负载型芴基胺基二甲基钛配合物催化<italic style="font-style: italic">α</italic>-烯烃聚合

周开猛; 孙俊芬; 陈龙; 李明远; 蔡正国

doi:10.11777/j.issn1000-3304.2026.26100

您当前的位置：

首页 >

文章列表页 >

负载型芴基胺基二甲基钛配合物催化α-烯烃聚合

研究论文 | 更新时间：2026-06-18

- 负载型芴基胺基二甲基钛配合物催化α-烯烃聚合
- Heterogeneous Fluorenylamidodimethyltitanium Catalyzed α-Olefin Polymerization
- 高分子学报 2026年页码：1-8
- 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：
  
  E-mail: mingyuanli@dhu.edu.cn
  E-mail: caizg@dhu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 52473002)
- DOI：10.11777/j.issn1000-3304.2026.26100
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7619
- 收稿：2026-03-30，
  
  录用：2026-05-08，
  
  网络首发：2026-06-18，
- 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, doi: 10.11777/j.issn1000-3304.2026.26100.

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), doi: 10.11777/j.issn1000-3304.2026.26100.
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, doi: 10.11777/j.issn1000-3304.2026.26100. DOI： 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), doi: 10.11777/j.issn1000-3304.2026.26100. DOI： 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 yi

elded 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., 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 weig ht 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

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

N-桥膦羰基钯配合物催化乙烯/一氧化碳非交替共聚反应

乙烯反应中的铁配合物催化剂：从概念到产业化

稀土催化极性单体配位均聚及与非极性单体共聚合的研究

配位聚合二烯烃橡胶的官能化

三中心卟啉铝配合物催化二氧化碳/环氧丙烷共聚反应

负载型芴基胺基二甲基钛配合物催化α-烯烃聚合

Heterogeneous Fluorenylamidodimethyltitanium Catalyzed α-Olefin Polymerization

DOI：10.11777/j.issn1000-3304.2026.26100

摘要

Abstract

关键词

Keywords

references