(一) Comb-like Polymer Complex
PEO / Dodecylbenzenesulfonic Acid( DBSA ) 錯合物

利用PEO與界面活性劑DBSA之間的鍵結形成錯合物，使PEO主鏈連結上烷鏈分子，在藉由自我聚集的行為形成似梳狀( comb-like )的分子組態。Fourier transform infrared spectrometry( FTIR )的實驗結果，證實兩者間具有氫鍵作用力。另外，在偏光顯微鏡( POM )下，PEO(DBSA)x具有雙折射的介相( mesophase )特性，加上小角度X光散射( SAXS )、廣角度X光散射( WAXS )的圖譜顯示，PEO(DBSA)x具有微相分離( microphase separation )之層狀結構，證實PEO(DBSA)x具有似梳狀( comb-like)的組態。

經由SAXS、熱差式掃描分析儀( DSC ) 、POM等實驗的分析與PEO(DBSA)x的結構式預測，可以證實PEO被分散在DBSA 層狀結構的極性層間，且為一高度延伸的狀態，即DBSA的存在，將使得PEO具有奈米級的分散。

確定PEO(DBSA)x的結構後，針對錯合物的結晶行為、介相消失溫度、介相形成速度等特性加以探討。DBSA的加入使得PEO主鏈受到相當的束縛，對其結晶性質產生相當大的影響，由實驗結果顯示，只有在低組成的DBSA含量時，才可發現PEO的結晶，但其結晶度將較純PEO下降許多。

測定PEO(DBSA)x的相圖顯示，其介相消失溫度比純DBSA高，顯示PEO的加入有助於介相結構的穩定 ，且發現錯合物mesophase形成速度較純DBSA快得許多，配合SAXS 熔融態的實驗，可證實是因為熔融態中PEO-DBSA氫鍵的作用力導致兩者間在熔融態時已具有局部的規則性或濃度擾動( concentration fluctuation )，進而造成錯合物mesophase的形成速度較純DBSA快。

(二) Star-like Polymer Complex

Amino-terminated Poly(ethylene oxide)( PEO-NH2 ) /4-sulfonic calix[n]arene ( SCA-n ) Complex

在本研究中，針對星狀高分子的結構，我們提出一種全新的製備方法：以末端具有-NH2官能基之PEO( PEO-NH2 )為手臂分子，和環狀具-SO3H基團的4-sulfonic calix[n]arene( SCA-n，其中n表示SCA具有之SO3H基團的數目 )為核產生錯合，以生成星狀分子架構。利用SCA-n上-SO3H基團產生質子化( protonation )成為-SO3-，使得H+ 離子跑到-NH2基團上成為-NH3+，進而在兩者間產生離子作用力以形成star complex。在這次的研究系統中，我們分別使用具有8和4個-SO3H基團的SCA為核，使其產生8根與4根手臂數目的star complexes，分別命名為star 1和star 3並進一步探討手臂數目對星狀高分子性質的影響。

藉由滴定實驗和model compound的FTIR圖譜，結果顯示-SO3-和NH3+ 間確實產生離子作用力。並比較純SCA-8、star 1、star 3、PEO-OH( 末端具有-OH官能基之PEO ) + SCA-8、PEO-OH + SCA-4和純PEO-NH2、PEO-OH於氯仿和甲苯的溶解度，結果顯示只有star complexes與純PEO-NH2、PEO-OH可溶於氯仿及甲苯中，故證實PEO-NH2和SCA-n鍵結在一起，導致star 1和star 3可溶於氯仿與甲苯。此外，從OM的結果顯示，熔融態的star 1、star 3為均勻態的單一相，而PEO-OH/SCA-8和PEO-OH/SCA-4具有巨觀的相分離現象，這也證明PEO-NH2與SCA-n之間確實因發生鍵結而改變了相容性。為了更精確的證實SO3-和NH3+間作用力足以形成星狀高分子，分別針對手臂分子、star 1、star 3以及同分子量的線性高分子進行intrinsic viscosity([h])的量測，比較star polymer與手臂分子的[h]證實PEO-NH2與SCA-n能形成star structure。另外由星狀高分子與手臂分子在水中，具有相似的[h]，證實在甲苯中星狀高分子與手臂分子明顯差異的[h]是因為SCA-n與PEO-NH2發生離子鍵結所導致，而此離子作用力在極性溶液中則會發生解離，使得PEO-NH2與SCA-n間無法形成星狀高分子，僅為單純的混合狀態。

熔融態( 約65℃ )的PEO與star complexes的SAXS圖形顯示，star complexes 呈現一個SAXS peak，此散射峰是由於熔融態中核與PEO matrix之間的電子密度差所致，因此，由qmax的位置可求出核與核之間的距離為7.3 nm。最後，比較star complexes與線性高分子的結晶行為，由WAXS的結果發現SCA-n的存在，不會影響PEO的晶體結構，但是star complexes中PEO的球晶成長速率大幅地下降，且與star complexes手臂的數目有關。

Abstract
This thesis contains investigated the microstructure of comb-like and star-like polymer complexes. The comb-like complexes were created through complexation of poly(ethylene oxide) (PEO) and dodecylbenzenesulfonic acid (DBSA). Hydrogen-bonding interaction between PEO and DBSA was observed from the result of fourier transform infrared spectrometry (FTIR), the birefringence pattern viewed under polarized optical microscopy (POM) showed that PEO(DBSA)x complexes exhibited mesomorphic phases. Small angle X-ray scatting (SAXS) and wide angle X-ray diffraction (WAXD) revealed the microphase separated lamellar structure in the complexes, where the POM chains were inserted into the DBSA layers and were highly-stretched. Since the PEO chains were confined in the DBSA lamella, the crystallization of PEO was completely prohibited except for very degree of complexation (x=0.1). The mesophase isotropization temperatures of the complexes were higher than that of DBSA. In other words, complexes with PEO had improved the stability of mesophase. The rate of mesophase formation in the complexes was much faster than that of pure DBSA. This was attributed to the presence of local concentration fluctuation in the melt of the complexes.

The second part of the thesis investigated the star-like polymer complexes. We report the creation of star-like chain architecture through complexation of a mono-amino terminated poly(ethylene oxide) (PEO-NH2) with a macrocyclic compound, 4-sulfonic calix[n]arene(n=4 and 8) (SCA-n). The complexes were prepared in aqueous solution to render proton transfer from the sulfonic acid groups in SCA-n to the amino groups in PEO-NH2, and thereby generated 4- and 8-arm star-like complexes with the PEO arms attached to the SCA-n cores via ionic bonding. Formation of the star-like complexes was verified by titration, solubility test, and dilute solution viscometry. The intrinsic viscosities ([h]) of the complexes in toluene were 60% higher than that of neat PEO-NH2, showing that the star structure retained in nonpolar solvents. On the other hand, PEO arms dissociated from the cores in water, so that the complexes and neat PEO-NH2 displayed similar [h]. The star-like complexes showed a SAXS peak associated with the core-core correlation in the melt with the inter-core distance of 7.3 nm. The concentration fluctuation in the melt was completely destroyed upon the crystallization of PEO arms. In the semicrystalline state, the SCA-n cores were excluded from the crystal lattice and resided in the interlamellar amorphous regions. Measurements of the crystal thickness by SAXS indicated that the crystals were once- and twice-folded in neat PEO-NH2 and the complexes crystallized at 40℃ respectively. The growth rate of the star-like complexes was slower than that of pure PEO, and the effect magnified as the number of arms increased.

PEO(DBSA)x
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