Heterogeneous Fluorenylamidodimethyltitanium Catalyzed <italic style="font-style: italic">α</italic>-Olefin Polymerization

Kai-meng Zhou; Jun-fen Sun; Long Chen; Ming-yuan Li; Zheng-guo Cai

doi:10.11777/j.issn1000-3304.2026.26100

您当前的位置：

首页 >

文章列表页 >

Heterogeneous Fluorenylamidodimethyltitanium Catalyzed α-Olefin Polymerization

Research Article | 更新时间：2026-07-30

- Heterogeneous Fluorenylamidodimethyltitanium Catalyzed α-Olefin Polymerization
- Acta Polymerica Sinica Vol. 57, Issue 8, Pages: 1712-1719(2026)
- 作者机构：
  
  东华大学材料科学与工程学院先进纤维材料全国重点实验室上海 201620
- 作者简介：
  
  Ming-yuan Li, E-mail: mingyuanli@dhu.edu.cn
  Zheng-guo Cai, E-mail: caizg@dhu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26100
  CLC：
- CSTR：32057.14.GFZXB.2026.7619
- Received：30 March 2026，
  
  Accepted：08 May 2026，
  
  Online First：26 June 2026，
  
  Published：20 August 2026
- 稿件说明：
移动端阅览
周开猛, 孙俊芬, 陈龙, 李明远, 蔡正国. 负载型芴基胺基二甲基钛配合物催化,α-烯烃聚合. 高分子学报, ,2026, 57(8), 1712-1719.

Zhou, K. M.; Sun, J. F.; Chen, L.; Li, M. Y.; Cai, Z. G. Heterogeneous fluorenylamidodimethyltitanium catalyzed ,α-olefin polymerization. ,Acta Polymerica Sinica (in Chinese), ,2026, 57(8), 1712-1719.
周开猛, 孙俊芬, 陈龙, 李明远, 蔡正国. 负载型芴基胺基二甲基钛配合物催化,α-烯烃聚合. 高分子学报, ,2026, 57(8), 1712-1719. DOI： 10.11777/j.issn1000-3304.2026.26100. CSTR： 32057.14.GFZXB.2026.7619.

Zhou, K. M.; Sun, J. F.; Chen, L.; Li, M. Y.; Cai, Z. G. Heterogeneous fluorenylamidodimethyltitanium catalyzed ,α-olefin polymerization. ,Acta Polymerica Sinica (in Chinese), ,2026, 57(8), 1712-1719. DOI： 10.11777/j.issn1000-3304.2026.26100. CSTR： 32057.14.GFZXB.2026.7619.

摘要

利用SiO

负载的改性甲基铝氧烷(dMMAO/SiO

)负载[

-BuNSiMe

Flu

]

TiMe

钛配合物制备非均相钛催化剂(Ti-dMMAO/SiO

)，所得到的Ti-dMMAO/SiO

用于催化

-烯烃聚合. 结果表明，1-己烯均聚活性随Al/Ti摩尔比的提高而增加，当Al/Ti摩尔比为1000时，活性最高达到1.34×10

g·mol

-1

·h

-1

；所得聚合物的重均分子量(

)随Al/Ti摩尔比的提升先增加后降低，当Al/Ti摩尔比为400时，

最高为0.90×10

g·mol

-1

. 尽管聚合活性随着

-烯烃的侧链长度增加而有所降低，但催化1-十八烯聚合的TOF值仍达到104 min

-1

，同时得到的聚(1-十八烯)仍具有较高的分子量(0.90×10

g·mol

-1

). 所得到的聚(1-十二烯)和聚(1-十八烯)由于具有较长的侧链而产生结晶，熔点(

)分别为-24和43 ℃. 为了改善该类聚合物在油品中的溶解性，将1-十八烯与1-辛烯进行共聚. 共聚结果表明，Ti-dMMAO/SiO

催化体系在保持高活性的同时得到高分子量的无规共聚物，且其形貌也能得到一定改善.

