Copolymerization of <italic style="font-style: italic">E</italic>-Pentadiene and Styrene Catalyzed by Half-Sandwich Rare Earth Catalysts

Jie Ma; Fang Guo

doi:10.11777/j.issn1000-3304.2024.24288

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Copolymerization of E-Pentadiene and Styrene Catalyzed by Half-Sandwich Rare Earth Catalysts

Research Article | 更新时间：2025-06-17

- Copolymerization of E-Pentadiene and Styrene Catalyzed by Half-Sandwich Rare Earth Catalysts
- Acta Polymerica Sinica Vol. 56, Issue 5, Pages: 789-799(2025)
- 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：
  
  Fang Guo, E-mail: guofang@dlut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24288
  CLC：
- CSTR：32057.14.GFZXB.2025.7345
- Received：04 December 2024，
  
  Accepted：17 January 2025，
  
  Published Online：21 March 2025，
  
  Published：20 May 2025
- 稿件说明：
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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

NMe

)

(

: Cp' = C

SiMe

Ln = Sc;

: Cp' = C

SiMe

Ln = Nd;

: Cp' = fluorene

Ln = Sc;

: Cp' = fluorene

Ln = Nd)催化

-间戊二烯(

-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

-PD和St聚合活性和选择性，而且影响

-PD-St共聚物的序列结构. 单茂钪

可以高活性的催化

-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%，

-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

获得的

-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

-PD-St多嵌段共聚物具有源自间规聚苯乙烯(

PS)嵌段的熔点(

= 249~266 ℃)和源自

-PD聚合物嵌段的玻璃化转变温度(

= -42~-49 ℃). 单茂钕

也可以催化

-PD和St均聚合及共聚合，但相比于单茂钪

其催化活性下降，而且聚合选择性也与单茂钪

不相同. 单茂钕

在70 ℃甲苯溶剂中催化

-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

催化不同比例

-PD和St共聚合4 h，共聚物收率达80%以上，获得组成可控的

-PD-St无规共聚物. 不同组成的

-PD-St无规共聚物在-28~84 ℃间具有一个

，

值随着共聚物中St含量的增加而提高.

Abstract

The homopolymerization and copolymerization of

-pentadiene (

-PD) and styrene (St) by half- sandwich rare earth complexes Cp'Ln(CH

NMe

)

(

: Cp' = C

SiMe

Ln = Sc;

: Cp' = C

SiMe

Ln = Nd;

: Cp' = fluorene

Ln = Sc;

: 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

-PD and St polymerization

as well as the sequence structure of

-PD-St copolymers. The scandium complex

can serve as an efficient catalyst for the homopolymerization and copolymerization of

-PD and St. The polymerization of

-PD and St in toluene at 25 ℃ for 5 min afforded the corresponding polymers in 100% yield. The

cis

-1

4 selectivity of

-PD polymerization was 72%

and the syndiotacticity (

rrrr

) of St polymerization was 99%. The copolymerization of

-PD and St catalyzed by the scandium complex

with different feed ratios afforded the multi-block

-PD-St copolymers

and the composition of

-PD-St copolymers can be controlled by changing the feed ratio of

-PD and St. The multi-block

-PD-St copolymers with different compositions possessed a melting point (

‍= ‍249~266 ‍℃‍) originating from syndiotactic polySt (

PS) blocks and a glass transition temperature (

= -42 - -49 ℃) originating from poly

-PD blocks. The neodymium complex

can also serve as an efficient catalyst for the homopolymerization and copolymerization of

-PD and St

however decreased in polymerization activity and changed in polymerization selectivity compared with the scandium complex

. The homopolymerization of

-PD catalyzed by the neodymium complex

in toluene solvent at 70 ℃ for 1 h afforded a polymer containing 80%

trans

-1

4 poly

-PD in 94% yield. Under the same conditions

the homopolymerization of St for 4 h resulted in

PS with 84% syndiotacticity in 90% yield. The copolymerization of

-PD and St in different feed ratios for 4 h afforded the random

-PD-St copolymers with different compositions in more than 80% yield. The random

-PD-St copolymers with different compositions possessed a

between -28 and 84 ℃

which increased with the increase of St content in the copolymers.

