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
1. [1]
  Rasal R M, Janorkar A V, Hirt D E. Prog Polym Sci, 2010, 35: 338 − 356 doi: 10.1016/j.progpolymsci.2009.12.003
2. [2]
  Inkinen S, Hakkarainen M, Albertsson A C. Biomacromolecules, 2011, 12(3): 523 − 532 doi: 10.1021/bm101302t
3. [3]
  Nampoothiri K M, Nair N R, John R P. Bioresource Technol, 2010, 101: 8493 − 8501 doi: 10.1016/j.biortech.2010.05.092
4. [4]
  Gupta A P, Kumar V. Eur Polym J, 2007, 43: 4053 − 4074 doi: 10.1016/j.eurpolymj.2007.06.045
5. [5]
  Zeng J, Li Y, Li W, Yang K, Wang X. Ind Eng Chem Res, 2009, 48(4): 1706 − 1711 doi: 10.1021/ie801391m
6. [6]
  Ulloa P A, Vidal J, Dicastillo C. J Appl Polym Sci, 2019, 136(8): 11
7. [7]
  Cao Y L, Yin J B, Yan S F. Chin Sci Bull, 2006, 16(10): 90 − 97
8. [8]
  Andreopoulos A G. J Mater Sci-Mater Med, 1999, 10(1): 29 − 33 doi: 10.1023/A:1008887910068
9. [9]
  Bendix D. Polym Degrad Stab, 1998, 59(1-3): 129 − 135 doi: 10.1016/S0141-3910(97)00149-3
10. [10]
  Xu Y, Zhang S, Peng X, Wang J. Eur Polym J, 2018, 99: 250 − 258 doi: 10.1016/j.eurpolymj.2017.12.032
11. [11]
  Chen G, Kim H S, Kim E S. Polymer, 2005, 46(25): 11829 − 11836 doi: 10.1016/j.polymer.2005.10.056
12. [12]
  Ferreira L P, Moreira A N, Pinto J C, de Souza F G. Polym Eng Sci, 2015, 55: 1889 − 1896 doi: 10.1002/pen.v55.8
13. [13]
  Luo S, Li F, Yu J, Cao A. J Appl Polym Sci, 2010, 115(4): 2203 − 2211 doi: 10.1002/app.v115:4
14. [14]
  Lu J, Qiu Z, Yang W. Polymer, 2007, 48(14): 4196 − 4204 doi: 10.1016/j.polymer.2007.05.035
15. [15]
  Lee P C, Lee W G, Lee S Y, Chang H N. Biotechnol Bioeng, 2001, 72: 41 − 48 doi: 10.1002/(ISSN)1097-0290
16. [16]
  Cheng K, Zhao X, Zeng J. Biofuel Bioprod Bior, 2012, 6: 302 − 318 doi: 10.1002/bbb.1327
17. [17]
  Bretz K, Kabasci S. Biotechnol Bioeng, 2012, 109: 1187 − 1192 doi: 10.1002/bit.24387
18. [18]
  Minh P D, Besson M, Pinel C, Fuertes P, Petitj J C. Top Catal, 2010, 53(15-18): 1270 − 1273 doi: 10.1007/s11244-010-9580-y
19. [19]
  Zhang W, Xu Y, Wang P, Hong J, Liu J, Ji J, Pual K C. J Polym Environ, 2018, 26(7): 1 − 9
20. [20]
  Jia L, Yin L, Li Y, Li Q, Yang J, Yu J, Shi Z, Fang Q, Cao A. Macromol Biosci, 2005, 5(6): 526 − 538 doi: 10.1002/(ISSN)1616-5195
21. [21]
  Ba C, Yang J, Hao Q, Liu X, Cao A. Biomacromolecules, 2003, 4(6): 1827 − 1834 doi: 10.1021/bm034235p
22. [22]
  Supthanyakul R, Kaabbuathong N, Chirachanchai S. Polym Degrad Stab, 2017, 142: 160 − 168 doi: 10.1016/j.polymdegradstab.2017.05.029
23. [23]
  Zhang B, Bian X, Xiang S, Li G, Chen X. Polym Degrad Stab, 2017, 136: 58 − 70 doi: 10.1016/j.polymdegradstab.2016.11.022
24. [24]
  Chan Woo Lee, Chao N, Yoshiharu Kimura, Kazunari Masutani. Macromol Mater Eng, 2016, 301: 1121 − 1131 doi: 10.1002/mame.v301.9
25. [25]
  Tan L, Chen Y, Zhou W, Nie H, Li F, He X. Polym Degrad Stab, 2010, 95: 1920 − 1927 doi: 10.1016/j.polymdegradstab.2010.04.010
26. [26]
