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单茂稀土催化剂催化
E -间戊二烯与苯乙烯共聚合的研究Copolymerization of
E -Pentadiene and Styrene Catalyzed by Half-Sandwich Rare Earth Catalysts- 高分子学报 2025年56卷第5期 页码：789-799
- 作者机构：
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
- 作者简介：
E-mail: guofang@dlut.edu.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2024.24288
中图分类号：- CSTR：32057.14.GFZXB.2025.7345
收稿日期：2024-12-04，
录用日期：2025-01-17，
网络出版日期：2025-03-21，
纸质出版日期：2025-05-20
- 稿件说明：
移动端阅览
马杰, 郭方. 单茂稀土催化剂催化E-间戊二烯与苯乙烯共聚合的研究. 高分子学报, 2025, 56(5), 789-799
Ma, J.; Guo, F. Copolymerization of E-pentadiene and styrene catalyzed by half-sandwich rare earth catalysts. Acta Polymerica Sinica, 2025, 56(5), 789-799
马杰, 郭方. 单茂稀土催化剂催化E-间戊二烯与苯乙烯共聚合的研究. 高分子学报, 2025, 56(5), 789-799 DOI： 10.11777/j.issn1000-3304.2024.24288. CSTR： 32057.14.GFZXB.2025.7345.
Ma, J.; Guo, F. Copolymerization of E-pentadiene and styrene catalyzed by half-sandwich rare earth catalysts. Acta Polymerica Sinica, 2025, 56(5), 789-799 DOI： 10.11777/j.issn1000-3304.2024.24288. CSTR： 32057.14.GFZXB.2025.7345.
摘要
研究了单茂稀土催化剂Cp'Ln(CH
2
C
6
H
4
NMe
2
-
o
)
2
(
1
: Cp' = C
5
Me
4
SiMe
3
Ln = Sc;
2
: Cp' = C
5
Me
4
SiMe
3
Ln = Nd;
3
: Cp' = fluorene
Ln = Sc;
4
: Cp' = fluorene
Ln = Nd)催化
E
-间戊二烯(
E
-PD)与苯乙烯(St)共聚合的性能，通过NMR、GPC、DSC和聚合动力学对所获聚合物的微观结构和热性能进行表征分析. 结果表明，单茂稀土催化剂的中心金属和茂配体结构不仅影响
E
-PD和St聚合活性和选择性，而且影响
E
-PD-St共聚物的序列结构. 单茂钪
1
可以高活性的催化
E
-PD和St均聚合及共聚合，在室温甲苯溶剂中聚合5 min，聚合物的收率达100%，
E
-PD聚合
cis
-1
4选择性为72%，St间规聚合的间规度为99%. 由单茂钪
1
获得的
E
-PD-St共聚物为多嵌段共聚物，通过控制加料比可以精确控制共聚物的组成. 不同组成的
E
-PD-St多嵌段共聚物具有源自间规聚苯乙烯(
s
PS)嵌段的熔点(
T
m
= 249~266 ℃)和源自
E
-PD聚合物嵌段的玻璃化转变温度(
T
g
= -42~-49 ℃). 单茂钕
4
也可以催化
E
-PD和St均聚合及共聚合，但相比于单茂钪
1
其催化活性下降，而且聚合选择性也与单茂钪
1
不相同. 单茂钕
4
在70 ℃甲苯溶剂中催化
E
-PD聚合1 h，聚合物收率达94%，
trans
-1
4选择性为80%；同样条件下催化St聚合4 h，聚合物收率达90%，间规度为84%. 单茂钕
4
催化不同比例
E
-PD和St共聚合4 h，共聚物收率达80%以上，获得组成可控的
E
-PD-St无规共聚物. 不同组成的
E
-PD-St无规共聚物在-28~84 ℃间具有一个
T
g
，
T
g
值随着共聚物中St含量的增加而提高.
Abstract
The homopolymerization and copolymerization of
E
-pentadiene (
E
-PD) and styrene (St) by half- sandwich rare earth complexes Cp'Ln(CH
2
C
6
H
4
NMe
2
-
o
)
2
(
1
: Cp' = C
5
Me
4
SiMe
3
Ln = Sc;
2
: Cp' = C
5
Me
4
SiMe
3
Ln = Nd;
3
: Cp' = fluorene
Ln = Sc;
4
: Cp' = fluorene
Ln = Nd) have been studied. The microstructure and thermal properties of the obtained polymers were characterized by NMR
GPC
DSC and copolymerization kinetics. The results indicated that the central metal (Ln) and ligand structures (Cp') of half-sandwich rare earth complexes directly influenced the activity and selectivity of
E
-PD and St polymerization
as well as the sequence structure of
E
-PD-St copolymers. The scandium complex
1
can serve as an efficient catalyst for the homopolymerization and copolymerization of
E
-PD and St. The polymerization of
E
-PD and St in toluene at 25 ℃ for 5 min afforded the corresponding polymers in 100% yield. The
cis
-1
4 selectivity of
E
-PD polymerization was 72%
and the syndiotacticity (
rrrr
) of St polymerization was 99%. The copolymerization of
E
-PD and St catalyzed by the scandium complex
1
with different feed ratios afforded the multi-block
E
-PD-St copolymers
and the composition of
E
-PD-St copolymers can be controlled by changing the feed ratio of
E
-PD and St. The multi-block
E
-PD-St copolymers with different compositions possessed a melting point (
T
m
= 249~266 ℃) originating from syndiotactic polySt (
s
PS) blocks and a glass transition temperature (
T
g
= -42 - -49 ℃) originating from poly
E
-PD blocks. The neodymium complex
4
can also serve as an efficient catalyst for the homopolymerization and copolymerization of
E
-PD and St
however decreased in polymerization activity and changed in polymerization selectivity compared with the scandium complex
1
. The homopolymerization of
E
-PD catalyzed by the neodymium complex
4
in toluene solvent at 70 ℃ for 1 h afforded a polymer containing 80%
trans
-1
4 poly
E
-PD in 94% yield. Under the same conditions
the homopolymerization of St for 4 h resulted in
s
PS with 84% syndiotacticity in 90% yield. The copolymerization of
E
-PD and St in different feed ratios for 4 h afforded the random
E
-PD-St copolymers with different compositions in more than 80% yield. The random
E
-PD-St copolymers with different compositions possessed a
T
g
between -28 and 84 ℃
which increased with the increase of St content in the copolymers.
关键词
Keywords
references
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