摘要：

相較於傳統benzoxazines 單體,主鏈型polybenzoxazines 具有優異的耐熱性質與高溫碳殘餘率,同時也具有更好的溶劑的抗侵蝕性與安定性,並具有一定程度可撓曲性.由文獻可知,大部分主鏈型polybenzoxazines 仍是藉由雙酚,脂肪族雙胺和甲醛的縮合或由click chemistry 形成.結構中往往含有長碳鏈脂肪族,或triazole (來自於clickchemistry),而這些基團均會影響結構的熱安定性.又根據本實驗室過去的研究成果顯示,芳香族雙胺所製備出的雙胺型benzoxazines 樹脂,比傳統雙酚型Bz 樹脂具有較好的性質.因此,本計劃將提出一系列以雙胺為基材的主鏈型polybenzoxazines 的合成方法.第一年的計劃中,我們將製備出具有雙胺結構benzoxazines,並與不同結構的雙馬來醯亞胺(bismaleimide)反應,而形成可交聯型polyaspartimides(5)(13).此外,我們也計畫合成一系列雙酚醛(hydroxybenaldehyde)單體,並和常見芳香族雙胺反應,合成出主鏈型polybenzoxazines(17)(26).第二年則導入氟原子及admantane 結構,合成新低介電benzoxazines (31)及低介電主鏈型polybenzoxazines (37)(41).第三年則則是導入矽氧烷結構,合成低體積收縮率的benzoxazine (48),特別的是,本計劃將3M ESPE 的環氧基團改成benzoxazine 基團,應足以突破3M 的專利,而創出新系列的低收縮率樹脂.最後合成熱固/熱塑複合型benzoxazines (52-53) (58-59) (64-65),並探討其morphology.Compared with benzoxazine monomers, thermosets based on linear polybenzxoazinesshow better thermal stability, higher char yield, chemical resistance, and most importantly, theflexible properties. According to the literatures, most of main-chain type polybenzoxazineswere prepared from the condensation of biphenols, aliphatic diamines and formaldehyde orfrom the coupling of click chemistry. The aliphatic alkyl chain and triazole linkage reducesthe thermal stability of polybenzoxazine thermosets. According to our previous researches, werevealed aromatic diamines-based benzoxazines show better thermal properties thanbiphenol-based benzoxazines. Continuing our effort in benzoxazines, we proposed athree-year project on aromatic diamine-based polybenzoxazines.In the first year's project, we will prepare a series of diamino-containing benzoxazines (4)and (12), and a series of crosslinkable polyaspartimides (5) and (13) will be prepared based onthem. In addition, we also prepare bis-hydroxybenzaldehyde monomers (14) and (23), and aseries of polybenzoxazines (17) and (26) will be prepared based on them. In the second year'sproject, we incorporate admantane linkage to prepare low dielectric benzoxazine (31) andpolybenzoxazines, (37) and (41). We also incorporate fluoro element to reduce the dielectricconstants. In the third year's project, we will synthesize a low-shrinking benzoxazine (48)form 1,3,5,7-tetramethyl-cyclotetrasiloxane. Besides, we also synthesize a series ofthermoplastic/thermosetting polybenzoxazines composites (52-53) (58-59) (64-65). Theirmorphologies will be analyzed and discussed.

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