Ring-opening polymerization of ε-caprolactone initiated by tin(II) octoate/n-hexanol: DSC isoconversional kinetics analysis and polymer synthesis.

IF 1.8 4区 化学 Q3 POLYMER SCIENCE Designed Monomers and Polymers Pub Date : 2021-04-11 DOI:10.1080/15685551.2021.1908657
Winita Punyodom, Wanich Limwanich, Puttinan Meepowpan, Boontharika Thapsukhon
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引用次数: 6

Abstract

The kinetics of ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) initiated by 1.0, 1.5 and 2.0 mol% of stannous(II) octoate/n-hexanol (Sn(Oct)2/n-HexOH) wase successfully studied by non-isothermal differential scanning calorimetry (DSC) at heating rates of 5, 10, 15 and 20 °C/min. The DSC polymerization kinetic parameters of ε-CL were calculated using differential (Friedman) and integral isoconversional methods (Kissinger-Akahira-Sunose, KAS). The average activation energy (Ea ) values obtained from Friedman and KAS methods were in the range of 64.9-70.5 kJ/mol and 64.9-80.4 kJ/mol, respectively. The values of frequency factor (A) were determined from model fitting method using Avrami-Erofeev reaction model. The average values of A for the ROP of ε-CL initiated by 1.0, 1.5 and 2.0 mol% of Sn(Oct)2/n-HexOH (1:2) were 7.3x107, 2.8x106 and 1.2x106 min-1, respectively. From kinetics studied, the polymerization rate of ε-CL increased with increasing initiator concentration. The performance of Sn(Oct)2/n-HexOH in the synthesis of poly(ε-caprolactone) (PCL) was investigated by bulk polymerization at temperatures of 140, 160 and 180 °C. Sn(Oct)2/n-HexOH (1:2) could produce high number average molecular weight ( M n = 9.0 × 104 g/mol) and %yield (89%) of PCL in a short period of time at Sn(Oct)2 concentration of 0.1 mol% and temperature of 160°C. The mechanism of the ROP of ε-CL with Sn(Oct)2/n-HexOH was proposed through the coordination-insertion mechanism.

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八酸锡/正己醇引发ε-己内酯开环聚合:DSC等转化动力学分析及聚合物合成
采用非等温差示扫描量热法(DSC)研究了1.0、1.5和2.0 mol%的八酸锡/正己醇(Sn(Oct)2/正己醇)溶液在5、10、15和20℃/min加热速率下引发ε-己内酯(ε-CL)开环聚合(ROP)的动力学。采用微分法(Friedman)和积分等转换法(Kissinger-Akahira-Sunose, KAS)计算了ε-CL的DSC聚合动力学参数。Friedman法和KAS法得到的平均活化能(Ea)分别在64.9 ~ 70.5 kJ/mol和64.9 ~ 80.4 kJ/mol之间。频率因子(A)采用Avrami-Erofeev反应模型拟合。当Sn(Oct)2/n-HexOH浓度为1.0、1.5和2.0 mol%(1:2)时,ε-CL的ROP平均值分别为7.3x107、2.8x106和1.2x106 min-1。从动力学研究来看,ε-CL的聚合速率随引发剂浓度的增加而增加。采用本体聚合的方法研究了Sn(Oct)2/n-HexOH在140、160和180℃条件下合成聚ε-己内酯(PCL)的性能。Sn(Oct)2/n- hexoh(1:2)在Sn(Oct)2浓度为0.1 mol%、温度为160℃的条件下,能在短时间内生成PCL较高的数平均分子量(mn = 9.0 × 104 g/mol)和%收率(89%)。通过配位插入机理,提出了ε-CL与Sn(Oct)2/n-HexOH的ROP机理。
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Designed Monomers and Polymers
Designed Monomers and Polymers 化学-高分子科学
CiteScore
3.30
自引率
0.00%
发文量
28
审稿时长
2.1 months
期刊介绍: Designed Monomers and Polymers ( DMP) publishes prompt peer-reviewed papers and short topical reviews on all areas of macromolecular design and applications. Emphasis is placed on the preparations of new monomers, including characterization and applications. Experiments should be presented in sufficient detail (including specific observations, precautionary notes, use of new materials, techniques, and their possible problems) that they could be reproduced by any researcher wishing to repeat the work. The journal also includes macromolecular design of polymeric materials (such as polymeric biomaterials, biomedical polymers, etc.) with medical applications. DMP provides an interface between organic and polymer chemistries and aims to bridge the gap between monomer synthesis and the design of new polymers. Submssions are invited in the areas including, but not limited to: -macromolecular science, initiators, macroinitiators for macromolecular design -kinetics, mechanism and modelling aspects of polymerization -new methods of synthesis of known monomers -new monomers (must show evidence for polymerization, e.g. polycondensation, sequential combination, oxidative coupling, radiation, plasma polymerization) -functional prepolymers of various architectures such as hyperbranched polymers, telechelic polymers, macromonomers, or dendrimers -new polymeric materials with biomedical applications
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