Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3840
標題: 巨環形碳二亞胺/醯基尿素之合成及其單組份水性聚胺酯之應用
Synthesis of Macrocyclic Carbodiimide/Acylurea and Its Application in One-Component Waterborne Polyurethane
作者: 陳建文
Chen, Chien-Wen
關鍵字: ring-blocked isocyanate (RBI)
環封閉型異氰酸鹽
macrocyclic carbodiimide (MC-CDI)
macrocyclic N-acylurea (MC-ACU)
high-dilution synthesis
end-to-end ring closure
isocyanate-terminated linear precursor
thermal dissociation
ring-opening deblocking
isocyanate precursor
1K WPU
巨環形碳二亞胺
巨環形醯基尿素
高度稀釋合成
末端接合環化反應
異氰酸鹽結尾線狀前趨物
熱解離
開環去封閉
異氰酸鹽前趨物
單組份水性聚胺酯
出版社: 化學工程學系所
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摘要: 在當今節能與環保的思維意識下,兼具低去封閉溫度與無揮發性有機化合物(VOC)排放的理想的封閉型異氰酸鹽(BI)早已成為眾所追求的目標。因此,本論文旨在開發具備低去封閉溫度的環封閉型異氰酸鹽(RBI)進而應用於單組份熱硬化型水性樹脂。RBI之設計乃採用巨環形碳二亞胺(MC-CDI)及其相稱之羧酸作為構成團基,用以製作關鍵的巨環形醯基尿素(MC-ACU)。 MC-CDI之合成是以廣泛使用的異氰酸鹽(NCO)結尾之胺酯預聚物為線狀前趨物,在甲苯高度稀釋與環磷烯氧化物催化下,經單分子末端接合環化程序製備。此線狀前趨物T2P700可由2,4-甲苯二異氰酸鹽(2,4-TDI)與聚丙烯醚醇700二元醇(PPG-700)輕易製得。許多巨環形分子製備的製程變數,包括反應濃度、溫度、催化劑、擬高稀合成法而後被審慎檢驗,使巨環化反應之產物兼具高品質與高產能。含80%自環化T2P700的MC-CDI-T2P700乃藉由擬高稀合成法,在迴流甲苯中(約110°C)於最適化之巨環化反應濃度18.1 g/L 下製得。結構明確之MC-CDI-T2P700可經管柱層析純化,由初步巨環化產物中單離出28%,並且進一步以IR、1H-NMR、與MALDI-TOF MS等光譜確認其結構。 為了辨認最適之醯化條件與結構效應對N-醯基尿素熱解離之影響,各種模式MC-ACU進一步由MC-CDI-T2P700與不同的單元芳香族或脂肪族羧酸反應製得。雖然MC-CDI-T2P700之醯化能以MC-ACU作為主要產物,但仍可察覺些微程度的副產物生成,包含酸酐/巨環形尿素(MC-U)以及異氰酸鹽。整體來說,醯化反應偏好於室溫下進行以便使副反應減少到最低限度。MC-ACU的熱開環反應接著以變溫IR(VTIR)與定溫IR(CTIR)來研究。N-醯基尿素的熱解離被發現受到分子內環形氫鍵模式所影響,特別是羧酸中的電子授予/共振與巨大基團顯現最重要的功效。由於這個研究結果,MC-CDI-T2P700已成功應用於帶有四級羧酸的聚(胺酯-羧酸)(PUCA)與聚(胺酯-羧酸三乙胺鹽)(PUC-TEA)中,作為有效的NCO前趨物以及隱性交聯劑。 最後,兩種熱硬化型單組份水性聚胺酯(1K WPU)乃藉由預先添加兩種環形交聯劑於WPU中作為隱性異氰酸鹽而製得,其中一種為MC-CDI-T2P700初步產物,而另一種為MC-CDI及其二元羧酸衍生之雙巨環形醯基尿素(bis(MC-ACU))之50/50混合物。熱硬化所得之WPU薄膜進而以凝膠含量、酒精吸收性、與拉伸性質作比較。所有的1K WPU皆比純WPU具備較佳之性質。此外,由於MC-CDI能即位生成可觀的NCO結尾分枝,因此似乎是比MC-CDI/bis(MC-ACU) 50/50混合物更好的硬化劑。
Ideal blocked isocyanate (BI) possessing low de-blocking temperatures with no volatile organic compound (VOC) emission has been a highly sought-after target under the current awareness of energy saving and environment protection consideration. Consequently, this dissertation is aimed to develop ring-blocked isocyanates (RBIs) with low de-blocking temperature for applications in one-component thermal curable waterborne resins. Macrocyclic carbodiimides (MC-CDI) and their matching carboxylic acids were used as our building blocks in making key macrocyclic N-acylurea (MC-ACU) as our approach to the designing of our RBI. The MC-CDI was synthesized from an isocyanate (NCO)-terminated linear precursor (i.e., the widely used urethane prepolymer) via a phospholene-oxide catalyzed uni-molecular end-to-end ring-closure process under high dilution in toluene. The linear precursor T2P700 was readily prepared from 2,4-toluene diisocyanate (2,4-TDI) and polypropylene glycol 700 