陰離子型水性聚胺酯合成與架橋反應、聚集結構之研究

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研究生：	黃義欽 Yi-Chin Huang
論文名稱：	陰離子型水性聚胺酯合成與架橋反應、聚集結構之研究 A Study on the Synthesis、Crosslinking and Aggregate structure of m-TMXDI based Anionic Aqueous Polyurethane Dispersions
指導教授：	邱顯堂 Hsien-Tang Chiu
口試委員:	馬振基 Chen-Chi M. Ma 張豐志 Feng-Chih Chang
學位類別：	博士 Doctor
系所名稱：	應用科技學院 - 應用科技研究所 Graduate Institute of Applied Science and Technology
論文出版年：	2007
畢業學年度：	95
語文別：	英文
論文頁數：	95
中文關鍵詞：	預聚合法、陰離子、架橋、自身縮合
外文關鍵詞：	Crosslinking, Self-condensation
相關次數：	點閱：185 下載：3
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本研究主要目的是利用預聚合法(Prepolymer mixing process)合成m-TMXDI based的陰離子型水性PU，利用GPC、FTIR、13C-NMR 鑑定分子結構，及探討DMPA用量對水性PU的物理化學性質影響。結果顯示隨著DMPA用量增加，水性PU的親水能力隨著增加，而平均粒徑逐漸減小，黏度也相對增加。
由於本實驗合成的水性PU分子結構中含有很多可架橋的>N-H基，當選用PMMF (Partially methylated melamine formaldehyde)做為水性PU架橋劑，可能生成多數的分支(Branch)與部份架橋(Partially crosslinking)結構。利用剛性擺錘振動減衰儀（Rigid-body Pendulum Rheometer）測試觀察在恆溫下的熱硬化行為。結果顯示在熱硬化過程中，水性PU與PMMF進行架橋時，PMMF自身縮合反應(Self-condensation)同時發生。而且PMMF自身縮合反應速率低於PU/PMMF的架橋反應。利用TGA熱分析，也可以證實PMMF自身縮合反應在120~150oC溫度下確實發生。實驗結果也發現30phr是最適量的PMMF架橋劑，120oC是最適當的反應溫度。
利用動態機械性質分析(Dynamic Mechanical Analysis)，發現當測試溫度低於玻璃轉移溫度以下，其儲存模數(Storage modulus)隨著PMMF用量增加而降低，這是因為受到分子鏈排列程度(Packing ability)的影響。但是當溫度升至-20oC時，很明顯的，儲存模數(Storage modulus)反而隨著PMMF用量增加而略為增加，這是因為多數的分支(Branch)與部份架橋(Partially crosslinking)結構會限制高分子鏈的運動。另外，利用拉力試驗機(Tensile testing machine)測試，也發現PMMF用量與反應溫度對力學性質有明顯的影響，當PMMF用量增加或提高反應溫度時，應變量(Strain) 會明顯降低，應力(Stress)則相對提高。這也是因為多數的分支(Branch)與部份架橋(Partially crosslinking)結構形成的影響。

