臺灣博碩士論文加值系統

封閉異氰酸酯(blocked isocyanates)是指高反應性的異氰酸酯(-NCO基團)被一種保護基團保護(封閉反應)，以減弱其高反應性，而在較高溫度下進行脫保護基(解封反應)，露出異氰酸酯高反應性的封閉的化合物。封閉型異氰酸酯在單組分塗料中得到廣泛的應用，如用封閉異氰酸酯製成的電絕緣漆具有良好的電絕緣性、耐水性、耐溶劑性以及良好的機械性能；封閉型異氰酸酯還在粉末塗料上有重要的應用價值，一些新的封閉劑已經商品化並且開發了一些新的用途；封閉型異氰酸酯應用於粘合劑中可增加其穩定性與儲存期，它主要應用於合成纖維織物與橡膠的粘接。另外，封閉異氰酸酯還廣泛應用於水性聚氨酯中，它具有成膜溫度低和膜性能好的特點。總之，封閉異氰酸酯的應用愈來愈廣泛，它逐漸由溶劑型向水溶液型過渡。
本研究採用的4,4-異氰酸二苯甲烷(MDI)是一種重要的異氰酸酯，主要用於製備聚氨酯彈性體、聚氨酯塗料等，在宇宙航空、建築、車船、冷藏及傢俱等各個部門都應用廣泛。為了提升合成之封閉型化合物與碳纖維及樹脂之共價鍵結力，分別採用水溶性較佳的Resorcinol(接著劑A)及N-methylaniline(接著劑B)作為保護基團，以封閉二苯甲烷二異氰酸酯之活潑性質，並且將測試利用實作碳纖維進行其拉身強度及應力之分析，以了解測試合成封閉型化合物之效用。針對原有製程進行設計相對應的架橋劑，讓螺絲產業可以採用水相漿液的方式進行塗裝，改善電鍍及有機塗料的缺點。

Blocked isocyanates means that highly reactive isocyanates (-NCO groups) are protected by a protecting group (blocking reaction) to attenuate their high reactivity, while deprotection is carried out at higher temperatures (unblocking) Reaction) to expose a blocked compound which is highly reactive with isocyanate. . Closed isocyanates are widely used in one-component coatings, such as electrical insulating varnishes made of blocked isocyanates with good electrical insulation, water resistance, solvent resistance and good mechanical properties; blocked isocyanates are also in powder coatings. There are important application values. Some new sealants have been commercialized and some new applications have been developed. Closed isocyanates are used in adhesives to increase their stability and shelf life. They are mainly used in synthetic fabrics and rubbers. Bonding. In addition, blocked isocyanates are also widely used in aqueous polyurethanes, which have the characteristics of low film formation temperature and good film properties. In summary, the use of blocked isocyanates is becoming more widespread, and it is gradually transitioning from solvent to aqueous.
The 4,4-isocyanate diphenylmethane (MDI) used in this study is an important isocyanate, mainly used in the preparation of polyurethane elastomers, polyurethane coatings, etc., in aerospace, construction, vehicle, ship, refrigeration and furniture sectors. Wide range of applications. In order to enhance the covalent bonding force of the synthesized blocked compound with carbon fiber and resin, the water-soluble Resorcinol (adhesive A) and N-methylaniline (adhesive B) were used as protective groups to block the diphenylmethane. The active nature of the diisocyanate and the analysis of the strength and stress of the drawn body using carbon fiber as a test to understand the utility of the test synthesis of the blocked compound. The bridging agent corresponding to the design of the original process allows the screw industry to paint with the use of aqueous slurry to improve the shortcomings of electroplating and organic coatings.

