臺灣博碩士論文加值系統

熱塑性聚胺甲酸酯TPU黏著劑，若具有高度軟鏈段結晶時，比非結晶型的TPU有諸多優點，不但有強的初期接著力，也可提升完成黏合後的接著力，以聚環己內酯多元醇（Polycaprolactone diol；PCL Diol）為主聚酯醇所製成的TPU，在TPU中，除了結晶度之提高外更可帶來相分離之迅速形成，因此，可作成性質極佳之TPU黏膠。為近幾年的發展趨勢。為了順應世界潮流，開發結晶型TPU是國內鞋用黏著劑的主要目標之一。
本實驗首先分析結晶型聚胺甲酸酯黏著劑的廣用商業化產品：Merquinsa（Pearlstick，45-60/18）、Bayer（Desmocoll-540）等二項產品，研究其原料組成、結晶程度與結晶速率、分子量大小對溶解度與接著力的影響，以分辨它們之間的差異，並做我們發展及製作TPU黏著劑配方的指南。
由分析之資料及可能應用之商業原料，以商業上的聚酯為例，如：聚環己內酯多元醇，依不同軟鏈之起始劑、軟鏈PCL Diol的分子量、硬鏈段與軟鏈段之比，可找出熱性質及結晶型態最接近Pearlstick的比例。以此莫耳數比值為主，再使用不同種類的PCL Diol來製成TPU，比照出最接近Pearlstick物性的PCL Diol分子結構。從儀器的分析中，得知最適當的（BDO/PCL）為0.6而PCL Diol為DEG-3000。由此實驗所得之的配方資訊，使用於雙螺桿反應押出機，以連續式反應程序，可做出非溶劑型之TPU黏著劑。

When thermoplastic polyurethane (TPU) adhesives possess crystalline components as their soft-segments, they generally exhibited superior performances over those without. The formers usually have higher green strengths and provide stronger bonding characteristics after applications. Utilization of polycaprolatone diols (PCL Diols) as the major soft segment component has become one of the most sought-after approach in making adhesive TPUs. Poly-caprolactone diols (PCL Diol) of high molecular weight are crystalline raw materials. TPUs prepared from PCL Diols have been shown to form rapid phase-segregation in the polymer morphology. As a result, the crystalline TPU adhesives possess excellent adhesive properties. Solubility of the TPU in non-toxic solvent such as acetone is also high. In short, crystalline TPUs have many advantages sought in industrial applications such as shoe-making industry.
Our research begins with composition analyses of some commercial crystalline TPU adhesives such as Pearlstick 45-60/18 from Merquinsa and Desmocoll-540 of Bayer. Then we studied their possible raw materials used and determined their crystalline characteristics, molecular weight distributions, solubility and their adhesive performances. From those analyses as our guide, we then developed similar formulations and attempted to prepare TPU adhesives using two processing techniques.
Since the analysis has shown that the major raw materials of TPU adhesives are consisting of methylene diphenyl diisocyanate (MDI), butanediol (BDO), and a polyester diols such as PCL Diols as the major raw materials, we have screened several commercial PCL Diols of different molecular weights and initiators for TPU preparations. In order to match properties of our TPU products with the commercial TPUs, four TPUs with hard to soft ratios of 1.0, 0.8, 0.6 and 0.4 (BDO/PCL Diols) were also prepared. Finally, the thermal and crystalline properties of all these prepared TPU were gathered. Among them, we were able to identify that a (BDO/PCL-3000 diol) ratio of 0.6 would have high similarity to the commercial products. A preliminary continuous preparation of the TPU adhesive using a twin-screw extruder has been tried.

摘要 I
Abstract 2
目錄 4
表目錄索引 6
圖目錄索引 7
符號說明 8
第一章、序論 1
第二章、文獻回顧 2
2-1、TPU合成之原料【1】 2
2-1-1、二元異氰酸鹽 2
2-1-2、聚醇 2
2-2、TPU之概論 5
2-2-1、TPU之製備方法【5】 7
2-2-2、TPU之微相分離理論 9
2-2-3、TPU之特性 10
2-3、PU黏著劑之特色【11】 14
2-4、PU黏著劑及用途【12】 15
2-4-1、鞋用黏著劑應具備的性能 15
2-4-2、影響膠粘劑性能的主要因素 15
2-5、結晶型TPU之特色 17
2-6、聚環己內酯二元醇（Polycaprolactone diol）作TPU的優點 17
2-7、聚環己內酯二元醇（Polycaprolactone diol）對TPU的影響 18
2-7-1、起始劑種類的影響【14】 18
2-7-2、分子量分佈指數的影響【14】 18
2-7-3、分子量大小的影響 18
2-7-4、軟鏈段大小的影響 19
第三章、實驗方法 20
3-1、實驗概述 20
3-2、實驗材料與藥品 21
3-2-1、聚環己內酯二元醇（Polycaprolactone diol；PCL diol） 21
3-2-2、鏈延長劑 23
3-2-3、二異氰酸鹽 23
3-2-4、催化劑（Catalysts） 24
3-2-5、溶劑（Solvent） 25
3-3、實驗步驟 29
3-3-1、實驗室製作的400公克級TPU 29
3-3-1-1、原料的前處理 29
3-3-1-2、TPU的實驗室之合成步驟 30
3-3-1-3、TPU產品的取樣（C sample之製作）（圖 3-3） 32
3-3-1-4、TPU產品的粉碎方法（C0 sample之製作）（圖 3-4） 32
3-3-1-5、TPU之混鍊程序：（C1與C2 sample之製作） 32
3-3-1-6、DMA的試片製作 33
3-3-2、以雙螺桿反應押出TPU的製作 36
3-3-2-1、原料的前處理 39
3-3-2-2、合成步驟 39
3-3-3、樣品分析 44
3-4、分析方法 45
3-5、分析儀器 48
3-6、反應設備 49
第四章、實驗結果 53
4-1、商業化產品（Pearlstick 45-60與Desmocoll-540）之分析 53
4-2、不同Polycaprolactone diol之分析 58
4-3、TPU-DEG-3000-（BDO/PCL）-C0之分析比較 64
4-4、不同Polycaprolactone diol之分析與比較 84
4-5、雙螺桿反應押出實驗之分析 114
第五章、實驗討論 120
5-1、商業TPU產品之NMR分析 120
5-2、商業TPU產品之DSC分析 123
5-3、由實驗室TPU（C0）的DSC推斷（BDO/PCL）莫耳數之比值 125
5-4、實驗室TPU經塑譜儀之混煉之結果 126
5-5、實驗室TPU（C0、C1、C2）的DSC分析結果 127
5-6、批次法製作實驗室TPU的其他觀察 130
5-6、催化劑及Polycaprolactone diol之選擇 131
5-7、雙螺桿反應押出之測試 134
第六章、結論 137
第七章、參考文獻 141

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