臺灣博碩士論文加值系統

本研究包含兩個部分，第一部分旨在探討以超臨界CO2流體進行聚己內酯(PCL)固態聚合及其對結晶形態之影響。結果顯示，PCL具有羰基(C=O)之特性基團與CO2存在著交互作用力關係，兩者具有互溶性，而且CO2流體對PCL之溶解能力受控於溫度、壓力及含浸時間的影響。在固定溫度(35℃)下，壓力增加可提高互溶能力，且隨著時間增加而增加，當超過60min時CO2分子溶解於PCL之量趨於飽和。超臨界CO2流體並可使PCL進行固態聚合反應(會提高分子量)及轉酯化反應(會降低分子量)。結果顯示，在CO2壓力36 atm下PCL發生較多的固態聚合反應；在壓力84及304 atm下除了進行固態聚合反應外也會進行轉酯化反應。此外，溶於超臨界CO2流體之PCL，在CO2洩壓過程會進行二階段結晶行為。由SAXS分析所獲得Lorentz- corrected圖譜上出現零角度散射(Zero-angle scattering)，表示PCL lamella中之無定形PCL會受到CO2分子的作用而被排擠到Interfibrillar 間，並且形成不均勻性區域塊(Morphous domain)。
第二部分則是探討超臨界CO2流體對聚己內酯(PCL)/聚氯乙烯(PVC)摻合體相形態之影響，由DSC測得熔點下降以及DMA測得單一玻璃轉移溫度，顯示此摻合體為一相容系統。藉由SAXS之分析發現：PCL/PVC摻合體之結晶層厚(lc)與非結晶層厚(la)隨著PVC組成增加而降低，使其φS<1，此乃PVC的稀釋結晶效應及被排擠到Interlamellar區域外之故。經超臨界CO2流體處理後，則PVC被排擠的距離愈遠，形成更大的不均勻區塊，此現象可由Lorentz- corrected圖譜上出現Zero-angle scattering強度變大而獲得證實。此外，摻合體受到超臨界CO2流體的作用會導致結晶與非結晶區域間之電子密度差異增加，使得摻合體之相形態發生變化。

This report includes two parts. The first part presents results on the investigated of solid-state polymerization and phase behavior of polycaprolactone (PCL) in supercritical carbon dioxide fluids (SCF CO2). PCL is found to be miscible with SCF CO2, the miscibility depending on CO2 conditions, via interactions between the carbonyl groups of PCL and CO2. In addition to solid state polymerizations, which could increase molecular weights of PCL, transesterification reactions of PCL are found as well, decreasing molecular weights of PCL. The extent of solid state polymerizations and transesterification reactions are dependent upon CO2 conditions, with the 36-atm CO2 giving a dominant solid state polymerization while 84-atm and 304-atm CO2 giving both reactions. PCL dissolved in SCF CO2 can perform a recrystallization during depressurizing of CO2 and exhibits a disordered structure of lamellar stacks as evidenced by zero-angle scattering from SAXS measurements.
The second part presents results on the effects of SCF CO2 on the phase behavior of PCL/PVC blends. Prior to SCF CO2 treatments, DSC and DMA data demonstrate that PCL/PVC blends in this study are compatible blends. SAXS data demonstrate that thickness of both crystalline layer and amorphous layer in the lamellar stacks increase with increasing PVC contents in the blends. The phase segregation distance of PVC increases with increasing PVC contents in the PCL/PVC blends during crystallization of PCL. For a given blend composition, the segregation distance of PVC during recrystallization of PCL after SCF CO2 treatments is relatively high as compared with the blend before SCF CO2 treatments.

