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研究生： 楊景丞
CHING-CHENG YANG
論文名稱： Hydroxyl Terminated Polyisoprene(HTIP)陰離子型水性PU合成與性質研究
The studies of synthesis and properties of anionic water-borned polyurethane as the soft segment is Hydroxyl Terminated Polyisoprene(HTIP)
指導教授： 陳登科
Teng Ko Chen
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
畢業學年度： 90
語文別： 中文
論文頁數： 99
中文關鍵詞： 聚烯類 、預聚合法
外文關鍵詞： Prepolyrmer mixing process, HTIP, H12MDI
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    • 環境污染日益嚴重及立法的限制亦趨嚴格的情況下，原本由溶劑製程的ＰＵ樹酯已部分的被由低污染、低溶劑使用量的製程所取代。而基於溶劑的價格昂貴、對環境的高污染性及產物物性的比較下﹔水性ＰＵ系統的開發與應用已延續了４０年。
    自1970年開始，水性ＰＵ的發展著重於工業生產價值，然而；公開文獻在軟、硬質兩相因離子基的導入；其熱性質的影響以及微相結構變化與物理性質之間的關係上，卻少有深入的探討。過去；不論是專利或文獻，大多都以極性式聚酯或聚醚類作為軟質段，對以非極性式軟質段的水性PU記載甚少。所以﹔本論文以分子量2500的聚烯類HTIP(Hydroxyl Terminated Polyisoprene)為軟質段，以預聚合混合法(pre- polymer mixing process)合成一系列以硬段含量(30wt.%、50 wt.%、70 wt.%)、離子基含量(1.0 wt.%〜3.0 wt.%不等)及中和劑種類(TEA、TPA、TBA)為變數的分散液，探討各分散液粒徑及黏度的變化，並以FTIR鑑定合成結構，以TGA及DSC探討其熱性質，以DMA探討其動態黏彈性質，以拉力測試探討應力應變的行為。
    非極性式WPU會隨著硬段含量增加及離子基含量減少，粒徑隨之減小。FTIR的結果可知道以成功合成一系列分散液。由DSC與HTPB based WPU的TEM的結果，可以知道水性PU的微相結構為一立體網狀構造，隨著離子基及硬段含量增加，網狀密度增加且更為連續。而DMA的結果顯示硬質段的relaxation溫度隨著離子基含量增加而下降；隨著硬段含量增加而升高，而當中合劑種類改變，隨著烷基氨類碳數增加，硬質段的relaxation溫度隨之下降。由應力-應變的結果，斷裂強度與起始模數隨著離子基含量及硬段含量而增加，斷裂延伸則隨之下降，烷基氨類碳數增加，斷裂強度與起始模數隨之下降，斷裂延伸則上升。

    Abstract
    Due to the need of environmental pollution control and strict legal limitation, conventional solvent-borned PU resin systems were replaced by low solvent or solvent-free aqueous PU dispersion.Water-borned PU use water as a solvent are less expensive,have excellent mechanical strengh and cause less pollution. So in the last 40 years,water-borned PU have generated interest.
    From 1970，since the fous on PU was mostly from industry,most of the literature was in the form of patents with emphasis only on synthesis and particle stability. The structure and property relationship, especially the effect of ionic group on the physical and morphological behaviors, has obtained very little attentions.In past,no matter patent or litrerature, polar polyester or polyether-polyol usually are the soft segment, but water-borned PU with nonpolar soft segment was received less attention. So,HTIP(Hydroxyl terminated Polyisoprene) as Mw 2500 was synthesized as soft segment in our series nonpolar water-borned PU dispersion by prepolymer mixing processes. The hard segment content was 30,50 and 70 wt.%). Ionic content was 1.0 - 3.0 wt.% and neutralizing agent were TEA,TPA and TBA. The variables were studied by ZetaSizer,Viscosity,FTIR,TGA,DSC,DMA and mechanical properties.
    The average diameter of dispersion particles become samaller with increasing hard segment content and decreasing ionic content. Successfully the series dispersion were synthesized and characterized by FTIR. The result of DSC and TEM of HTPB based WPU showed that the micro-structure of water-borned polyurethane was three-dimensional network and the density of network increased with increasing ionic content and hard segment content. The result of DMA showed that the relaxation temperature decreases with the increasing ionic content and increase with hard segment content. The relaxation temperature decreses with increasing number of carbons in various neutralizing agents. From the results of mechanical behavior,tensile strengh and initial modulus increase with increasing ionic content and hard segment content,elongation at break decrease with increasing ionic content and hard segment content. Tensile strengh and initial modulus decreases and elongation at break increases with increasing number of carbons in various neutralizing agents.

    摘要 目錄---------------------------------------------Ⅰ 圖目錄-------------------------------------------Ⅴ 表目錄-------------------------------------------Ⅷ 第一章序論----------------------------------------1 第二章、文獻回顧-----------------------------------3 2.1 水性PU的介紹-----------------------------------------3 2.1.1 線性嵌段式PU結構---------------------------------3 2.1.2 PU離子體(PU ionomers) -----------------------------4 2.1.2.1陰離子型-------------------------------------5 2.1.2.2陽離子型-------------------------------------7 2.1.2.3陰陽離子共存型(Zwiteerionomer)---------------8 2.1.2.4非離子型-------------------------------------8 2.1.3 PU水性化的製程------------------------------------8 2.1.3.1 Solution process------------------------------9 2.1.3.2 Prepolymer mixing process--------------------10 2.1.3.3 Hot melt process-----------------------------11 2.1.3.4 Ketimine(and ketazine) process---------------11 2.2 WPU分散液的行程機制與物理安定性質-------------------12 2.2.1 水分散的機制-----------------------------------12 2.2.2 電雙層理論-------------------------------------15 2.2.3 WPU成膜性質------------------------------------21 2.3 非極性式與極性式PU系統熱性質之比較------------------21 2.3.1軟質相的玻璃轉變性質----------------------------21 2.3.2硬質相的玻璃轉變性質----------------------------23 2.4 影響WPU機械性質的主因-------------------------------25 2.4.1 離子基含量-------------------------------------25 2.4.2 軟段種類----------------------------------26 2.4.3 軟段分子量-------------------------------------26 2.4.4 異氫酸鹽種類-----------------------------------28 2.4.5 硬質段含量-------------------------------------28 2.4.6 中和劑種類-------------------------------------29 第三章、實驗部份-----------------------------31 3.1 化學藥品---------------------------------------------31 3.2 儀器設備---------------------------------------------32 3.3 水性PUU(Polyurethane urea)合成-----------------------32 3.3.1 反應物------------------------------------------32 3.3.2 合成步驟----------------------------------------33 3.3.3 二丁基胺滴定法(ASTM-D1368)----------------------33 3.3.4 試片的製造---------------------------------------34 3.4 水性PU sample 的鑑定---------------------------------35 3.4.1 Zetasier ------------------------------------------35 3.4.2 黏度的量測----------------------------------------35 3.4.3 FTIR----------------------------------------------35 3.4.4 TGA-----------------------------------------------36 3.4.5 DSC-----------------------------------------------36 3.4.6 DMA-----------------------------------------------36 3.4.7 機械性質-----------------------------------------37 第四章、結果與討論---------------------------38 4.1 合成-------------------------------------------------38 4.2分散液平均粒徑與黏度----------------------------------41 4.3 FTIR-------------------------------------------------44 4.4 TGA--------------------------------------------------53 4.5 DSC--------------------------------------------------60 4.6 DMA--------------------------------------------------71 4.7 機械性質---------------------------------------------76 第五章、結論---------------------------------79 參考文獻------------------------------------82

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