Abstract

A heterogeneous titanium catalyst (Ti-dMMAO/SiO

) was prepared by loading the titanium complex [

-BuNSiMe

Flu

]

TiMe

onto SiO

-supported modified methylalumoxane (dMMAO/SiO

). The resulting Ti-dMMAO/SiO

was used to catalyse the polymerization of

-olefins. The results indicated that the activity for the homopolymerization of 1-hexene increased with an increase in the Al/Ti molar ratio; when the Al/Ti molar ratio was 1000

the activity reaches a maximum of 1.34×10

g·mol

-1

·h

-1

; The weight-average molecular weight (

) of the resulting polymer first increased and then decreased with an increase in the Al/Ti molar ratio; when the Al/Ti molar ratio was 400

the

reached a maximum of 0.90×10

g·mol

-1

. Although the polymerization activity decreased somewhat with increasing side-chain length of the

-olefins

the TOF value for the polymerization of 1-octadecene still reached 104 min

-1

whilst the resulting poly(1-octadecene) retained a high molecular weight (0.90×10

g·mol

-1

). The resulting poly(1-dodecene) and poly(1-octadecene) crystallized due to their long side chains

with melting points (

) of -24 and 43 ℃

respectively. To improve the solubility of this class of polymers in oil

1-octadecene was copolymerized with 1-octene in

a random copolymerization process. The copolymerization results indicated that the Ti-dMMAO/SiO

catalytic system yielded high-molecular-weight random copolymers whilst maintaining high activity and appearance can also be improved.

关键词

Keywords

references

Busico V. Metal-catalysed olefin polymerisation into the new millennium: a perspective outlook . Dalton Trans. , 2009 ( 41 ), 8794 - 8802 . doi: 10.1039/b911862b http://dx.doi.org/10.1039/b911862b

郭红军 . 聚烯烃高值化改性及其应用研究进展 . 工程塑料应用 , 2019 , 47 ( 9 ), 158 - 162 .

韩书亮 , 潘亚男 . 聚烯烃弹性体极具发展前景 . 中国石化 , 2024 , ( 8 ), 57 - 59 .

Ziegler K. ; Holzkamp E. ; Breil H. ; Martin H. Das mülheimer normaldruck-polyäthylen-verfahren . Angew. Chem. , 1955 , 67 ( 19-20 ), 541 - 547 . doi: 10.1002/ange.19550671902 http://dx.doi.org/10.1002/ange.19550671902

Natta G. ; Pino P. ; Mazzanti G. ; Giannini U. ; Mantica E. ; Peraldo, M. The nature of some soluble catalysts for low- pressure ethylene polymerization . In: Natta, G., ed. Stereoregular Polymers and Stereospecific Polymerizations . Oxford : Pergamon Press , 1967 . 180 - 184 . doi: 10.1016/b978-1-4831-9883-5.50030-1 http://dx.doi.org/10.1016/b978-1-4831-9883-5.50030-1

Shao H. Q. ; Wang R. F. ; Li H. ; Guo X. Y. ; Jiang T. Synthesis of low-molecular-weight poly- α -olefins using silicon-bridged zirconocene catalyst for lubricant basestock . Arab. J. Chem. , 2020 , 13 ( 1 ), 2715 - 2721 . doi: 10.1016/J.ARABJC.2018.07.003 http://dx.doi.org/10.1016/J.ARABJC.2018.07.003

Klosin J. ; Fontaine P. P. ; Figueroa R. Development of group IV molecular catalysts for high temperature ethylene- α -olefin copolymerization reactions . Acc. Chem. Res. , 2015 , 48 ( 7 ), 2004 - 2016 . doi: 10.1021/acs.accounts.5b00065 http://dx.doi.org/10.1021/acs.accounts.5b00065

Zhao R. D. ; Mi P. K. ; Xu S. ; Dong S. Q. Structure and properties of poly- α -olefins containing quaternary carbon centers . ACS Omega , 2020 , 5 ( 16 ), 9142 - 9150 . doi: 10.1021/acsomega.9b04361 http://dx.doi.org/10.1021/acsomega.9b04361

Nifant'ev I. E. ; Shlyakhtin A. V. ; Tavtorkin A. N. ; Korchagina S. A. ; Chinova M. S. ; Vinogradov A. A. ; Vinogradov A. A. ; Roznyatovsky V. A. ; Khaidapova D. D. ; Ivchenko P. V. The synthesis of ultra-high molecular weight poly(1-hexene)s by low-temperature Ziegler-Natta precipitation polymerization in fluorous reaction media . Polymer , 2018 , 139 , 98 - 106 . doi: 10.1016/j.polymer.2018.02.011 http://dx.doi.org/10.1016/j.polymer.2018.02.011

