In part A, the solid of the complex between poly (acrylic acid) (PAA) and poly(ethylene oxide)(PEO), and that between poly(methacrylic acid)(PMAA) and PEO formed via hydrogen bonding was studied by differential-scanning calorimeter(DSC) and by Fourier-transform infrared(FTIR) spectroscopic measurements. Melting temperature $T_m$ and the degree of the crystallinity $X_c$ of PEO in the systems PAA (or PMAA)/PEO blends obtained from aqueous or dimethyl sulfoxide(DMSO) medium were measured in various mol % of PEO. It was found that 50 mol % of PEO is a critical composition, which gives a new evidence for 1:1 complex formation between PAA(or PMAA) and PEO. From the FTIR spectroscopic analysis in conjunction with DSC measurements we also found that the effects of solvent and of hydrophobic interaction (due to the α-methyl group of PMAA) are the important factors also affect the crystallization behavior and the microstructure of the PAA(or PMAA)/PEO blend in solid state.
In part B, interpolymer complex formation between poly(L-proline)(PLP) with helical structure and PMAA with random-coiled structure through hydrogen bonding in aqueous medium has been studied by several experimental techniques, e.g. viscosity, turbidimetry, potentiometry, conductometry, sacanning electron microscopy, and X-ray diffraction measurements. The decreases in reduced viscosity with increasing quantity of PLP into a constant amount of PMAA reveals the formation of complex between PLP and PMAA. The minimum in reduced viscosity at [PLP]/[PMAA]=1.0 suggests 1:1 complex formation. A distinct change of slope at [PLP]/[PMAA] in curves for turbidity, pH, and conductance supports this conclusion. A scanning electron micrograph for PLP-PMAA 1:1 complexes shows that the the PLP-PMAA complexes has the shape of entangled long fibers. A X-ray diffraction curve for the PLPPMAA complexes gives no diffraction patterns, indicating the destruction of helical structure of PLP interpolymer complexation with PMAA. Another complex system between PMAA and poly($\gamma$-hydroxy-L-proline)(PHLP) which has been known that the conformation is similar to PLP, but inter-or intramolecular hydrogen bonds are involved in itself, has been also investigated by viscometry. The viscosity of the solution with increasing [PHLP] increases additively, indicating no formation of complex. This result reveals that the magnitudeand the nature of the secondary forces maintaining a helical structure plays a important role on the interpolymer complexation.
In part C, interpolymer complex formation between a helical form II PLP and a random-coiled PMAA through hydrogen bonding in aqueous medium by polarimetric measurements has been studied. The specific optical rotation for the PLP/PMAA mixture systems deviates largely from the additive value, indicating the complexation between PMAA and PLP via hydrogen bonding interaction. The degree of such deviation shows a maximum at 50 unit mole % of PLP for the PLP/PMAA mixture, suggest another critical evidence for 1:1 complex formation. Another feature that the experimental specific optical rotation for the complex system between PMAA and form II PLP with only trans configuration changes positively with compared to the additive value according to increasing of the complexation, showing the increase of cis configuration. In conjuction with X-ray diffraction data reported peviously, it was concluded that owing to interpolymer complexation the ordered PLP changes into disordered structure with conformation, which cis and trans configuration is randomly distributed. The specific optical rotation for the PHLP/PMAA system gives another evidence for no complex formation.
In part D, selective interpolymer complex formation in a ternary system involving polymers with different conformation, i.e. PLP, PEO, and PMAA, has been studied by the experimental techniques such as viscometry, potentiometry, and FTIR spectroscopic analysis. From the reduced viscosity and pH results for the ternary system, it was clarified that the ralative complexation ability of a helical PLP is greater than that of a coiled PEO with respect to PMAA. FTIR spectra reveals that such selective complexation reaction occurs via open chain mechanism.
In part E, preparation and interpolymer complexation properties of water soluble A-B-A type Triblock copolymer consisting of a helical PLP and a random-coiled PEO(POP) has been studied. From polymerization of L-proline N-caboxy anhydride initiated by the primary amino groups terminated PEO as the middle block component in benzene, and then isomerization of the product obtained by using a solvent, POP was prepared. From NMR spectra, specific optical rotation, X-ray diffraction data, it was found that the PLP component of POP exists nearly as form II PLP with trans configuration, and interferes with the growth of crystal of crystalline PEO component in solid state. Interpolymer complex formation between PMAA and POP was investigated by viscosity, pH, and turbidity measurements. With addition of PMAA Into an aqueous POP solution, dramatic decreases of reduced viscosity and of pH, and distinct increase of turbidity at unit mole ratio [PMAA]/[POP]=1.0 shown an 1:1 interpolymer complex formation between PMAA and POP in aqueous medium through hydrogen bonding, A break in viscosity, pH and turbidity curves at unit mole ratio [PMAA]/[POP]=0.3, suggests the selective complexation of PLP component (ca. 30 unit mole %) of POP with respective to PMAA shows no diffraction patterns, indicating that the ordered POP structure mainly due to that of PLP component was completely disrupted to disordered one owing to the complexation between POP and PMAA.
폴리 메타크릴산(PMAA), 폴리아크릴산(PAA)와 같은 폴리카르복실산과 폴리에틸렌옥사이드(PEO) 사이의 수소결합을 통한 고분자 복합체 형성을 고체상에서 시차열분석기(DSC)와 푸리에변환 적외선분광기(FTIR)을 이용해 분석하였다. PMAA-PEO 복합체상에서 PEO의 용융점과 결정화도의 감소 현상으로부터 1:1고분자 복합체 형성을 관측하였다. 고분자 복합체형성에 용매효과와 소수성 상호인력효과가 매우 중요함이 또한 인식되었다.
나선 구조를 가진 폴리-L-푸롤린(PLP)과 코일구조의 PMAA 사이의 고분자 복합체 형성이 연구되었다. 수용액상에서 그 두 고분자는 수소결합, 이온-쌍극자, 소수성 상호인력등을 통하여 1:1고분자 복합체를 형성한다는 것이 밝혀졌다. 또한 복합체화로 인해 나선구조의 PLP는 코일구조로 변함됨이 X-선 회절분석으로 밝혀졌다. PLP-PEO-PMAA 삼성분계에서는, PLP가 PEO에 비해 선택적으로 PMAA와 결합해 고분자 복합체를 형성하였다. 나선구조를 가진 PLP성분 (A) 과 코일구조를 가진 PEO성분 (B) 으로 구성된 새로운 수용성 ABA형태 블락공중함체 ( POP)가 합성되었다. POP 와 PMAA는 수소결합을 통해 수용액상에서 1:1 고분자 복합체를 형성하여, PLP성분이 선택적으로 먼저 PMAA와 결합하였다.
