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Highly Syndiotactic Polymerizationof
增强出版ortho- Methoxystyrene withβ -Diketiminato Rare-earth Metal Complexes- Acta Polymerica Sinica Vol. 55, Issue 6, Pages: 729-737(2024)
- 作者机构：
1.中国科学院长春应用化学研究所 高分子物理与化学国家重点实验室 长春 130022
2.中国科学技术大学应用化学与工程学院 合肥 230026
- 作者简介：
Chun-ji Wu, E-mail: wuchunji@ciac.ac.cn
Dong-mei Cui, E-mail: dmcui@ciac.ac.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2023.23276
CLC：Published：20 June 2024，
Published Online：12 March 2024，
Received：30 November 2023，
Accepted：05 January 2024
- 稿件说明：
移动端阅览
王田田, 孙碧玮, 吴春姬, 崔冬梅. β-双亚胺稀土双烷基配合物催化邻甲氧基苯乙烯高间规聚合研究. 高分子学报, 2024, 55(6), 729-737
Wang, T. T.; Sun, B. W.; Wu, C. J.; Cui, D. M. Highly syndiotactic polymerizationof ortho-methoxystyrene with β-diketiminato rare-earth metal complexes. Acta Polymerica Sinica, 2024, 55(6), 729-737
王田田, 孙碧玮, 吴春姬, 崔冬梅. β-双亚胺稀土双烷基配合物催化邻甲氧基苯乙烯高间规聚合研究. 高分子学报, 2024, 55(6), 729-737 DOI： 10.11777/j.issn1000-3304.2023.23276.
Wang, T. T.; Sun, B. W.; Wu, C. J.; Cui, D. M. Highly syndiotactic polymerizationof ortho-methoxystyrene with β-diketiminato rare-earth metal complexes. Acta Polymerica Sinica, 2024, 55(6), 729-737 DOI： 10.11777/j.issn1000-3304.2023.23276.
摘要
设计合成了一类氮原子上含脂肪族取代基的
β
-双亚胺的配体及其相应的稀土金属配合物
1
~
3
. 在助催化剂有机硼盐和烷基铝的作用下，将配合物
1
~
3
用于催化邻甲氧基苯乙烯(
o
MOS)聚合中，制得了高间规选择性(
rrrr
>
99%)聚合物，所得聚合物的玻璃化转变温度
T
g
为-90 ℃，熔点
T
m
为240 ℃. 将配合物
2
用于催化异戊二烯(IP)均聚合，得到了以1
4-结构为主(含量约88.6%)的聚合物，玻璃化转变温度
T
g
为-57 ℃. 此外，借助DFT理论计算，发现配位模式是决定邻甲氧基苯乙烯聚合物立体选择性的关键.
Abstract
The coordination polymerization of polar monomers encounters the significantly challenging and long standing problem in the academic research field
similar to other olefins bearing polar functional groups. However
the key to polymerization is the design of the catalyst.
β-
Diketiminate ligands have gained increasing popularity since the mid 1990s due to their suitability as spectator ligands.Additionally
β
-diketiminate ligands have become some of the most widely used bidentate N-donor ligands in coordination chemistry nowadays. Interest in
β
-diketiminate complexes was focused mostly on their application in olefin
notably ethylene
polymerization or on investigations of the ligand coordination mode
which varies between in-plane
κ
2
-coordination and out-of-plane
η
4/5
-coordination. In this work
a series of rare earth metal complexes
1-3
bearing
β
-diketiminiato ligands featuring aliphatic substituents were designed and synthesized readily. In the presence of cocatalysts [Ph
3
C
]
[B(C
6
F
5
)
4
]
and Al
i
Bu
3
complexes
2
and
3
were highly active for polymerization of
ortho
-methoxystyrene (
o
MOS) to afford syndiotactic polymers (
rrrr
>
99%). These methoxyl functionalized polystyrenes have melting temperatures around 240 ℃ and a
T
g
of -90 ℃. Complex
2
showed high 1
4 selectivity (88.6%) for isoprene polymerization. Finally
we demenstrate that the stereoselectivity was determined by the coordination patterns of monomer using density functional theory (DFT) calculations clearly.
关键词
稀土催化剂高间规选择性邻甲氧基聚苯乙烯
Keywords
Rare-earth metal catalystsSyndiotacticOrtho-methoxystyrene
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