含磷矽紫外線硬化丙烯酸酯系聚胺基甲酸酯透明耐燃塗料之製備及性質

• Main Authors: Shih-Ming Kung, 龔世明
• Other Authors: Jin-Cherng Huang
• Format: Others
• Language: zh-TW
• Online Access: http://ndltd.ncl.edu.tw/handle/70858289100796490141

博士 === 國立嘉義大學 === 農業科學博士學位學程 === 104 === In this study, firstly, phosphoric acid and polypropylene glycol with a molar ratio of 1:3 were used to synthesize tripolypropylene glycol phosphate (TPPGP), and 2,4-toluene diisocyanate and hydroxyethyl acrylate with a molar ratio of 1:1 were used to synthesize toluene-2-isocyanate 4-urethane ethyl acrylate (TIUEA). Then, TPPGP and TIUEA with a molar ratio of 1:1 were used to synthesize phosphorus-containing acrylated polyurethane resins (PAPU). Next, PAPU and trimethoxysilane acrylate (TMSA) with a molar ratio of 3:1 were mixed to synthesize phosphorus silicon-containing acrylated polyurethane resins (PSAPU). Finally, additives, flame retardants and photoinitiators, were sequentially added into PSAPU to 32 formulas of ultraviolet curing flame retardant coatings. Their physicochemical properties were evaluated, glass transition temperature (Tg) was evaluated by dynamic mechanical analysis (DMA), thermal stability by Thermogravimetric analysis (TGA), flame retardant mechanism by Thermogravimetric analysis/Fourier transform infrared spectroscopy (TGA-FTIR), value of CNS 6532 standards by CNS 6532 tests, element, ash content by XPS analysis and Elemental analysis, the carbon characteristics of charred layer by Raman spectroscopy(Raman). The results showed that when TMSA was introduced, the IR spectra showed new Si-O-CH3 peak at 987 cm-1 and the increasing in vinyl C-H vibration at 810 cm-1. It also significantly reduced shoulder band hydroxyl peak(-OH) at 3100～3700 cm-1 range and CH3 peak at 1380 cm-1, proving the following three results : a condensation reaction occurred between PAPU and TMSA, PSAPU was successfully synthesized, and the addition of a phosphorus flame retardant did not have any influence on coating adhesion. The hardness, gloss, and gel content of the film slightly decreased, while its moisture absorption, pyrolysis temperature, and glass transition temperature (Tg) slightly increased. The first pyrolysis temperature of TGA is higher, which is advantageous to form a relatively compact char layer to block heat conduction and steam transfer, thus demonstrating excellent thermal behavior. PSAPU-P2 and PSAPU-P3 corresponded with CNS 6532 standards. After Raman analysis, PSAPU-P3 was better than PSAPU of graphitization degree because amount of phosphorus flame retardant increased. The peak at around 1596 cm-1（G-band）corresponds to an E2g mode of hexagonal graphite and is related to the vibration of sp2-hybridized carbon atoms in a graphite layer. The D-band at about 1356 cm-1 is attributed to the vibration of carbon atoms with dangling bonds in the plane terminations of disordered graphite or glassy carbons. General speaking, the intensity of these two peaks is related with the regularity for the structure of char layer. Hence, the addition of reactive phosphorus esters flame retardant could advance the regularity of carbon layer. The results of TGA-FTIR, element, ash content and XPS analysis showed that the coatings blended with reactive phosphorus esters flame retardant could raise the pyrolysis temperature of the organics and reduced the amount of fired organics effectively. Thus, PSAPU-P2 and PSAPU-P3 flame retardant performance was better. The transparency and curing rate of this kind of coating were better than those of the present commercial flame retardant coatings on the market. The application value of these coatings was quite great.