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파라-페닐렌 다이이소시아네이트의 사슬 연장이 PLA/PBT 블렌드의 결정화 거동과 생분해성에 미치는 영향

Chain extension effects of para-phenylene diisocyanate on crystallization behavior and biodegradability of poly(lactic acid)/poly(butylene terephthalate) blends

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초록

PPDI(para-phenylene diisocyanate)와의 반응 압출을 통해 PLA(poly(lactic acid))/PBT(poly(butylene terephthalate)) 블렌드를 제조하였다. DSC, WAXD, 접촉각 측정기 및 esterase를 함유한 완충 용액을 이용하여 결정화 거동과 생분해도를 연구하였다. PLA 고분자 매트릭스에 PBT를 첨가하면 PLA 상의 냉결정화가 일어났고, PBT와 PPDI가 동시에 PLA와의 반응에 참여했을 때 PLA 상의 결정화 속도가 크게 가속되었다. 그러나 PPDI에 의한 사슬 연장은 PLA와 PBT 상의 결정화도와 친수성을 감소시켰다. 결정화도와 친수성은 PLA/PBT 블렌드의 생분해도에 있어 크게 영향을 미치지 못했다. 하지만 PLA/PBT 블렌드에서 PLA와 PBT 사이의 상분리는 효소의 가수분해에 노출될 수 있는 계면적을 증가시켰고, 이로 인해 PLA 상의 생분해 속도를 향상시켰다. 대조적으로 PPDI와의 반응에 의한 PLA와 PBT 매트릭스 사이의 계면접착력의 향상은 효소에 노출된 면적을 감소시켜 PLA 상의 생분해 속도를 떨어뜨렸다.

Abstract

Blends of poly(lactic acid) (PLA) and poly(butylene terephthalate) (PBT) were prepared by reaction extrusion with para-phenylene diisocyanate (PPDI). The crystallization behavior and biodegradability were investigated by using a differential scanning calorimeter (DSC), a wide angle X-ray diffractometer (WAXD), a contact angle goniometer, and a buffer solution containing esterase. The addition of PBT into PLA polymer matrix induced the cold crystallization of PLA phase, and the crystallization rate of PLA phase was significantly accelerated when both PBT and PPDI participated in the reaction with PLA simultaneously. But the chain extension caused by PPDI decreased the crystallinity and hydrophilicity of PLA and PBT phases. The crystallinity and hydrophilicity did not affect the biodegradability of PLA/PBT blends. However, phase separation between PLA and PBT in PLA/PBT blends increased the interfacial area exposed to the hydrolysis of enzyme, resulting in the improved degradability rate of PLA phase. In contrast, the improved interfacial adhesion between PLA and PBT matrices by the reaction with PPDI reduced the area exposed to the enzyme to decrease the degradation rate of PLA phase.

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