diol (PPG-700). Several process variables in macrocycle preparations, including the reaction concentration, temperature, catalyst, and pseudo-high dilution procedure, were then examined critically in achieving macrocyclization product with good quality and high productivity. A MC-CDI-T2P700 with 80% self-cyclized T2P700 was obtained under an optimized high macrocyclization concentration of 18.1 g/L by pseudo-high dilution synthesis in refluxing toluene (ca. 110C). Structurally well-defined MC-CDI-T2P700 can be isolated in 28% from the crude macrocyclization products by column chromatography and was further confirmed by IR, 1H-NMR, and MALDI-TOF mass spectra. Various model MC-ACUs were prepared by acylation of MC-CDI-T2P700 with different mono-functional aromatic and aliphatic carboxylic acids in order to identify an optimal acylation condition and study the structural effect on thermal dissociation of N-acylureas. Although the acylations of MC-CDI-T2P700 afforded MC-ACUs as the major products, subtle degree of by-product formations, including carboxylic anhydride/ macrocyclic urea (MC-U) and isocyanate species, was discernable. In general, the acylation is preferably carried out at room temperature so as to minimize side reactions. The thermal ring-opening of MC-ACUs was investigated by variable-temperature IR (VTIR) and constant-temperature IR (CTIR). The thermal dissociation of N-acylurea was found to be influenced by the intermolecular cyclic hydrogen bonding model, and particularly the electron donation/resonance and bulky groups in the carboxylic acid groups show the most critical effect. Because of this study, MC-CDI-T2P700 has been successfully applied as an efficient NCO precursor in poly(urethane carboxylic acid) (PUCA) and poly(urethane triethylammonium carboxylate) (PUC-TEA) bearing carboxyl groups bonded to quaternary carbons to serve as the latent crosslinkers. Finally, two thermal curable one-component waterborne polyurethanes (1K WPUs) were prepared by pre-adding two cyclic crosslinkers into WPU as the latent isocyanates, one with crude MC-CDI-T2P700, and another with 50/50 mixture of the MC-CDI and its dicarboxylic acid derived bis(MC-ACU). The gel content, ethanol uptake, and tensile properties of the resulting thermal cured WPU films were obtained and compared. All the 1K WPUs have exhibited better properties than those of the neat WPU. Furthermore, MC-CDI appears to be a better curing agent than the 50/50 mixture of the MC-CDI and bis-(MC-ACU) because MC-CDI formed considerable NCO-terminated branches in-situ.
URI: http://hdl.handle.net/11455/3840
其他識別: U0005-2308201009305300
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2308201009305300
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