The objective of this study is to prepare the isocyanic acid, m-phenylenediiso- propylidene (m-TMXDI) based poly(urethane-urea) dispersions containing various amount of DMPA. The colloidal stability of poly(urethane-urea) dispersions arose entirely from the presence of ionized carboxylic acid groups. The chemical structure of poly(urethane-urea) dispersions with various amount of DMPA were identified by FTIR and 13C NMR analysis. The test results showed the hydrophilicity of poly(urethane-urea) dispersions were increased with increasing in DMPA content. The average particle size of poly(urethane-urea) dispersions were decreased with an increase in DMPA content, and this leaded to an increase in viscosity.
The anionic poly(urethane-urea) dispersion has a large number of >N-H crosslinking or branching sites in urethane and urea groups per molecule, that allows a large number of partially methylated melamine formaldehyde (PMMF) to couple into elastic PUD backbone to form branched structure with partially crosslinking. A rigid-body pendulum rheometer was used to observe the isothermal cure behavior of anionic poly(urethane- urea) dispersion crosslinked with different amount of PMMF. The test results showed that cure response of PU dispersion crosslinked with PMMF was a function of the concentration of PMMF, and indicated that 30 phr PMMF used can be the optimum amount of crosslinking agent, the reaction at 120oC is the optimum temperature for the curing process. In addition, PMMF self-condensation could take place during the curing process. The self-condensation of PMMF also can be monitored by thermal gravimetric method.
It is observed from the dynamic mechanical analysis that non-crosslinked PUD exhibits high storage modulus value than PMMF crosslinked PUD at the temperature scanned below glassy region, this is attributed to the polymer packing ability. However, a turning point occurs at temperature scanned higher than -20oC, PMMF crosslinked PUD exhibit higher storage modulus than non-crosslinked PUD, due to PMMF branched PUD structure is formed with partially crosslinking, which can restrict the motion of polymer chains. It was further shown that the tensile properties were strongly influenced by the concentration of PMMF and curing temperature. This strong decrease in strain at break with high tensile strength is also reasonable to assume that PMMF branched PU is formed with partially crosslinking.

Abstract (in Chinese) 						I
Abstract								II
Acknowledgment							IV
Contents								V
List of figures and tables						VIII

Chapter 1 Introduction						1
1.1 Introduction of aqueous polyurethane dispersions			2
1.2 Chemistry and dispersions					2
1.2.1 PU chemistry							2
1.2.2 Ionomer					          	5
1.2.3 Non ionomer							5
1.2.4 Dispersion mechanism						6
1.2.5 Particle stabilization		                   	6
1.3 Preparation process						7
1.3.1 Acetone process						7
1.3.2 Prepolymer mixing process					8
1.3.3 Melt dispersion process					8
1.3.4 Ketimine and Ketazine processes				8
1.4 Dispersion and film properties 					9
1.5 Crosslinking of aqueous polyurethanes 				10
1.5.1 Azilidines 							11
1.5.2 Carbodiimides						11
1.5.3 Blocked isocyanates						11
1.5.4 Radiation induced crosslinking					11
1.5.5 Melamine-formaldehyde						12
1.6 Aqueous polyurethane/acrylic emulsion hybrid			13
References							13

Chapter 2 Synthesis and characterization of Isocyanic acid, m-phenylenediiso- propylidene based poly(urethane-urea) dispersions containing different amount
 of DMPA								26
Abstract								27
2.1 Introduction							28
2.2 Experimental							29
2.2.1 Materials							29
2.2.2 Preparation of anionic poly(urethane-urea) dispersions		29
2.2.3 Characterization						30
2.3 Results and discussion						31
2.3.1 Synthesis of anionic poly(urethane-urea) dispersions		31
2.3.2 Chemical structure of poly(urethane-urea) dispersions		34
2.3.3 Effect of DMPA content on colloidal properties 			35
2.4 Conclusion							36
References							37

Chapter 3 Curing behavior of anionic poly(urethane-urea) dispersion crosslinked with partially methylated melamine formaldehyde		55
Abstract								56
3.1 Introduction							57
3.2 Experimental							58
3.2.1 Materials							58
3.2.2 Sample preparation						59
3.2.3 Rigid-body pendulum rheometer measurement			59
3.2.4 Thermal gravimetric analysis					60
3.2.5 Structure characterization					60
3.3 Results and discussion						61
3.3.1 Curing behavior of PU dispersion crosslinked with PMMF		61
3.3.2 Thermal degradation behavior					62
3.3.3 Crosslinking mechanism					63
3.4 Conclusions							65
References							65

Chapter 4 Structure- property relationsips of PMMF crosslinked PU dispersions                                                              75
Abstract								76
4.1 Introduction							77
4.2 Experimental							78
4.2.1 Materials							78
4.2.2 Sample preparation						78
4.2.3 Dynamic mechanic analysis					78
4.2.4 Tensile properties analysis					78
4.3 Results and discussion						79
4.3.1 Dynamic mechanic properties analysis				79
4.3.2 Tensile properties analysis					80
4.4 Conclusions							81
References							81