Haas I. ; Dietel T. ; Press K. ; Kol M. ; Kempe R. Aminopyridinate-FI hybrids, their hafnium and titanium complexes, and their application in the living polymerization of 1-hexene . Chem. Eur. J. , 2013 , 19 ( 42 ), 14254 - 14262 . doi: 10.1002/chem.201301511 http://dx.doi.org/10.1002/chem.201301511

Cai Z. G. ; Ohmagari M. ; Nakayama Y. ; Shiono T. Highly active syndiospecific living polymerization of higher 1-alkene with ansa-fluorenylamidodimethyltitanium complex . Macromol. Rapid Commun. , 2009 , 30 ( 21 ), 1812 - 1816 . doi: 10.1002/marc.200900413 http://dx.doi.org/10.1002/marc.200900413

Cai Z. G. ; Nakayama Y. ; Shiono T. Living random copolymerization of propylene and norbornene with ansa -fluorenylamidodimethyltitanium complex: synthesis of novel syndiotactic polypropylene- b -poly(propylene- ran -norbornene) . Macromolecules , 2006 , 39 ( 6 ), 2031 - 2033 . doi: 10.1021/ma060122x http://dx.doi.org/10.1021/ma060122x

Saito J. ; Suzuki Y. ; Makio H. ; Tanaka H. ; Onda M. ; Fujita T. Polymerization of higher α -olefins with a bis(phenoxyimine)Ti complex/ i -Bu 3 Al/Ph 3 CB(C 6 F 5 )4: formation of stereo- and regioirregular high molecular weight polymers with high efficiency. Macromolecules, 2006, 39 ( 12 ), 4023 - 4031 .

Cai Z. G. ; Su H. H. ; Shiono T. Precise synthesis of olefin block copolymers using a syndiospecific living polymerization system . Chinese J. Polym. Sci. , 2013 , 31 ( 4 ), 541 - 549 . doi: 10.1007/s10118-013-1250-7 http://dx.doi.org/10.1007/s10118-013-1250-7

Cai Z. G. ; Ikeda T. ; Akita M. ; Shiono T. Substituent effects of tert-butyl groups on fluorenyl ligand in syndiospecific living polymerization of propylene with ansa-fluorenylamidodimethyltitanium complex . Macromolecules , 2005 , 38 ( 20 ), 8135 - 8139 . doi: 10.1021/ma050898i http://dx.doi.org/10.1021/ma050898i

Segal S. ; Goldberg I. ; Kol M. Zirconium and titanium diamine bis(phenolate) catalysts for α -olefin polymerization:

from atactic oligo( 1 -hexene) to ultrahigh-molecular-weight isotactic poly(1-hexene) . Organometallics , 2005, 24 ( 2 ), 200 - 202 .

Tshuva E. Y. ; Goldberg I. ; Kol M. ; Goldschmidt Z. Zirconium complexes of amine-bis(phenolate) ligands as catalysts for 1polymerization-hexene: peripheral structural parameters strongly affect reactivity. Organometallics , 2001 , 20 ( 14 ), 3017 - 3028 . doi: 10.1021/om0101285 http://dx.doi.org/10.1021/om0101285

Nomura K. ; Pengoubol S. ; Apisuk W. Synthesis of ultrahigh molecular weight polymers with low PDIs by polymerizations of 1-decene, 1-dodecene, and 1-tetradecene by Cp*TiMe2 (O-2 , 6 -iPr 2 C 6 H3catalyst)-borate. Molecules, 2019, 24 ( 8 ), 1634 .

