Synthesis of PLLA-block-PMMA Copolymer and Characteristics of Biaxially Oriented PLA Film Including the Same

본 연구에서는 L-lactide를 이용하여 수평균분자량(Mn)과 중량평균분자량($M_w$)이 각각 12,000, 14,000 g/mol인 PLLA (Poly L-lactic acid) 수지를 합성하였으며, 이 PLLA를 이용하여 PLLA-Br 중간체를 합성하였다. PLLA-Br 중간체를 이용하여 수평균분자량($M_n$)과 중량평균분자량($M_w$)이 각각 84,000, 126,000 g/mol인 PLLA-block-PMMA (Poly L-lactic acid-block-Polymethyl methacrylate) 공중합체를 최종적으로 합성하였으며 PLLA-block-PMMA 공중합체의 유리전이온도($T_g$)는 $95.5^{\circ}C$, 열분해 개시온도는 $289^{\circ}C$이었다. PLA에 PLLA-block-PMMA를 9 phr 혼용하고 $95^{\circ}C$에서 3배 이축연신한 다음 $120^{\circ}C$에서 2 min 동안 저온열처리하여 두께가 $50{\pm}3{\mu}m$인 PLA 필름을 제조하였다. 550 nm 파장에서 측정한 PLA 필름의 빛투과율은 88.5%, 인장강도는 44.5 MPa이었으며 PLA 필름의 인장강도를 현 수준보다 개선하기 위해서는 이축연신후 $120^{\circ}C$의 온도조건에서 2 min보다 긴 저온열처리시간이 필요하였다. In the study, PLLA with 12,000 g/mol ($M_n$) and 14,000 g/mol ($M_w$) was synthesized from L-lactide, and used to synthesize PLLA-Br intermediate. PLLA-block-PMMA with 84,000 g/mol ($M_n$) and 126,000 g/mol ($M_w$) was finally synthesized from PLLA-Br intermediate. The glass transition temperature ($T_g$) and initial pyrolysis temperature of PLLA-block-PMMA are $95.5^{\circ}C$ and $289^{\circ}C$, respectively. The PLA film of $50{\pm}3{\mu}m$ thickness was prepared by blending PLA with 9 phr PLLA-block-PMMA followed by stretching biaxially at 3 times under $95^{\circ}C$, and annealing at $120^{\circ}C$ for 2 min. The light transmittance at 550 nm and tensile strength of the film are 88.5% and 44.5 MPa, respectively. To enhance the tensile strength of PLA film, it was required to keep the film more than 2 min at $120^{\circ}C$ during the annealing step after a biaxially orientation.