispersing agent, white pigment, and flowing agent. Various properties were examined on the film coated with the prepared polyurethane. They showed excellent physical properties such as abrasion resistance, accelerated weathering resistance, and yellowness index. They also showed good physical properties such as flexibility, impact resistance, 60$^{\circ}$ specular gloss, cross hatch adhesion, hydrocarbon resistance, and lightness index difference. Hardness of coating showed a little poor character. The introduction of polycaprolactone 0201 as diol in the polyurethane coatings improved the hydrocarbon resistance, impact resistance, and flexibility of coatings. According to the drying and curing behavior with the contents of benzoic acid, they seem to have reasonable coating properties such as drying time of 2 to 4 hours and pot-life time of 20 to 37 hours.

• Polymer(Korea)
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• v.37 no.2
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• pp.167-176
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• 2013

Linear and cross-linked waterborne polyurethanes (WPUs) based on isophorone diisocyanate and mixed diols of poly(tetramethylene glycol)/hydroxyethyl-terminated polydimethylsiloxane (PDMS-OH) were synthesized with dimethylol propionic acid as an anionic component, trimethylolpropane as a cross-linking agent, and butanediol as a chain extender and characterized. The hydrophobicity, $T_g$, stress-strain behaviors of the linear or cross-linked siloxane-containing WPU (WPU-Si) films with different PDMS content were analyzed by using water contact shape analyzer, energy dispersive spectrometer, dynamic mechanical analyzer, and universal testing machine. The results reveal that as the PDMS content increased, the hydrophobicity of WPU-Si films increased, $T_g$ moved to higher temperature, the breaking stress increased, and the breaking strain decreased.

• Korean Chemical Engineering Research
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• v.49 no.1
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• pp.75-82
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• 2011

Five different composition UV-cured poly(urethane acrylate-co-acrylic acid) (PU-co-AA) films have been prepared by reacting isophorone diisocyanate(IPDI), polycaprolactone triol(PCLT), 2-hydroxyethyl acrylate(HEA), and different weight ratio trimethylolpropane triacrylate(TMPTA) and acrylic acid(AA) as diluents, and characterized using a Fourier transform infrared spectroscopy(FT-IR). The adhesion properties onto the stainless steel, morphology, mechanical hardness, and electrical property of UV-cured PU-co-AA films were investigated as a function of acrylic acid(AA) content. All the PU-co-AA films are structure-less and the molecular ordering and packing density decreased with increasing content of AA due to the flexible structure and -COOH side chains in AA. The crosscut test showed that PU-co-AA films without AA and with low content of AA showed 0% adhesion(0B) and the adhesion of PU-co-AA films in the range of 40-50% AA increased dramatically as the content of AA increases. The pull-off measurements showed that the adhesion force of PU-co-AA films to stainless steel substrate varied from 6 to 31 kgf /$cm^2$ and increased linearly with increasing AA content. The mechanical hardness also decreased as the content of AA increases. This may come from relatively linear and flexible structure in AA and low crystallinity in PU-co-AA films with higher content of AA. The higher AA-containing PU-co-AA films showed higher dielectric constant due to the increase of polarization by introducing AA monomer. In conclusion, the physical properties of UV-cured PU-co-AA films are strongly dependent upon the content of AA and the incorporation of AA in polyurethane acrylate is very useful way to increase the adhesion strength of UV-curable polymers on the stainless steel substrate.

• Applied Chemistry for Engineering
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• v.2 no.2
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• pp.175-184
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• 1991

Ultraviolet curable coatings are often used to protect the surface of polymer materials exposed to the ultraviolet radiation. However, the adhesion of epoxy acrylate on poly(vinyl chloride) and the UV curable coating on polystyren are poor. The objective of this work was to improve the adhesion of coating according to various formulations of the reactive diluents and finishing methods using the photografting of multifunctional acrylate and the surface activation on polymer surface impregnated a phtoinitiator. The addition of Tripropylene glycole diacrlate in the formulation of coating results in the improvement of adhesion of coating due to the flexibility. But the increase of the crosslinking density which results from the oxidation of surface during the exposure of UV radiation caused the loss of adhesion of coating exept the photografting method. In the trimethylolpropane triacrylate the improvement of adhesion are considerable due to the chemical bond between multifundtional acrylate and surface. From this work we expect to achieve the varity and functionality in the formulation of coating according to the photografting and surface activating of polymer.