紫外線硬化型含磷矽丙烯酸酯系聚胺基甲酸酯耐燃塗料之物化性質及熱行為

Physicochemical Properties and Thermal Behavior of the Ultraviolet Curing Phosphorus Silane-Contained Acrylated Polyurethane Flame-resistance Coatings

龔世明(Shin-Ming Kung) ； 黃金城(Jin-Cherng Huang) ； 夏滄琪(Tsang-Chyi Shiah) ； 阮巽雯(Sun-Wun Juan)

《林產工業》 34卷4期 (2015/12) Pp. 179-189

https://doi.org/10.6561/FPI.2015.34(4).3

摘要

本研究係先分別將磷酸及聚丙二醇134以莫耳比1：3合成三羥聚丙氧基磷酸酯（Tripolypropylene glycol etherphosphate，TPPGEP），以及以莫耳比1：1 之2,4-甲苯二異氰酸酯（2,4-toluene diisocyanate，TDI）及羥乙基丙烯酸酯（Hydroxyethyl acrylate，HEA）合成甲苯-2-異氰酸酯,4-胺基甲酸丙烯酸乙酯（Toluene-2-isocyanate,4-urethane ethylacrylate，TIUEA），再將TPPGEP 及TIUEA 依照莫耳比1：1合成含磷丙烯酸酯系聚胺基甲酸酯樹脂（Phosphorus-containing acrylated polyurethane，PAPU），接續以PAPU：含矽的三甲氧基矽烷丙烯酸酯（Trimethoxysilaneacrylate，TMSA）莫耳比3：1之比例反應成含磷矽丙烯酸酯系聚胺基甲酸酯樹脂（Phosphorus silane-containing acrylatedpolyurethane resins，PSAPU），最後PSAPU依序添加耐燃劑及光引發劑等添加劑，調配成紫外線硬化型耐燃塗料，並評估其塗膜物化性質及熱行為。試驗結果得知，導入TMSA 後之光譜於987 cm^(-1) 出現Si-O-CH_3的波峰及810 cm^(-1)的乙烯基C-H振動增加，且3100-3700 cm^(-1) 的寬帶羥基（-OH）及1380 cm^(-1)的CH_3峰波明顯減少，證明PAPU與TMSA之間有發生縮合反應，成功合成出PSAPU，而添加耐燃劑對塗膜的附著性沒有影響，但硬度、光澤度及膠化量會略微下降，吸濕性、熱裂解溫度及玻璃轉移溫度（Tg）則略微上升。各樣品的Tg點溫度介於20.80~161.14°C之間，因此在高於Tg溫度下才裂解有利於產生較緻密的炭層，來阻擋熱傳導及蒸氣轉移，其熱性質極佳。

關鍵字

紫外線硬化 ； 含磷矽丙烯酸酯系聚胺基甲酸酯樹脂 ； 耐燃塗料 ； 物化性質 ； 熱行為

並列摘要

In this study, firstly, phosphoric acid and polypropylene glycol 134 with a molar ratio of 1:3 were used to synthesize tripolypropylene glycol ether phosphate (TPPGEP), 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, TPPGEP 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 silane-containing acrylated polyurethane resins (PSAPU). Lastly, additives, flame retardants and photoinitiators, were sequentially added into PSAPU to formulate ultraviolet curing flame-resistante coatings. Their physicochemical properties and thermal behavior were evaluated. 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 CH_3 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 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 (T_g) slightly increased. The T_g temperatures of different samples were between 20.80 and 161.14 °C. The first pyrolysis temperature of TGA is higher, that is advantageous to form a relatively compact char layer to block heat conduction and steam transfer, thus demonstrating excellent thermal behavior.

並列關鍵字

Ultraviolet curing ； Phosphorus silane-contained acrylated polyurethane resins ； Flame-resistante coating ； Physicochemical properties ； Thermal behavior