关键词

Keywords

references

Ricci G. ; Italia S. ; Porri L. Polymerization of (Z)‍- 1 ,‍ 3 -pentadiene with CpTiCl 3 /MAO . Effect of temperature on polymer structure and mechanistic implications. Macromolecules, 1994, 27 ( 3 ), 868 - 869 . doi: 10.1021/ma00081a037 http://dx.doi.org/10.1021/ma00081a037

Lopez-Sanchez J. A. ; Lamberti M. ; Pappalardo D. ; Pellecchia C. Polymerization of conjugated dienes promoted by bis(phenoxyimino) titanium catalysts . Macromolecules , 2003 , 36 ( 24 ), 9260 - 9263 . doi: 10.1021/ma035038l http://dx.doi.org/10.1021/ma035038l

Costabile C. ; Capacchione C. ; Saviello D. ; Proto A. Mechanistic studies on conjugated diene polymerizations promoted by a titanium complex containing a tetradentate [OSSO ] ‍-type bis(phenolato) ligand. Macromolecules , 2012 , 45 ( 16 ), 6363 - 6370 . doi: 10.1021/ma3011697 http://dx.doi.org/10.1021/ma3011697

Ricci G. ; Motta T. ; Boglia A. ; Alberti E. ; Zetta L. ; Bertini F. ; Arosio P. ; Famulari A. ; Meille S. V. Synthesis, characterization , and crystalline structure of syndiotactic 1 , 2 -polypentadiene: the trans polymer. Macromolecules, 2005, 38 ( 20 ), 8345 - 8352 . doi: 10.1021/ma047605q http://dx.doi.org/10.1021/ma047605q

Jia X. Y. ; Hu Y. M. ; Dai Q. Q. ; Bi J. F. ; Bai C. X. ; Zhang X. Q. Synthesis of syndiotactic cis-1 ,‍ 4 -polypentadiene by using ternary neodymium-based catalyst . Polymer, 2013, 54 ( 12 ), 2973 - 2978 . doi: 10.1016/j.polymer.2013.04.022 http://dx.doi.org/10.1016/j.polymer.2013.04.022

Purevsuren B. ; Allegra G. ; Meille S. V. ; Farina A. ; Porri L. ; Ricci G. Cis -isotactic 1,4-polypentadiene. NMR solution characterization and crystal structure of polymers prepared with neodymium-catalytic systems . Polym. J. , 1998 , 30 ( 5 ), 431 - 434 . doi: 10.1295/polymj.30.431 http://dx.doi.org/10.1295/polymj.30.431

Nishii K. ; Kang X. H. ; Nishiura M. ; Luo Y. ; Hou Z. M. Regio- and stereospecific living polymerization and copolymerization of (E)‍- 1 ,‍ 3 -pentadiene with 1,‍ 3 -butadiene by half-sandwich scandium catalysts . Dalton Trans., 2013, 42 ( 25 ), 9030 - 9032 . doi: 10.1039/c3dt50357g http://dx.doi.org/10.1039/c3dt50357g

Nishii K. ; Zhou G. L. ; Saito Y. ; Yamamoto A. ; Nishiura M. ; Luo Y. ; Hou Z. M. Synthesis of thermoplastic elastomers by yttrium-catalyzed Isospecific Trans-1 ,‍ 4 -polymerization of (E)‍-1,‍ 3 -pentadiene . Bull. Chem. Soc. Jpn., 2021, 94 ( 4 ), 1285 - 1291 . doi: 10.1246/bcsj.20210026 http://dx.doi.org/10.1246/bcsj.20210026

Ricci G. ; Battistella M. ; Porri L. Chemoselectivity and stereospecificity of chromium(II) catalysts for 1 ,‍ 3 -diene polymerization . Macromolecules, 2001, 34 ( 17 ), 5766 - 5769 . doi: 10.1021/ma010247w http://dx.doi.org/10.1021/ma010247w

Longo P. ; Proto A. ; Oliva P. ; Sessa I. ; Zambelli A. Copolymerization of styrene with (Z)‍- 1 ,‍ 3 -pentadiene in the presence of a syndiotactic-specific catalyst . J. Polym. Sci. Part A, 1997, 35 ( 13 ), 2697 - 2702 . doi: 10.1002/(sici)1099-0518(19970930)35:13<2697::aid-pola14>3.3.co;2-a http://dx.doi.org/10.1002/(sici)1099-0518(19970930)35:13<2697::aid-pola14>3.3.co;2-a

Loria M. ; Proto A. ; Capacchione C. Styrene-isoprene and styrene-1 ,‍ 3 -pentadiene copolymerisation catalyzed by titanium [OSSO ]‍-type catalysts . RSC Adv., 2015, 5 ( 81 ), 65998 - 66004 . doi: 10.1039/c5ra11866b http://dx.doi.org/10.1039/c5ra11866b

