Abstract
本研究的第一部份是以陽離子開環聚合反應合成環氧丙烷衍生物與四氫夫喃之三團聯共聚合物，以作為固態火箭推進劑之膠合劑之用。研究中首先以三氟甲磺酸酐為陽離子聚合起始劑，建立環氧丙烷衍生物之雙端成長活性聚合系統，結果顯示此系統之聚合反應活性體為環狀氧陽離子與三氟甲磺酸聚酯基並存，並形成一平衡關係，具有推電子性的取代基及較高極性的溶劑有助於氧陽離子活性體的形成與安定化。進一步建立環氧丙烷衍生物與四氫夫喃之三團聯共聚合物之合成系統，分析結果顯示，本研究成功獲得結構為ABA形式的三團聯共聚合物，其中A為硬鏈段之聚環氧丙烷衍生物，B為軟鏈段之聚四氫夫喃；這些共聚合物並具有玻璃轉移溫度低、機械性質良好、高能量特性與熱可塑性彈性體等特性達到做為新一代火箭推進劑，膠合劑的要求。最後本部份研究並開發出利用環氧丙烷環為反應團基之新型加成反應，此新型加成反應可用於具特殊官能基之側鏈高分子之合成，本研究中即據以合成玻璃轉移溫度高及熱安定性良好之可交聯型非線性光學高分子。本研究的第二部份在開發含磷高分子，以作為反應型高分子難燃劑之用。首先開發出具膦酸酯基及磷酸酯基之含磷環氧樹脂單體，與具膦酸酯基、磷酸酯基及膦基之含磷雙胺化合物作為硬化劑，製備含磷環氧樹脂；這些含磷單體具有高的磷含量及簡便的有機合成及後處理程序。探討這些含磷單體與其他商業化單體之硬化反應性、硬化反應動力學、硬化反應條件等。所合成出來的硬化含磷環氧樹脂受熱時，由含磷團基開始裂解，磷團基的裂解形成保護層，除提高裂解殘餘物的的熱穩定性而延遲高分子的熱裂解外，並大幅提高焦炭殘餘率，而發生難燃效應。研究結果顯示這些含磷環氧樹脂具有相當高的焦炭殘餘率及極限氧指數值，且隨著磷含量的增加而增加，表現出優異的難燃性質。此外，導入含矽化合物增加焦炭之高溫抗氧化能力，可進一步大幅提昇含磷環氧樹脂的難燃特性，證實磷矽在難燃特性上的協成效應。含磷高分子另經由高分子磷化反應製得，這些含磷高分子的磷含量亦可經由反應條件加以調控，並皆表現出優異的難燃性質。此高分子磷化法可應用於磷化大部份熱塑性高分子，故可製備各種熱塑性難燃高分子。The goal of this endeaver in the first part is to synthesizeoxetane derivatives and tetrahydrofuran based triblockcopolymers as rocket propellant binders. A two-end livingcationic polymerization system is first established by usingtriflic anhydride as an initiator. The active species of thepropagating reaction in this polymerization system aredetermined to be macro-oxonium ions and triflic macro-esters.The two end living polymerization system is utilized tosynthesize A-B-A type triblock copolymers. The A-B-A triblockcopolymers possess hard segments A of poly(oxetanes) and softsegment B of poly(tetrahydrufuran). Copolymers with variousmolecular weights, narrow polydispersities, low glass tran-sition temperatures, good mechanical property, and thermo-plastic elastomer characteristics, and energetic properties areobtained. The energetic thermoplastic elastomers are useful inserving as propellant binders. In addition, a novel additionreaction on oxetane rings are also developed using triflic acidas an intermediate. The addition reaction is utilized inpolymer reaction to synthesize functional side-chain polymers.The second part of this endeaver aims at developing phosphorus-containing polymers for reactive polymer flame retardants.Polymers with various controlled phosphorus contents areobtained via changing the feed ratios of the reactants in thepolymer phosphorylation. Moreover, phosphorus-containing epoxyresins are prepared. High char yields and limiting oxygen index(LOI) values are founded for the phosphory- lated epoxy resins.This confirmed the high flame retardancy of these phosphorus-containing epoxy resins. Moreover, the flame retardantefficiency could be further leveled up by intro- ducing siliconinto the resins. As a result, the P/Si synergistic effect onflame retardancy is confirmed.