Citation: Zi-yu Wang, Wen-wen He, Yun-long Xu, Wei Huang, Wei Jiang, Hong Li, Quan-xing Zhang. Controlled Synthesis of PLA-series Environment-friendly Polymers with Guanidine Catalysts[J]. Acta Polymerica Sinica, ;2018, 0(7): 786-796. doi: 10.11777/j.issn1000-3304.2018.18036 shu

Controlled Synthesis of PLA-series Environment-friendly Polymers with Guanidine Catalysts

Zi-yu Wang ¹ ,
Wen-wen He ¹ ,
Yun-long Xu ¹ ,
Wei Huang ¹ ,
Wei Jiang ¹ ,
Hong Li ^1,2,, ,
Quan-xing Zhang ¹

1.
National Engineering Research Center for Organic Pollution Control and Resource Reuse, School of the 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
Received Date: 1 February 2018
Revised Date: 5 April 2018
Available Online: 3 May 2018

Controlled polymerization is of great significance for the tailoring of macromolecular structure and synthesis of polymers with excellent properties. Several non-toxic organic guanidinines were prepared/selected in our laboratory in recent years and used as the catalysts/initiators to realize controlled melt polycondensation (MP), ring-opening polymerization (ROP), and depolymerization (DEP). Isotactic melt polycondensation (Iso-MP) of L-lactic acid/D-lactic acid (LLa/DLa) was carried out for the first time with biogenic creatinine (CR) catalyst and poly(L-lactic acid)/poly(D-lactic acid) (PLLA/PDLA) with high isotacticity (Iso. > 98%) was obtained; Combined MP with solid-state polycondensation (MP-SSP) of the medium molecular weight PLLA/PDLA ( M_w = 2.2 × 10⁴, Iso. = 98.2%), prepared by the Iso-MP with CR, was carried out, and high molecular weight PLLA/PDLA (M_w > 1.0 × 10 ⁵) with high isotacticity (Iso. > 98%) was obtained. The initial decomposition temperature ( T_d,i) of the synthesized PLLA reached up to 324.5 °C, which was 120 °C higher than that of PLLA synthesized by SnCl₂·2H₂O catalyst; Optical pure (e.e. 100%) L-lactide/D-lactide (OP-LLA/OP-DLA) were synthesized via Iso-MP and the subsequent depolymerization (DEP) of LMW-PLLA/LMW-PDLA (M_w = 8.0 × 10² – 9.0 × 10 ²) with CR catalyst. The polymer residues (r-PLLA/r-PDLA), produced accompanying with the lactides formation, were reused as the raw material for LLA/DLA synthesis after being hydrolyzed. The total yield of OP-LLA/OP-DLA reached up to 98%; Several sterically hindered guanidine carboxylates (HBG·OAc, CRA, CRG, CRL, TBDA) were synthesized and used to realize living ROP of LLA. An optical pure morpholine-2,5-dione (3S,6S-BMMD), derived from LLa and L-serine, was synthesized. Living ROP of 3S,6S-BMMD was carried out with CRA catalyst for the first time. After debenzylation of the synthesized P(3S,6S-BMMD), an amphiphillic copolymer P(LLa-co-Ser) was obtained, which is a useful support material in biomedical areas. The fine molecular structures and isotacticities of growing polymeric species were characterized by in situ monitoring with ¹H-NMR, ¹³C-NMR. And the mechanisms of the above mentioned controlled polymerizations were proposed.
- Organic guanidine,
- Isotactic polycondensation,
- Living ring-opening polymerization,
- Environment-friendly polymers
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沈阳化工大学材料科学与工程学院沈阳 110142

Controlled Synthesis of PLA-series Environment-friendly Polymers with Guanidine Catalysts

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com