Luo Y. J. ; Baldamus J. ; Hou Z. M. Scandium half-metallocene-catalyzed syndiospecific styrene polymerization and styrene-ethylene copolymerization: Unprecedented incorporation of syndiotactic styrene-styrene sequences in styrene-ethylene copolymers . J. Am. Chem. Soc. , 2004 , 126 ( 43 ), 13910 - 13911 . doi: 10.1021/ja046063p http://dx.doi.org/10.1021/ja046063p

Li X. F. ; Wang X. Y. ; Tong X. ; Zhang H. X. ; Chen Y. Y. ; Liu Y. ; Liu H. ; Wang X. J. ; Nishiura M. ; He H. ; Lin Z. G. ; Zhang S. W. ; Hou Z. M. Aluminum effects in the syndiospecific copolymerization of styrene with ethylene by cationic fluorenyl scandium alkyl catalysts . Organometallics , 2013 , 32 ( 5 ), 1445 - 1458 . doi: 10.1021/om3011036 http://dx.doi.org/10.1021/om3011036

Guo F. ; Nishiura M. ; Koshino H. ; Hou Z. M. Scandium-catalyzed cyclocopolymerization of 1 ,‍ 5 -hexadiene with styrene and ethylene: efficient synthesis of cyclopolyolefins containing syndiotactic styrene‍–‍styrene sequences and methylene-1,3-cyclopentane units. Macromolecules, 2011, 44 ( 16 ), 6335 - 6344 . doi: 10.1021/ma201271r http://dx.doi.org/10.1021/ma201271r

Lin F. ; Wang X. B. ; Pan Y. P. ; Wang M. Y. ; Liu B. ; Luo Y. ; Cui D. M. Nature of the entire range of rare earth metal-based cationic catalysts for highly active and syndioselective styrene polymerization . ACS Catal. , 2016 , 6 ( 1 ), 176 - 185 . doi: 10.1021/acscatal.5b02334 http://dx.doi.org/10.1021/acscatal.5b02334

段阳芷 , 姜磊 , 刁凯颖 , 郭方 . 单茂钪催化苯乙烯衍生物与异戊二烯共聚合的研究 . 高分子学报 , 2020 , 51 ( 9 ), 1059 - 1064 . doi: 10.11777/j.issn1000-3304.2020.20027 http://dx.doi.org/10.11777/j.issn1000-3304.2020.20027

孟蕊 , 郭方 , 史正海 , 李杨 . 单茂钪催化合成高顺式异戊二烯/苯乙烯共聚物的研究 . 高分子学报 , 2015 , ( 10 ), 1189 - 1195 . doi: 10.11777/j.issn1000-3304.2015.15062 http://dx.doi.org/10.11777/j.issn1000-3304.2015.15062

Nishiura D. M. ; Baldamus D. J. ; Shima D. T. ; Mori K. ; Hou P. Z. Synthesis and structures of the C 5Me4SiMe3-supported polyhydride complexes over the full size range of the rare earth series. Chem. Eur. J. , 2011 , 17 ( 18 ), 5033 - 5044 . doi: 10.1002/chem.201002998 http://dx.doi.org/10.1002/chem.201002998

Chien J. C. ; Tsai W. M. ; Rausch M. D. Isospecific polymerization of propylene catalyzed by rac-ethylenebis(indenyl)methylzirconium cation . J. Am. Chem. Soc. , 1991 , 113 ( 22 ), 8570 - 8571 . doi: 10.1021/ja00022a081 http://dx.doi.org/10.1021/ja00022a081

Kang X. H. ; Zhou G. L. ; Wang X. B. ; Qu J. P. ; Hou Z. M. ; Luo Y. Alkyl effects on the chain initiation efficiency of olefin polymerization by cationic half-sandwich scandium catalysts: a DFT study . Organometallics , 2016 , 35 ( 6 ), 913 - 920 . doi: 10.1021/acs.organomet.6b00081 http://dx.doi.org/10.1021/acs.organomet.6b00081

Li X. F. ; Nishiura M. ; Hu L. H. ; Mori K. ; Hou Z. M. Alternating and random copolymerization of isoprene and ethylene catalyzed by cationic half-sandwich scandium alkyls . J. Am. Chem. Soc. , 2009 , 131 ( 38 ), 13870 - 13882 . doi: 10.1021/ja9056213 http://dx.doi.org/10.1021/ja9056213

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Related Institution

State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

School of Applied Chemistry and Engineering, University of Science and Technology of China

Department of Polymer Science and Engineering, University of Science and Technology of China

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institue of Applied Chemistry, Chinese Acadamy of Sciences

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⁰

Copolymerization of E-Pentadiene and Styrene Catalyzed by Half-Sandwich Rare Earth Catalysts

DOI：10.11777/j.issn1000-3304.2024.24288

摘要

Abstract

关键词

Keywords

references