Chapter 5 Conclusions						91
List of publications						94
Introduction to the author						95


List of figures and tables

Figure index
Scheme 1-1	Acetone process					17
Scheme 1-2	Prepolymer mixing process				18
Scheme 1-3	Melt dispersion process				19
Scheme 1-4	Ketimine and Ketazine process			20
Scheme 1-5	Crosslinking with polyfunctional aziridines		21
Scheme 1-6	Crosslinking with multifunctional carbodiimide	22
Scheme 1-7	Crosslinking with blocked isocyanate			23
Scheme 1-8	Crosslinking with melamine formaldehyde		24
Scheme 2-1	Prepolymer mixing process				47
Figure 1-1	Schematic representation of electric double layer	25
Figure 2-1	Chemical structure of m-TMXDI			48
Figure 2-2	FTIR spectra of the polyurethane-urea) dispersions
                  containing  different DMPA content			49
Figure 2-3	13C-NMR spectrum of polyurethane dispersions containing
                  different DMPA content				50
Figure 2-4	Chemical structure of anionic poly(urethane-urea)
                  dispersion                                             51
Figure 2-5	Effect of DMPA content on the particle size and
                  distribution of the dispersions			52
Figure 2-6	Effect of DMPA content on the average particle size and
                  viscosity of the dispersions			53
Figure 2-7	Thermal gravimetric curves of anionic poly(urethane-urea)
                  dispersions					54
Figure 3-1	Chemical structure of partially methylated melamine
                  formaldehyde					67
Figure 3-2	The device of rigid-body pendulum rheometer		68
Figure 3-3	The oscillation pattern of the pendulum		69
Figure 3-4	Isothermal curing behavior of PU dispersion crosslinked
                  with various amount of PMMF (a)at120oC ; (b)at150oC	70
Figure 3-5	A comparison of the curing curves of PMMF crosslinked
                  PU  dispersion and PMMF self-condensation		71
Figure 3-6	Thermal gravimetric curves of PMMF self-condensation	72
Figure 3-7	Thermal gravimetric curves of PU dispersion crosslinked
                  with   PMMF					73
Figure 3-8	FTIR spectra of PU dispersion crosslinked with various
                  amount of PMMF					74
Figure 4-1	(a)Storage modulus, (b) Loss modulus and (c) Loss tangent
                  versus temperature plots of PUD crosslinked with PMMF	86
Figure 4-2	Stress strain curve of PUD crosslinked with various amount
                   of PMMF (120oC x 30min.) 				87
Figure 4-3	Stress strain curve of PUD crosslinked with various amount
                   of PMMF (150oC x 30min.) 				88
Figure 4-4	The effect of curing temperature on the tensile properties
                  of PUD crosslinked with PMMF			89
Figure 4-5	Possible approaches of PUD crosslinked with PMMF	90

Table index
Table 2-1	    Compositions of NCO terminated prepolymer	           	39
Table 2-2	    Compositions of water dispersion and chain extension	40
Table 2-3	    Average molecular weight of NCO term inated prepolymer	41
Table 2-4	    Molecular weight of chain extended poly(urethane-urea)
             dispersions 						42
Table 2-5	    Ionic content of anionic poly(urethane-urea) dispersions	43
Table 2-6	    Assignment of IR spectrum of anionic poly(urethane-urea)
             dispersions						44
Table 2-7	    Assignment of 13C chemical shifts of anionic poly(urethane-urea)
             dispersions						45
Table 2-8	   Colloid properties of anionic poly(urethane-urea) dispersions46
Table 4-1	   The glass transition temperature of PUD crosslinked with various
             amount of PMMF						83
Table 4-2	   Mechanical properties of PUD crosslinked with PMMF
            (120oC x 30min.) 					84
Table 4-3	   Mechanical properties of PUD crosslinked with PMMF
            (150oC x 30min.) 					85

                                

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