Citation: Shen-ying Ding, Yun-long Xu, Ma-lin Ding, Yan-kai Zhang, Li-heng Li, Hong Li, Quan-xing Zhang. Controlled Synthesis of a Multi-block Copolymer Poly(L-lactic acid)-co-Poly(butylene succinate) with Creatinine-based Guanidine Catalysts[J]. Acta Polymerica Sinica, ;2019, 50(8): 816-825. doi: 10.11777/j.issn1000-3304.2019.19041 shu

Controlled Synthesis of a Multi-block Copolymer Poly(L-lactic acid)-co-Poly(butylene succinate) with Creatinine-based Guanidine Catalysts

1.
National Engineering Research Center for Organic Pollution Control and Resource Reuse, School of Environment, Nanjing University, Nanjing 210023
2.
Key Laboratory of Functional Polymer Materials of Education, Ministry Institute of Polymer Chemistry, Nankai University, Tianjin 300071

Corresponding author: Hong Li, hongli@nankai.edu.cn Quan-xing Zhang, zhqx@nju.edu.cn
Received Date: 26 February 2019
Revised Date: 24 March 2019
Available Online: 30 April 2019

Medium molecular weight multi-block copolymers of poly(L-lactic acid) (PLLA) and poly(butylene succinate) (PBS), MMW-mb(PLLA-PBS)s, were controlled-synthesized via melt block copolycondensation (bc-MP) of two macromonomers, i.e. oligo-PLLA (OPLLA) and oligo-PBS (OPBS) with four creatinine (CR)-based organic guanidine (OG) catalysts. The catalytic performance of the four OGs is far superior to that of Sn(Oct)₂ in terms of molecular weight (M_w = 14.2 – 28.6 kDa versus 12.9 kDa), apparent yield of synthesized block copolymers (74.15% – 82.02%), as well as the by-product (lactide, LA) yield (1.08% – 6.71% versus 20.7%). Among the OGs, creatinine acetate (CRA) shows the best catalytic performance. ¹H-NMR structural characterization of the MMW-mb(PLLA-PBS) synthesized with CRA indicates that the measured molar ratio of the two blocks, f_OPLLA/f_OPBS, of MMW-mb(PLLA-PBS) is 89.3/10.7, close to the designed value (\begin{document}$\,f\!_{\rm{OPLLA}_0} $\end{document}/\begin{document}$ \,f\!_{\rm OPBS_0}$\end{document} = 90/10). A high molecular weight (M_w = 114.0 kDa) block copolymer, HMW-mb(PLLA-PBS), was synthesized via bc-MP of two macromonomers with CRA for the first time. The tensile strength of the block copolymer (50.67 MPa) is close to that of PLLA (54.10 MPa), and the elongation at break of the copolymer (BE = 60.66%) is 15 times greater than that of PLLA. TGA analysis indicates that the original decomposition temperature (T_d,0 = 272 °C) is 22 °C higher than that of PLLA. The molar ratio of two blocks, f_OPLLA/f_OPBS (89.7/10.3) in HMW-mb(PLLA-PBS), measured by ¹H-NMR, is very close to the designed value (90/10). This is the first controlled synthesis of multi-block copolymer of PLLA-PBS via bc-MP with a biogenic guanidine-based catalyst CRA. The mechanism of the bc-MP is proposed on the basis of experimental investigation.
- Organic guanidine,
- Multi-block copolymer,
- Poly(L-lactic acid),
- Poly(butylene succinate),
- Melt copolycondensation
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