Citation: Zheng Bo-tuo, Tao Xin-feng, Ling Jun. Water Tolerated Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride Initiated by Primary Amines[J]. Acta Polymerica Sinica, ;2018, (1): 72-79. doi: 10.11777/j.issn1000-3304.2018.17172 shu

Water Tolerated Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride Initiated by Primary Amines

Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027

Corresponding author: Ling Jun, lingjun@zju.edu.cn
Received Date: 3 July 2017
Revised Date: 10 August 2017

N-Substituted glycine N-carboxyanhydride (NNCA) polymerization cannot tolerate H₂O, because the presence of H₂O leads to oligopolymerization or deterioration of NCA. In contrast, its analogue N-substituted glycine N-thiocarboxyanhydride (NNTA) is stable to H₂O. In this work, by comparing ¹H-NMR spectra signal of NNTA with that of internal standard (trioxane, TOX) before and after heating for 24 h in presence of water, it is shown the tolerance of NNTA to water amount was monomer-equivalent (14000 μg/g). The polymerization of NNTA initiated by benzylamine was carried out in presence of water. ¹H-NMR, MALDI-ToF-MS and SEC were used to confirm the structure of polypeptoid products. The polymerization of N-ethyl glycine NTA (NEG-NTA) initiated by benzylamine showed good tolerance to initiator-equivalent water amount (100-650 μg/g). From this polymerization, high yield (> 70%) was obtained with controlled molecular weights (1600-7500) and low molecular weight distribution (PDI, i.e. polydispersity index:1.22-1.25). Increasing amount of water (14000 μg/g) suppressed the polymerization, resulting in low yields and low molecular weights to some extent, while PDI remained low. All polymers contained benzylamine end group according to MALDI-ToF-MS, which demonstrated that all the polymerization of NNTA followed the normal amine mechanism (NAM) regardless of different water contents. Polymerizations of sarcosine NTA (Sar-NTA) and N-butyl glycine NTA (NBG-NTA) in presence of initiator-equivalent water amount were also investigated. Polymerization of sarcosine NTA resulted in high yield (89%) with controlled molecular weight and low PDI (1.13), which showed that the polymerization of NNTA with higher activity was more tolerant to water. Furthermore, the polymerization kinetics confirmed the controllability of the resulting polymer by demonstrating that the polymerization followed pseudo-first order kinetics with regard to monomer up to high conversion (~90%). In addition, molecular weights of polypeptoids exhibited linear relationship with monomer conversion while PDIs kept low. It is of great interest that well-controlled NEG-NTA polymerization was carried out in commercial THF with water content (about 190 μg/g) without dehydration. This work demonstrated that the polymerization of NNTA was a robust approach to prepare polypeptoids since both the monomer synthesis and the polymerizations did not require an anhydrous environment, which would benefit the further application of polypeptoids in bioengineering and medical field.
- Polypeptoid,
- Poly(α-amino acid),
- Poly(N-substituted glycine),
- Amino acid N-thiocarboxyanhydride,
- Ring-opening polymerization
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