Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/97583
標題: 磷系甲基壓克力及其環氧樹脂固化物性質
Synthesis and characterization of phosphorous containing methacrylate monomers, curing with epoxy and studied their polymers properties
作者: 林于翔
Yu Hsiang Lin
關鍵字: 間苯二酚
甲基丙烯酸酐
環氧樹脂固化
Resorcinol
methacrylic anhydride
Epoxy thermoset
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摘要: 本實驗是藉由低成本的DOPO、Acetone、Resorcinol(及Catechol)利用兩步反應合成兩種低成本、更高含磷量的雙酚單體。再將單體中的羥基結構以甲基丙烯酸酐進行改質,與市售環氧樹酯HP-7200進行固化,在固化的同時甲基丙烯酸基團也會進行自身交聯固化,使其有更高的交聯密度,更高的熱性質。測試其固化物的玻璃轉移溫、熱裂解溫度、介電性質等等。Resorcinol系統經MMA改質後Tg約237 oC ;氮氣環境下Td5%約407 oC ; Dk和Df分別為2.91及0.008。Catechol系統經MMA改質後Tg約208 oC ; 氮氣環境下Td5%約416 oC ; Dk和Df分別為2.87及0.008。此固化物之熱性質和介電性質,Resorcinol系統優於商品DMP進行甲基壓克力改質後之性質 (Tg約220 oC ; 氮氣環境下Td5%約403 oC ; Dk和Df分別為3.07及0.007)。 第二部分是利用本研究合成之單體DPAC-mma和DPAR-mma作為商品SA9000/HP7200固化物之阻燃添加劑,成功將UL-94難燃測試V-1等級之SA9000/HP7200固化物提升至V-0等級。 於實驗過程我們由H-NMR發現兩個現象 (1)DOPO和Acetone反應後的單體,當Temperature >140 oC時會脫去Acetone還原成DOPO (2) 兩個羥基會因為立體障礙的不同,而有不同的反應性。
In this experiment, two low-cost, higher phosphorus-containing bisphenol monomers were synthesized by a two-step reaction using low-cost DOPO, acetone, and resorcinol (or catechol). The hydroxyl structure in the monomer was modified with methacrylic anhydride and cured with commercially available epoxy resin, HP7200. At the same time of curing, the methacrylic group will also undergo self-crosslinking and solidification to achieve its higher crosslinking density, which gives the corresponding polymer the enhanced thermal properties. The cured polymers were tested for glass transition temperature, thermal cracking temperature and dielectric properties. In resorcinol system, the Tg is about 237 oC and Td5% is about 407 oC under the nitrogen atmosphere; Dk and Df values are 2.91 and 0.008, respectively. The catechol system has a Tg of about 208 oC; in a nitrogen atmosphere, Td5% is about 416 oC; Dk and Df values are 2.87 and 0.008, respectively. The thermal and dielectric properties of resorcinol system containing cured polymers are superior to the DMP-mma (Tg = 220 oC, Td5% under nitrogen is 403 oC, and Dk, Df values are 3.07 and 0.007, respectively). In second part of this thesis, we used two monomers DPAC-mma, and DPAR-mma, which were cured by using commercial SA9000/HP7200 curing agents. The cured product has enhanced properties under UL-94 flame retardant test from V-1 grade to V-0 grade. The experimental investigation revels, that the monomer DPA will undergo reverse reaction when temperature is greater than 140 oC, and the two hydroxyl groups will be different in reactivity due to the influence of steric hindrance.
URI: http://hdl.handle.net/11455/97583
文章公開時間: 2021-08-10
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