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大连理工大学化工学院高分子材料系,精细化工国家重点实验室,大连 116024
*郭方,E-mail: guofang@dlut.edu.cn
纸质出版日期:2023-12-20,
收稿日期:2023-04-10,
修回日期:2023-05-17,
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张春阳, 孙涵阳, 屈甜甜, 郭方. 醚链改性聚环氧乙烷的合成及性能研究[J]. 高分子通报, 2023,36(12):1660-1668.
ZHANG Chun-yang, SUN Han-yang, QU Tian-tian, GUO Fang. Synthesis and Properties of Ether Chain Modified Poly(ethylene oxide)[J]. Polymer Bulletin, 2023,36(12):1660-1668.
张春阳, 孙涵阳, 屈甜甜, 郭方. 醚链改性聚环氧乙烷的合成及性能研究[J]. 高分子通报, 2023,36(12):1660-1668. DOI: 10.14028/j.cnki.1003-3726.2023.12.006.
ZHANG Chun-yang, SUN Han-yang, QU Tian-tian, GUO Fang. Synthesis and Properties of Ether Chain Modified Poly(ethylene oxide)[J]. Polymer Bulletin, 2023,36(12):1660-1668. DOI: 10.14028/j.cnki.1003-3726.2023.12.006.
考察烷基磷酸铝催化剂
i
-Bu
3
Al/H
3
PO
4
/DBU 催化环氧乙烷(EO)、甘醇甲基缩水甘油醚(
n
GE)与烯丙基缩水甘油醚(AGE)二元及三元共聚合的催化性能
通过核磁共振波谱(NMR)、凝胶渗透色谱(GPC)和示差扫描量热仪(DSC)对共聚物微观结构和热性能进行表征分析。结果表明25 ℃甲苯溶剂中
i
-Bu
3
Al/H
3
PO
4
/DBU催化剂可以高效催化不同比例的EO、
n
GE和AGE共聚合
以100%收率获得组成精确可控的高分子量EO-
n
GE二元及EO-AGE-
n
GE三元无规共聚物;
n
GE的醚链长度对聚合性能无影响
二甘醇甲基缩水甘油醚(2GE)和四甘醇甲基缩水甘油醚(4GE)均可实现可控引入聚环氧乙烷制备醚链改性聚环氧乙烷。EO-AGE-
n
GE三元共聚物以1
2-乙二硫醇为交联剂制备了交联聚合物。测试醚链改性聚环氧乙烷的性能
发现醚链长度、含量及交联对聚合物电导率和力学性能有很大影响。4GE为共聚单体的聚环氧乙烷电导率高于2GE。随着醚链含量增大
聚合物电导率上升
力学性能下降。合适的交联程度不仅能提高聚环氧乙烷的力学性能
还可以进一步提升其电导率。4GE含量为39 mol%
AGE含量为2 mol%时
EO-4GE-AGE交联聚合物电解质的拉伸强度可达1.41 MPa
30 ℃电导率可达9×10
-5
S·cm
-1
。
The copolymerization of ethylene oxide (EO)
glycol methyl glycidyl ether (nGE) and allyl glycidyl ether (AGE) catalyzed by
i
-Bu
3
Al/H
3
PO
4
/DBU has been examined. The microstructures
thermal properties and molecular weights of the obtained polymers were characterized by nuclear magnetic resonance spectroscopy (NMR)
gel permeation chromatography (GPC) and differential scanning calorimeter (DSC). The results showed that the
i
-Bu
3
Al/H
3
PO
4
/DBU catalyst serves as an excellent catalyst for the copolymerization of EO
n
GE
and AGE to afford a family of ether chain modified poly(ethylene oxide). The obtained EO-
n
GE copolymers and EO-
n
GE-AGE terpolymers with controllable contents were conveniently obtained in 100% yield within 30 min by changing the feed ratio. The ether chain length of
n
GE has no effect on the copolymerization. The cross-linked copolymers were prepared using the EO-
n
GE-AGE terpolymer as precursors and 1
2-ethanedithiol as a crosslinking agent. The properties of copolymers revealed that the ether chain length and content
crosslinking had a significant impact on the conductivity and mechanical properties of copolymers. The copolymers with tetraethylene glycol methyl glycidyl ether (4GE) as a comonomer exhibited higher conductivity than that of diethylene glycol methyl glycidyl ether (2GE). With the increase of the content of 4GE in the EO-4GE copolymers
the conductivity increased
but the mechanical properties decreased. The appropriate crosslinking degree improved not only the mechanical properties but also conductivity. The cross-linked EO-4GE-AGE polymer electrolytes containing 39 mol% 4GE and 2 mol% AGE showed the tensile strength and conductivity of 1.41 MPa and 9×10
-5
S·cm
-1
at 30 ℃
respectively.
聚环氧乙烷固体聚合物电解质锂电池
Poly(ethylene oxide)Solid polymer electrolyteLithium battery
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