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单茂钪催化对氟苯乙烯间规聚合及与乙烯共聚合的研究
Syndiotactic Homo- and Co-polymerization of
p -Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes- 高分子学报 2017年第12期 页码：1922-1929
- 作者机构：
大连理工大学化工学院 精细化工国家重点实验室 大连 116024
- 作者简介：
郭方, E-mail: guofang@dlut.edu.cn Fang Guo, E-mail: guofang@dlut.edu.cn
李杨, E-mail: liyang@dlut.edu.cn Yang Li, E-mail: liyang@dlut.edu.cn
- 基金信息：国家自然科学基金(21674016);自然科学基金联合基金(U1508204)
DOI：10.11777/j.issn1000-3304.2017.17051
中图分类号：纸质出版日期：2017-12-20，
收稿日期：2017-3-20，
修回日期：2017-4-3，
扫 描 看 全 文
焦娜, 郭方, 李杨. 单茂钪催化对氟苯乙烯间规聚合及与乙烯共聚合的研究[J]. 高分子学报, 2017,(12):1922-1929.
Na Jiao, Fang Guo, Yang Li. Syndiotactic Homo- and Co-polymerization of
p -Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes[J]. Acta Polymerica Sinica, 2017,(12):1922-1929.焦娜, 郭方, 李杨. 单茂钪催化对氟苯乙烯间规聚合及与乙烯共聚合的研究[J]. 高分子学报, 2017,(12):1922-1929. DOI： 10.11777/j.issn1000-3304.2017.17051.
Na Jiao, Fang Guo, Yang Li. Syndiotactic Homo- and Co-polymerization of
p -Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes[J]. Acta Polymerica Sinica, 2017,(12):1922-1929. DOI： 10.11777/j.issn1000-3304.2017.17051.
摘要
采用（C
5
Me
4
SiMe
3
）Sc（CH
2
C
6
H
4
NMe
2
-
o
）
2
（
1
）和（C
5
Me
4
SiMe
3
）Sc（CH
2
SiMe
3
）
2
（THF）（
2
）2种单茂钪催化剂，考察了其催化对氟苯乙烯均聚合以及与乙烯共聚合的性能，并通过
1
H-NMR、
13
C-NMR、GPC和DSC对所获聚合物的微观结构和热性能进行了分析.结果表明，单茂钪
1
可以催化对氟苯乙烯均聚合，获得间规聚合物，但聚合活性较低.采用单茂钪
2
，控制溶剂种类和用量可以获得间规和无规2类聚合物：控制对氟苯乙烯单体在氯苯溶剂中浓度低于2.4 mol/L，可获得间规聚对氟苯乙烯（
rrrr
≥ 99%，
T
m
≥ 319℃），且聚合活性高达10
5
g polymer mol
Sc
-1
h
-1
；控制对氟苯乙烯单体在氯苯溶剂中浓度高于4.8 mol/L或者选用氟苯做溶剂，可获得无规聚对氟苯乙烯；固定单体浓度调控对氟苯乙烯和催化剂的比例，可获得分子量（
M
n
）在3.10×10
4
~2.08×10
5
间调控的间规和无规聚对氟苯乙烯.在常压乙烯下，单茂钪
1
和
2
还可以催化对氟苯乙烯与乙烯共聚合，获得了组成（对氟苯乙烯含量41 mol%~88 mol%）和分子量（3.10 x 10
4
~1.84 x 10
5
）可控的两元共聚物，共聚合活性高达10
6
g polymer mol
Sc
-1
h
-1
.当共聚物中乙烯含量高于对氟苯乙烯含量时，共聚物仅有源自聚乙烯嵌段的熔点（119~126℃）.当共聚物中对氟苯乙烯含量高于乙烯含量时，共聚物出现聚对氟苯乙烯嵌段；由单茂钪
1
获得聚对氟苯乙烯嵌段为间规结构，共聚物具有熔点（269~282℃）和玻璃化转变温度（
T
g
，79~82℃）；单茂钪
2
获得聚氟苯乙烯嵌段为无规结构，共聚物仅有1个
T
g
（94~96℃）.
Abstract
Syndiotactic polymerization of
p
-fluorostyrene and its copolymerization with ethylene catalyzed by half-sandwich scandium complex (C
5
Me
4
SiMe
3
)Sc(CH
2
C
6
H
4
NMe
2
-o)
2
(
1
) and (C
5
Me
4
SiMe
3
)Sc(CH
2
Si-Me
3
)
2
(THF) (
2
) have been examined. The microstructures and thermal properties of the obtained polymers were characterized by
1
H-NMR
13
C-NMR
GPC and DSC. Scandium complex
1
showed syndiotactic selectivity for the polymerization of
p
-fluorostyrene with low activity (10
3
g polymer mol
Sc
-1
h
-1
). Scandium complex
2
proved to be a high activity catalyst for the polymerization of
p
-fluorostyrene to afford syndiotactic or atactic poly(
p
-fluorostyrene) by controlling the type and the volume of the solvent. When the concentration of
p
-fluorostyrene in chlorobenzene was below 2.4 mol/L
the syndiotactic poly(
p
-fluorostyrene) (
rrrr
>
99%) was obtained with scandium complex
2
possessing high activity (10
5
g polymer mol
Sc
-1
h
-1
). The melting point (
T
m
) of syndiotactic poly(
p
-fluorostyrene) reached up to 324℃
suggesting the semicrystalline morphology of this polymer. The molecular weight of the syndiotactic poly(
p
-fluorostyrene) (
M
n
=3.10×10
4
-2.08×10
5
) was easily controlled by changing the feed ratio of
p
-fluorostyrene to catalyst. When the concentration of
p
-fluorostyrene in chlorobenzene was above 4.8 mol/L or fluorobenzene used as solvent
atactic poly(
p
-fluorostyrene) with controllable molecular weight (3.80×10
4
-1.88×10
5
) was obtained. Moreover
the copolymerizations of
p
-fluorostyrene with ethylene catalyzed by complexes
1
or
2
have also been prepared
leading to novel copolymers with controlled composition (
p
-fluorostyrene content:41 mol% -88 mol%) and molecular weight (3.10×10
4
-1.84×10
5
)
and with high activity (up to 10
6
g polymer mol
Sc
-1
h
-1
). When ethylene content in the copolymer is higher than that of
p
-fluorostyrene
the copolymers showed a
T
m
around 119 -126℃ owing to polyethylene blocks. When
p
-fluorostyrene content in the copolymer is higher than that of ethylene
the obtained copolymers with syndiotactic poly(
p
-fluorostyrene) blocks
prepared by scandium complex
1
showed a
T
m
around 269 -282℃ and a
T
g
around 79 -82℃; In contrast
the copolymers with atactic poly(
p
-fluorostyrene) blocks prepared by scandium complex
2
showed their
T
g
around 94 -96℃.
关键词
钪对氟苯乙烯间规聚合乙烯共聚
Keywords
Scandiump-FluorostyreneSyndiotactic polymerizationEthyleneCopolymerization
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