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研究生:林弘曄
研究生(外文):Lin Hong Ye
論文名稱:異氰酸鹽衍生之高分子型界面活性劑
論文名稱(外文):Syntheses and Identification of Polymeric Surfactants Derived from Isocyanante
指導教授:戴 憲 弘林 江 珍
指導教授(外文):S. H. DaiJ. J. Linr
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:147
中文關鍵詞:界面活性劑異氰酸鹽預聚合物活性自由基聚合聚環氧乙烯聚環氧丙烯
外文關鍵詞:surfactantisocyanateLiving free radicalpoly(oxyethylene) glycolpoly(oxypropylene) glycol
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摘要
非離子型的界面活性劑其中結構式通常以Poly(oxyethylene) / Poly(oxypropylene)之block copolymer為主。若將苯環結構式存在於高分子型界面活性劑分子中,可提供高分子界面活性劑於界面上時,可能促成π-π電子的影響,若構造上介入Urea的官能基,則Urea上之H-bond可使分子呈規則性排列之特性。
設計一異氰酸鹽預聚合物,再利用多種異氰酸鹽反應而衍生出如線狀、星狀、梳狀等結構的高分子界面活性劑。實驗首先針對異氰酸鹽預聚合物之合成,做一詳細的反應評估,以利合成高選擇性的異氰酸鹽預聚合物,此乃是製備本實驗所有高分子界面活性劑的第一步。再來試圖利用urethane、Isocyanurate、Nylon-1等反應,欲分別合成線狀、星狀、梳狀等結構的高分子型界面活性劑,此部份也將詳細的評估各反應的可能性及其適當的合成條件。於合成梳狀高分子型界面活性劑的部分,另外設計以活性自由基聚合法合成一帶有多個氫氧基的高分子主鏈,再與異氰酸鹽預聚合物進行urethane反應,而生成梳狀結構。
最後測試所合成的界面活性劑之物性並與一般無urethane官能基的非離子型界面活性劑做比較。

Abstract
Many industrial non-ionic surfactants are based on linear polyethers consisting of poly(oxyethylene) as hydrophilic group and poly(oxypropylene) or poly(oxybutylene) as hydrophobic group. If one adds aromatic components into these polyether chain, it could promote interchain reinforcement through π-π interactions. Whereas, when urea or urethane functional groups are introduced into similar polyether structures, they could also provide tighter arrangements between chain through hydrogen bonding. Both of these effects seem desirable if one seeks to prepare an improved polyether surfactant with better-organized surfactant structure.
In this research, we have designed and synthesized several isocyanate prepolymers from diisocyanate, polyether monols, and have subsequently utilized them to synthesize linear, starburst, and comb-shape surfactants. In all these syntheses, the prepolymers made from TDI or IPDI with polyether monols, were synthesized and subjected to specific catalysts and conditions in order to transform them into isocyanate derivatives, such as urethane (linear), isocyanurate (starburst), and Nylon-1 (combs). In addition, a second comb-shape surfactant also has been synthesized from a living free radical polymerization of styrene and HEMA, followed by the addition of isocyanate prepolymers to the OH-groups of the P-styrene/HEMA chain.
All these non-linear surfactants with varied geometric shape were characterized structurally. Their surface activities in water and solutions also have been determined and compared for their relative effectiveness.

目錄
摘要I
AbstractII
目錄III
圖表目錄VII
第一章、緒論1
1-1 前言1
1-2 異氰酸鹽之反應3
1-3 界面活性劑6
1-3.1 界面活性劑之結構(7)6
1-3.2 界面活性劑之分類6
1-3.3 微胞7
1-3.4 單分子層膜理論9
1-3.5 乳液之穩定因素(7)9
1-3.6 雙子星型界面活性劑(63)10
1-4總結11
第二章、文獻回顧12
2-1 具有反應選擇性的異氰酸鹽單體之反應12
2-1.1 2,4-TDI之反應選擇性12
2-1.2 IPDI之反應選擇性15
2-1.3總結22
2-2 Nylon-1之合成文獻回顧23
2-3 TEMPO/BPO系統之活性自由基聚合反應27
第三章、實驗目的29
第四章、實驗方法31
4-1. 實驗概述31
4-2 藥品:32
A、異氰酸鹽單體類32
B、醇類33
C、用於自由基聚合之單體類34
D、觸媒及起使劑相關類35
E、溶劑及添加劑類37
F、其他類38
4-3 實驗步驟39
壹.以具有OH官能基的polyether polyol合成Isocyanate Prepolymer39
貳.以陰離子聚合法聚合具有活性端的Polystyrene或Polybutadiene40
參.利用living free radical polymerization的方法合成具側鏈官能基的Block copolymer41
肆.以陰離子聚合法聚合Nylon-142
伍.Isocyanate Trimer及星狀高分子型界面活性劑之合成42
陸.由Isocyanate prepolymer合成線狀高分子型界面活性劑43
柒.以陰離子聚合法合成PB-Nylon 1(梳狀高分子型界面活性劑)43
捌.將Isocyanate Prepolymer接到具側鏈官能基的Block copolymer上,合成梳狀高分子型界面活性劑44
4-4 分析方法46
(一)Cloud Point:46
(二)OH Value:46
(三)NCO%滴定:47
(四)胺滴定:48
4-5 分析儀器51
(一)紅外線光譜儀(Infrared spectrum analysis;IR):51
(三)表面張力測定儀(tensionmeter):51
(四)核磁共振光譜儀(Nuclear Magnetic resonance spectroscopy;NMR):51
(五)微差熱掃描分析儀(Differential scanning calorimeter;DSC):51
(六)熱重損失儀(Thermal gravimetric analysis;TGA):51
4-6 反應設備52
第五章、結果與討論53
5-1 異氰酸鹽預聚合物之合成53
5-1.1 聚醚醇原料之處理54
5-1.2 以2,4-TDI合成異氰酸鹽預聚合物54
5-1.2 以IPDI合成異氰酸鹽預聚合物63
5-1.4 GPC Area Ratio 意義84
5-1.5 DBTL觸媒對異氰酸鹽預聚合物的影響評估85
5-1.6 結論89
5-2線狀高分子型界面活性劑之合成與界面性質90
5-2.1 線狀高分子型界面活性劑之合成方法90
5-2.2 合成線狀高分子型界面活性劑之界面性質91
5-2.3 合成線狀高分子型界面活性劑之水溶性92
5-2.4 結論93
5-3 星狀高分子型界面活性劑之合成94
5-3.1 Phenyl Isocyanurate以polycat-46合成三元化之評估95
5-3.2 以polycat-46之合成星狀高分子型界面活性劑98
5-4 第一系統梳狀型高分子界面活性劑之合成(Nylon-1系統)101
5-4.1 Poly(Phenyl Isocyanate)之合成評估101
5-4.2 Poly(Butadiene)-b-(Polyisocyanate-g-PEG)之合成結果103
5-5 TEMPO/BPO系統活性自由基聚合之反應111
5-5.1 Synthesis of block copolymer:111
5-5.2 帶OH官能基2 4-hydroxy-TEMPO polystyrene之合成118
5-5.3 PS5-PHEMA1分析119
5-5.4 結論121
5-6 第二系統梳狀型高分子界面活性劑之合成122
5-7 利用異氰酸鹽預聚合物合成Amine之預聚合物(Amine Prepolymer)125
5-7.1 單官能基Amine之預聚合物之合成126
5-7.2 雙官能基polyamine之合成128
5-8 物性評估131
5-8.1 DSC131
5-8.2 TGA131
第六章、結論135
參考文獻138
附錄146
Polyol原料之分析及其他資訊146

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