中文摘要 --------- i
英文摘要 --------- iii
誌謝-------------- v
目錄-------------- vi
表目錄------------ ix
圖目錄------------ xi
符號說明 --------- xv
第一章 聚己內酯在超臨界CO2流體之固態聚合反應及結晶形態變化
之研究
一.緒論-----------------------------------------1
1 . 1 前言----------------------------------1
1 . 2 文獻回顧------------------------------4
1 . 2. 1 二氧化碳溶解量之文獻回顧-----------4
1 . 2. 2 固態聚合之文獻回顧-----------------7
1 . 2. 3 聚己內酯(PCL)結晶動力學之文獻回顧--12
1 . 3 研究目的與動機------------------------13
二.理論-----------------------------------------15
2 . 1 超臨界流體----------------------------15
2 . 1. 1 何謂超臨界流體---------------------15
2 . 1. 2 超臨界流體之特性-------------------16
2 . 1. 3 為何選用超臨界流體CO2--------------19
2 . 1. 4 高分子含CO2之基礎特性--------------20
2 . 2. 固態聚合-----------------------------21
2 . 2. 1 何謂固態聚合-----------------------21
2 . 3 結晶熱力學----------------------------23
2 . 3. 1 平衡熔點與熔點---------------------23
2 . 3. 2 結晶性高分子摻合體的平衡熔點-------27
2 . 4 結晶動力學----------------------------29
2 . 4. 1 結晶動力學理論---------------------29
2 . 4. 2 球晶成長動力學理論-----------------31
2 . 5 X-ray相關理論-------------------------35
2 . 5. 1 X光的產生--------------------------35
2 . 5. 2 X射線管----------------------------35
2 . 5. 3 布拉格定律(Bragg’s Law) ----------37
2 . 5. 4 X-ray繞射--------------------------37
2 . 6 小角度X-光散射(SAXS)簡介--------------39
2 . 6. 1 SAXS基本原理-----------------------39
2 . 6. 2 相關函數(Correlation function)分析-40
2 . 6. 3 低限q值的近似----------------------44
2 . 6. 4 無限大q值的近似--------------------46
三.實驗部分-------------------------------------49
3 . 1 實驗藥品------------------------------49
3 . 2 實驗設備------------------------------49
3 . 3 實驗方法------------------------------51
3 . 3. 1 試樣之製備-------------------------51
3 . 3. 2 試樣之分析-------------------------52
四.結果與討論-----------------------------------54
4 . 1 超臨界CO2流體對聚己內酯(PCL)之溶解行為-54
4 . 2 PCL在超臨界CO2流體中之固態聚合反應-----59
4 . 3 超臨界CO2流體對聚己內酯（PCL）結晶行為之影響---71
4 . 3. 1等溫程序 PCL在不同壓力CO2下之結晶行為-------71
4 . 3. 2非等溫程序 PCL在不同壓力CO2下之結晶行為-----73
4 . 3. 3PCL分子量效應在超臨界CO2流體下之結晶行為----75
4 . 4 以SAXS測定PCL經超臨界CO2流體處理前後之結晶
形態變化------------------------------------------------83
五.結論-----------------------------------------97
六.參考文獻-------------------------------------98
第二章 超臨界CO2流體對PCL/PVC摻合體相形態之影響
一.緒論-----------------------------------------102
1 . 1 前言----------------------------------102
1 . 2 文獻回顧------------------------------105
二.理論-----------------------------------------109
2 . 1 摻合體之相容性------------------------109
2 . 1. 1 聚摻合原理-------------------------109
2 . 1. 2 聚摻合體之親合性-------------------109
2 . 1. 3 研究摻合體相容的方法---------------112
2 . 1. 4 玻璃轉移點(Tg)法-------------------112
2 . 2 聚摻合體的結晶形態--------------------114
2 . 3 動態機械分析－分子運動之分析----------119
三.實驗部分-------------------------------------121
3 . 1 實驗藥品------------------------------121
3 . 2 實驗設備------------------------------122
3 . 3 實驗方法------------------------------123
3 . 3. 1 聚摻合體製備-----------------------123
3 . 3. 2 分析試樣之方法---------------------123
四.結果與討論-----------------------------------129
4 . 1 PCL/PVC摻合體系統相容性之探討---------129
4. 1. 1 熔點(Tm)的測定----------------------129
4 . 1. 2 玻璃轉移溫度(Tg)的測定-------------131
4 . 2 PCL/PVC摻合體系統之交互作用力對結晶與熔融行為
之影響------------------------------------------132
4 . 3 以小角度X光散射(SAXS)探討PCL/PVC摻合系統經
超臨界CO2流體處理前後之結構形態變化-------------134
五.結論-----------------------------------------158
六.參考文獻-------------------------------------159
自述--------------------------------------------162

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