  Supthanyakul R, Kaabbuathong N, Chirachanchai S. Polymer, 2016, 105: 1 − 9 doi: 10.1016/j.polymer.2016.10.006
27. [27]
  Zhang M, Han W, Li W Q, Wang L, Qiu J H. Modern Chem Ind, 2007, 27(2): 39 − 43
28. [28]
  Ma Lili(马丽莉), Shao Jun(邵俊), Yang Chenguang(杨晨光), Tang Zhaohui(汤朝晖), Chen Xuesi(陈学思). Chem J Chin Univ(高等学校化学学报), 2015, 36(11): 2329 − 2334
29. [29]
  Ji Deyun(季得运), Liu Zhengying(刘正英), Lan Xiaorong(兰小蓉), Wu Feng(吴枫), Hua Sun(华笋), Yang Mingbo(杨鸣波). Acta Polymerica Sinica(高分子学报), 2012, (7): 694 − 697
30. [30]
  Sionkowska A. Prog Polym Sci, 2011, 36: 1254 − 1276 doi: 10.1016/j.progpolymsci.2011.05.003
31. [31]
  Yokohara T, Yamaguchi M. Eur Polym J, 2008, 44: 677 − 685 doi: 10.1016/j.eurpolymj.2008.01.008
32. [32]
  Wang Ziyu(王子羽), He Wenwen(何文文), Xu Yunlong(徐云龙), Huang Wei(黄伟), Jiang Wei(江伟), Li Hong(李弘), Zhang Quanxing(张全兴). Acta Polymerica Sinica(高分子学报), 2018, (7): 786 − 796 doi: 10.11777/j.issn1000-3304.2018.18036
33. [33]
  Huang W, Qi Y, Cheng N, Zong X, Zhang T, Jiang W, Li H, Zhang Q. Polym Degrad Stab, 2014, 101: 18 − 23 doi: 10.1016/j.polymdegradstab.2014.01.022
34. [34]
  Sheng Jiaye(盛家业), Wang Ziyu(王子羽), Xu Yunlong(徐云龙), Huang Wei(黄伟), Jiang Wei(江伟), Li Hong(李弘), Zhang Quanxing(张全兴). Ion Exchange and Adsorption(离子交换与吸附), 2017, 33(3): 193 − 202
35. [35]
  Wang Ch, Li H, Zhao X. Biomaterials, 2004, 25(27): 5797 − 5801 doi: 10.1016/j.biomaterials.2004.01.030
36. [36]
  Li H, Wang C, Jin Y, Zhao X, Feng B. J Polym Sci, Part A: Polym Chem, 2004, 42(15): 3775 − 3781 doi: 10.1002/(ISSN)1099-0518
37. [37]
  Li Hong(李弘), Zhang Saihui(张赛晖), Jiao Zhifeng(焦志峰), Zuo Jiaqing(左佳卿). Acta Polymerica Sinica(高分子学报), 2008, (7): 667 − 672 doi: 10.3321/j.issn:1000-3304.2008.07.007
38. [38]
  Li H, Zhang S, Jiao J, Jiao Z, Kong L, Xu J, Zuo J, Zhao X, Li J. Biomacromolecules, 2009, 10(5): 1311 − 1314 doi: 10.1021/bm801479p
39. [39]
  Li Hong(李弘), Jiao Jieping(焦洁平), Kong Lijun(孔丽君), Jiao Zhifeng(焦志峰), Zhang Donglai(张东来), Xu Jie(徐杰), He Peiru(何培茹). Chinese Journal of Organic Chemistry(有机化学), 2009, 29(5): 736 − 741
40. [40]
  Pang Z, Li H, He P, Wang Y, Ren H, Wang H, Zhu X X. J Polym Sci, Part A: Polym Chem, 2012, 50(19): 4004 − 4009 doi: 10.1002/pola.v50.19
41. [41]
  Lohmeijer B G G, Pratt R C, Leibfarth F, Logan J W, Long D A, Dove A P, Nederberg F, Choi J, Wade C, Waymouth R M, Hedrick J L. Macromolecules, 2006, 39(25): 8574 − 8583 doi: 10.1021/ma0619381
42. [42]
43. [43]
  Dove A P, Li H, Pratt R C, Lohmeijer B G G, Culkin D A, Waymouth R M, Hedrick J L. Chem Commun, 2006, 0(27): 2881 − 2883
44. [44]
45. [45]
  Woo H G, Li H. Advanced Functional Materials. Berlin, Heidelberg: Springer, 2011. 227
46. [46]
  Jiang W, Huang W, Cheng N, Qi Y, Zong X, Li H, Zhang Q. Polymer, 2012, 53(24): 5476 − 5479 doi: 10.1016/j.polymer.2012.09.044
47. [47]
48. [48]
  Huang W, Cheng N, Qi Y, Zhang T, Jiang W, Li H, Zhang Q. Polymer, 2014, 55(6): 1491 − 1496 doi: 10.1016/j.polymer.2014.01.054
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