含磷基团聚合物与聚醚：从合成到应用

Polymers containing phosphorus groups and polyethers: from synthesis to application.

作者信息

Iliescu Smaranda, Zubizarreta Leire, Plesu Nicoleta, Macarie Lavinia, Popa Adriana, Ilia Gheorghe

机构信息

Institute of Chemistry, Romanian Academy, 24 Mihai Viteazul Bvd, Timisoara 300223, Romania.

出版信息

Chem Cent J. 2012 Nov 8;6(1):132. doi: 10.1186/1752-153X-6-132.

DOI:10.1186/1752-153X-6-132

PMID:23134834

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3549764/

Abstract

BACKGROUND

Phosphorus-containing high performance polymers have aroused wide interest, mainly due to good mechanical properties and their excellent fire resistance. The flexibility of synthetic polyphosphoesters allows the development of polymers in order to obtain solid polymer electrolytes for rechargeable lithium batteries based on solid films with superior fire resistance.

RESULTS

Novel linear Phosphonate-PEG polymers were synthesized by solution polycondensation of 4-chlorophenyldichlorophosphonate as a linking agent and poly(ethylene glycol)s with different molecular weights in the presence of triethylamine or 1-methylimidazole as acid scavenger. The yields were between 54% and 88% and inherent viscosity between 0.18-0.48 dl/g. Molar masses, Mn were about 26300 g/mol for polyphosphonates with PEG 2000 and 4600 g/mol for polyphosphonates with PEG 200. The LOI values for these polymers and membranes are in the range of 26-29. The membranes based on polyphosphonate with PEG 200 and 2000 showed conductivity between 6 × 10-8 S.cm-1 and 6 × 10-7 S.cm-1 at room temperature and total ionic transference number between 0.87- 0.96. The evolution of conductivity vs. temperature is linear.

CONCLUSIONS

1-methylimidazole was found to be better HCl scavenger than triethylamine, and allowed higher yields and more eco-friendly synthesis of the Phosphonate-PEG polymers for SPE. These polymers and membranes based on these polymers showed good LOI values and indicate an improvement of the safety of lithium batteries. The membranes present conductivities around 6 × 10-7 S.cm-1at room temperature and total ionic transference number is higher for membranes based on polymers with high EG unit content. Best results yield 88%, inherent viscosities 0.48 dl/g and Mn 26000 were obtained with 1-methylimidazole and PEG 2000. These membranes based on these polymers showed good LOI values (in the range 26-29%) and indicate an improvement of the safety of lithium batteries.

摘要

背景

含磷高性能聚合物引起了广泛关注，主要是由于其良好的机械性能和出色的耐火性。合成聚磷酸酯的灵活性使得能够开发聚合物，以获得基于具有卓越耐火性的固体薄膜的可充电锂电池固体聚合物电解质。

结果

以4-氯苯基二氯膦酸酯为连接剂，在三乙胺或1-甲基咪唑作为酸清除剂的存在下，与不同分子量的聚乙二醇通过溶液缩聚反应合成了新型线性膦酸酯-聚乙二醇聚合物。产率在54%至88%之间，特性粘度在0.18 - 0.48 dl/g之间。对于含PEG 2000的聚膦酸酯，摩尔质量Mn约为26300 g/mol，对于含PEG 200的聚膦酸酯，Mn为4600 g/mol。这些聚合物和膜的极限氧指数（LOI）值在26 - 29范围内。基于含PEG 200和2000的聚膦酸酯的膜在室温下的电导率在6×10⁻⁸ S·cm⁻¹至6×10⁻⁷ S·cm⁻¹之间，总离子迁移数在0.87 - 0.96之间。电导率随温度的变化呈线性关系。

结论

发现1-甲基咪唑是比三乙胺更好的HCl清除剂，并且能够以更高的产率和更环保的方式合成用于固体聚合物电解质（SPE）的膦酸酯-聚乙二醇聚合物。这些聚合物以及基于这些聚合物的膜显示出良好的LOI值，表明锂电池的安全性有所提高。这些膜在室温下的电导率约为6×10⁻⁷ S·cm⁻¹，对于基于高乙二醇（EG）单元含量聚合物的膜，总离子迁移数更高。使用1-甲基咪唑和PEG 2000可获得最佳结果，产率为88%，特性粘度为0.48 dl/g，Mn为26000。这些基于这些聚合物的膜显示出良好的LOI值（在26 - 29%范围内），表明锂电池的安全性有所提高。