Wang X. Y. ; Yang F. ; Cao D. F. ; Ma Z. ; Pan L. ; Li Y. S. Structure and property of comb-like polyolefins derived from highly Stereospecific homo-polymerization of higher α -olefins . Polymer , 2021 , 213 , 123223 . doi: 10.1016/j.polymer.2020.123223 http://dx.doi.org/10.1016/j.polymer.2020.123223

López-Barrón C. R. ; Hagadorn J. R. ; Mattler S. J. ; Throckmorton J. A. Syndiotactic α -olefin molecular bottlebrushes: crystallization, melting, and hierarchical microstructure . Macromolecules , 2020 , 53 ( 10 ), 3778 - 3788 . doi: 10.1021/acs.macromol.0c00420 http://dx.doi.org/10.1021/acs.macromol.0c00420

Chum P. S. ; Swogger K. W. Olefin polymer technologies: history and recent progress at The Dow Chemical Company . Prog. Polym. Sci. , 2008 , 33 ( 8 ), 797 - 819 . doi: 10.1016/j.progpolymsci.2008.05.003 http://dx.doi.org/10.1016/j.progpolymsci.2008.05.003

Wang Z. B. ; Zhu H. R. ; Wang L. J. ; Yang Q. ; Chen S. J. ; Wang Y. T. ; Jiang T. ; Li J. Metallocene catalyst supported with the pretreated methylaluminoxane-modified silica for ethylene polymerization . Mater. Today Commun. , 2025 , 48 , 113510 . doi: 10.1016/j.mtcomm.2025.113510 http://dx.doi.org/10.1016/j.mtcomm.2025.113510

Ribeiro M. R. ; Deffieux A. ; Portela M. F. Supported metallocene complexes for ethylene and propylene polymerizations: preparation and activity . Ind. Eng. Chem. Res. , 1997 , 36 ( 4 ), 1224 - 1237 . doi: 10.1021/ie960475s http://dx.doi.org/10.1021/ie960475s

Zanoni S. ; Nikolopoulos N. ; Welle A. ; Vantomme A. ; Weckhuysen B. M. Early-stage particle fragmentation behavior of a commercial silica-supported metallocene catalyst . Catal. Sci. Technol. , 2021 , 11 ( 15 ), 5335 - 5348 . doi: 10.1039/d1cy00930c http://dx.doi.org/10.1039/d1cy00930c

Nishii K. ; Hagihara H. ; Ikeda T. ; Akita M. ; Shiono T. Stereospecific polymerization of propylene with group 4 ansa-fluorenylamidodimethyl complexes . J. Organomet. Chem. , 2006 , 691 ( 1-2 ), 193 - 201 . doi: 10.1016/j.jorganchem.2005.08.027 http://dx.doi.org/10.1016/j.jorganchem.2005.08.027

Tanaka R. ; Kawahara T. ; Shinto Y. ; Nakayama Y. ; Shiono T. An alternative method for the preparation of trialkylaluminum-depleted modified methylaluminoxane (dMMAO) . Macromolecules , 2017 , 50 ( 15 ), 5989 - 5993 . doi: 10.1021/acs.macromol.7b01003 http://dx.doi.org/10.1021/acs.macromol.7b01003

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

N-Bridged Phosphine Carbonyl Palladium Complex Catalysts for Nonalternating Copolymerization of Ethylene and Carbon Monoxide

Iron Complex Catalysts in Ethylene Reactivity: from Concept to Commercialization

Studies on Homo- and Co-polymerizations of Polar and Non-polar Monomers Using Rare-earth Metal Catalysts

Synthesis and Degradation of CO2/Propylene Oxide/Phthalic Anhydride/o-Phthalaldehyde Copolymers

A Polydimethylsiloxane Membrane-regulated Oxygen-generating System Based on Multi-interface Reaction-Transport Coupling for Chronic Wound Therapy

Related Author

Ye Liu

Shi-Yu Chen

Shi-Huan Li

Xin-Jun Li

Yun Wang

Wen-juan Zhang

Xing Wang

Yan-ping Ma

Related Institution

State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology

Beijing Key Laboratory of Clothing Materials R&D and Assessment, Beijing Engineering Research Center of Textile Nanofiber, School of Materials Design & Engineering, Beijing Institute of Fashion Technology

Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences

Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

AI问答

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802046899号
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰

Heterogeneous Fluorenylamidodimethyltitanium Catalyzed α-Olefin Polymerization

DOI：10.11777/j.issn1000-3304.2026.26100

摘要

Abstract

关键词

Keywords

references