目錄
明志科技大學碩士學位論文指導教授推薦書 ..................................................... I
明志科技大學碩士學位論文口試委員審定書 .................................................... II
致謝 .......................................... III
中文摘要 .................................. IV
Abstract ..................................... V
目錄 .......................................... VII
圖目錄 ...................................... IX
表目錄 ....................................... X
第1章 緒論 ............................. 1
第2章 文獻回顧 ..................... 3
2.1 螺絲王國-台灣 ............ 3
2.2 保護塗料：電鍍、油性漆和水性漆 ......................... 3
2.2.1 電鍍 ......................... 3
2.2.2 油性漆 ..................... 4
2.2.3 水性漆 ..................... 4
2.3 水性體系 ...................... 4
2.3.1 使用水分散性封端異氰酸酯 .................................. 5
2.3.2 使用賦予水分散性的封閉基團 .................................... 5
2.4 封閉型異氰酸酯 ......... 5
2.4.1 封端異氰酸酯 .......... 5
2.4.2 活性亞甲基化合物反應機理封閉異氰酸酯 ...................... 6
2.4.3 亞硫酸氫鹽封閉異氰酸酯的反應機理 ............................ 6
2.5 異氰酸酯結構的影響 ......................................... 7
第3章 研究目的 .................... 9
第4章 實驗步驟與方法 ....... 10
4.1 Resorcinol封閉劑合成方法（接著劑A） ........................... 10
4.1.1 封閉流程 ............... 10
4.1.2 解封閉溫度檢測 .................................... 10
4.2 以N-methylaniline封閉MDI的合成方法（接著劑B） ................. 11
4.2.1 封閉流程 ............... 11
4.2.2 解封閉溫度檢測 .............................. 11
4.2.3 接著劑B乳化 .......................... 11
4.2.4 摻混接著劑B與未摻混接著劑B之漿液粒徑 .............................. 12
4.2.5 上漿碳纖維物性差異 ................................... 12
4.2.6 複材物性差異 .................... 13
第5章 實驗結果 .................... 14
5.1 接著劑A合成法 ......... 14
5.2 接著劑B合成方法 ................................... 15
5.2.1 摻混接著劑B對漿液粒徑大小的響................................ 17
5.2.2 摻混接著劑B對碳纖維物性影響......................................... 18
5.2.3 摻混接著劑B對碳纖維複材物性影響...................... 18
第6章 結果討論與未來研究 ............................ 19
參考文獻 .................................. 20
圖目錄
圖 1-1台灣螺絲外銷近五年概況 .............................................. 1
圖 1-2–NCO反應示意圖 ..................................................... 1
圖 2-1麥德魯姆酸形成可封閉異氰酸酯 ........................... 5
圖 2-2通過與活性氫化合物反應而封端的異氰酸酯................... .... 6
圖 2-3異氰酸酯與丙二的反應 ................................ ... 6
圖 2-4亞硫酸氫鹽封閉異氰酸酯的形成和水解反應 ........................ ....... 6
圖 2-5五種具有不同空間和電子環境的異氰酸酯 ........................ 7
圖 2-6二異氰酸酯單體-H6XDI，XDI和 TMXDI .............................. 8
圖 4-1Resorcinol（間苯二酚）封閉劑合成 ............... ................. 10
圖 4-2以N-methylaniline封閉MDI的合成的合成 ...... ................... 11
圖 5-1MDI與封閉與封閉MDI之FTIR分析圖 ............................... 15
圖 5-2MDI與封閉與封閉MDI之FTIR分析圖 ............................... 16
圖 5-3封閉MDI之NMR分析圖 .................................... .... 17
表目錄
表 2-1封閉型異氰酸酯的解溫度： ................................... 7
表 4-1 摻混接著劑B與未摻混接著劑B之漿液粒徑： ................... 12
表 4-2 上漿碳纖維物性差異： ........................................ 12
表 4-3複材物性差異： ....................................... 13
表 5-1 MDI之FTIR分析： ............................................. 16
表 5-2 封閉MDI之NMR分析： ................................... 17
表 5-3 摻混接著劑B對碳纖維複材物性影響：............ 18

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