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題 名 | Block Copolymerization of Carbon Dioxide with Butylene Oxide, Propylene Oxide and 4-Vinyl-1-Cyclohexene-1,2-Epoxide in Based Poly (Cyclohexene Carbonate)=以聚環氧環己烷碳酸酯為基材進行二氧化碳與環氧環丁烷、環氧環丙烷、4-乙基-1-環氧環己烷-1,2-環氧基之共聚 |
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作 者 | 許宗儒; 談駿嵩; | 書刊名 | Journal of the Chinese Institute of Chemical Engineers |
卷 期 | 34:3 2003.05[民92.05] |
頁 次 | 頁335-344 |
分類號 | 460.02 |
關鍵詞 | 二氧化碳; 團聯共聚; 環氧化合物; Carbon dioxide; Epoxide; Block copolymerization; Rare-earth catalyst; Thermal properties; Mechanical properties; |
語 文 | 英文(English) |
中文摘要 | 由於以三氟醋酸釔-二乙基鋅-glycerine 為解媒時,可有效自二氧化碳及環氧環己烷共聚成聚環氧環己烷碳酸酯,故以此為基材,將另一單體環氧環丁烷(BO)、環氧環丙烷(PO)或4-乙基-1-環氧環己烷-1,2-環氧基(VCHO)加入進行共聚反應以生成團聯共聚物。 由IR及1 H-NMR 光譜以及玻璃轉化溫度,可知共聚所生成之聚合物確為團聯共聚物,在353K時,環氧化合物之反應性為VCHO>PO>BO。就產率、分子量及分子量分佈而言,CO2與PO共聚之最佳溫度為333K,但以聚環氧環己烷碳酸酯為基材時,團聯共聚之最佳溫度提昇至353K。至於CO₂與BO及CO₂與VCHO團聯共聚之最佳溫度分別為343K與353K。 在最適條件下所得到之團聯共聚物分子量均可超過2×10^5,其分子量分佈介於6.2與9.9之間。碳酸酯在團聯共聚物中之比例佔86%與100%間。團聚物之熱及機械性質介於聚環氧環己烷碳酸酯及CO₂與PO或BO或VCHO聚合物之間。由實驗結果可知,使用不同單體進行團聯共聚是一有效生成所欲熱及機械性質聚合物之方法。 |
英文摘要 | Poly(cyclohexene carbonate) (PCHC) resulting from the copolymerization of CO₂ with cyclohexene oxide (CHO) could be effectively synthesized using the coordination system Y(CF₃CO₂)₃ (l) - diethyl zinc (II) - glycerine (Ill) and 1 ,3-dioxolane as the catalyst and solvent. t therefore was used as the base to synthesize block copolymers. Block copolymerization in the based PCHC was carried out by introducing an epoxide other than CHO right after the copolymerization of CO₂ with CHO. The IR and ¹H-NMR spectra as well as the glass transition temperatures indicated that the resultant copolymers from the block copolymerization of CO₂ with butylene oxide (BO), propylene oxide (PO), and 4-vinyl-l-cyclohexene-1,2-epoxide (VCHO) in PCHC were indeed block copolymers. The epoxide activity followed the sequence VCHO> PO > 80 at 353 K. While the most appropriate temperature regarding yield, molecular weight and the 353 K in the block copolymerization. The most appropriate temperatures for the block copolymerization of CO₂ with BO as well as CO₂ with VCHO in the based PCHC were 343 K and 353 K, respectively. The molecular weights of the resulting block copolymers were found to exceed 2×10^5, and the polydispersity indexes were in a range of 6.2 to 9.9. The carbonate Contents (fco₂) were observed to be in the range of 86% to 100%. The thermal and mechanical properties of the resulting block copolymers lay between those of the copolymers resulting from CO₂ with an individual epoxide, such as BO, PO, CHO and VCHO. These results indicated that block copolymerization was an effective means of generating a polymer with the desired thermal and mechanical properties. |
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