Controllable Preparation of Branched Polyolefins with Various Microstructural Units <italic style="font-style: italic">via</italic> Chain-walking Ethylene and Pentene Polymerizations

Hong-Ju Liu; Wan-Lu Tian; Xiao-Yue Wang; Tong Lei; Pei Li; Guo-Yong Xu; Chao Li; Shao-Jie Zhang; Fu-Zhou Wang

doi:10.1007/s10118-022-2875-1

Your Location：

Home >

Browse articles >

Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations

RESEARCH ARTICLE | Updated：2023-05-26

- Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations
- Chinese Journal of Polymer Science Vol. 41, Issue 6, Pages: 905-914(2023)
- Affiliations：
  
  Institutes of Physical Science and Information Technology, School of Computer Science and Technology, Anhui University, Hefei 230601, China
- Author bio：
  
  lichao22049@ahu.edu.cn (C.L.)
  zhangshaojie@ahu.edu.cn (S.J.Z.)
  wangfuzhou@ahu.edu.cn (F.Z.W.)
- Funds：
- DOI：10.1007/s10118-022-2875-1
  CLC：
- Received：04 August 2022，
  
  Revised：2022-9-10，
  
  Accepted：19 September 2022，
  
  Online First：18 November 2022，
  
  Published：01 June 2023
- Accepted：
Scan QR Code
Liu, H. J.; Tian, W. L.; Wang, X. Y.; Lei, T.; Li, P.; Xu, G. Y.; Li, C.; Zhang, S. J.; Wang, F. Z. Controllable preparation of branched polyolefins with various microstructural units via chain-walking ethylene and pentene polymerizations. Chinese J. Polym. Sci. 2023, 41, 905–914

Hong-Ju Liu, Wan-Lu Tian, Xiao-Yue Wang, et al. Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations[J]. Chinese Journal of Polymer Science, 2023, 41(6): 905-914. DOI: 10.1007/s10118-022-2875-1.
Liu, H. J.; Tian, W. L.; Wang, X. Y.; Lei, T.; Li, P.; Xu, G. Y.; Li, C.; Zhang, S. J.; Wang, F. Z. Controllable preparation of branched polyolefins with various microstructural units via chain-walking ethylene and pentene polymerizations. Chinese J. Polym. Sci. 2023, 41, 905–914 DOI： 10.1007/s10118-022-2875-1.

Hong-Ju Liu, Wan-Lu Tian, Xiao-Yue Wang, et al. Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations[J]. Chinese Journal of Polymer Science, 2023, 41(6): 905-914. DOI: 10.1007/s10118-022-2875-1. DOI：

摘要

The chain-walking (co)polymerization of ethylene

1-pentene and 2-pentene was carried out using

α-

diimine Ni(II) catalysts in combination with Et

AlCl

leading to the formation of branched polyolefins with various types of branches and microstructural units. This catalyst system can efficiently obtain highly branched amorphous polyethylene with alkyl chains including Me

sec-

Bu branches and longer chains. Compared with the 1-pentene polymerization

this catalyst system successfully conducted polymerization of 2-pentene to give highly branched polymers of approximately 195 branches/1000C possessing Me

and

Pr branches and a long methylene sequence.

Abstract

Branched polyolefins with controllable topology structures were generated from the chain-walking (co)polymerizations of ethylene

1-pentene (1P) and 2-pentene (2P) using Brookhart-type

α-

diimine Ni(II)-based catalysts possessing different

para-

substituted groups

{[(4-R-2-Et-6-Me-C

N＝C)

Nap]NiBr

Nap: 1

8-naphthdiyl; R = CHMePh

Ni1

; R = Ph

Ni2

; R = H

Ni3

}. The X-ray diffraction analysis demonstrated that the crystalline structure of

Ni1′

is in centrosymmetric dimer structure mode with the bimetallic Ni center connected by two bromide bridges. The

para-sec-

phenethyl moiety in the catalyst

Ni1

obviously improved its catalytic performance and thermal stability in the ethylene polymerization. The

Ni1

/Et

AlCl system showed great catalytic activities (up to 7.73×10

g·mol

−1

·h

−1

) and achieved polyethylene (PE) with alkyl chains

including Me

sec-

Bu branches and longer chains (Lg). Compared with the 1-pentene polymerization

this catalyst system successfully mediated the polymerization of 2P to give highly branched polymers with approximately 195 branches/1000C possessing Me

and

Pr branches and a long methylene sequence due to the monomer isomerization. The Et branches derived from 2

3-insertion is slightly less than the sum of Me and

Pr branches derived from 3

2-insertion

indicating that the 3

2-insertion mode is a slightly favorable pathway in the polymerization of 2P.

关键词

Keywords

references

Valente,A.;Mortreux,A.;Visseaux,M.;Zinck,P.Coordinativechaintransferpolymerization. Chem. Rev. 2013 , 113 ,3836−3857..

Chen,Y.;Wang,L.;Yu,H.;Zhao,Y.;Sun,R.;Jing,G.;Huang,J.;Khalid,H.;Abbasi,N.M.;Akram,M.Synthesisandapplicationofpolyethylene-basedfunctionalizedhyperbranchedpolymers. Prog. Polym. Sci. 2015 , 45 ,23−43..

Chen,C.L.Designingcatalystsforolefinpolymerizationandcopolymerization:beyondelectronicandsterictuning. Nat. Rev. Chem. 2018 , 2 ,6−14..

Chen,C.L.Redox-controlledpolymerizationandcopolymerization. ACS Catal. 2018 , 8 ,5506−5514..

Kaiser,J.M.;Long,B.K.Recentdevelopmentsinredox-activeolefinpolymerizationcatalysts. Coord. Chem. Rev. 2018 , 372 ,141−152..

Johnson,L.K.;Killian,C.;Brookhart,M.NewPd(II)-andNi(II)-basedcatalystsforpolymerizationofethyleneandalpha-olefins. J. Am. Chem. Soc. 1995 , 117 ,6414−6415..

Wang,F.;Chen,C.L.Acontinuinglegend:theBrookhart-type α -diiminenickelandpalladiumcatalysts. Polym. Chem. 2019 , 10 ,2354−2369..

Muhammad,Q.;Muhammad,S.B.;Shahid,I.;Qaiser,M.Recentadvancementsin α- diimine-nickeland-palladiumcatalystsforethylenepolymerization. Eur. Polym. J. 2021 , 160 ,110783..

Mahmood,Q.;Zemg,Y.;Yue,E.;Solan,G.;Liang,T.;Sun,W.H.Ultra-highmolecularweightelastomericpolyethyleneusinganelectronicallyandstericallyenhancednickelcatalyst. Polym. Chem. 2017 , 8 ,6416−6430..

Mahmood,Q.;Sun,W.H. N,N -chelatednickelcatalystsforhighlybranchedpolyolefinelastomers:asurvey. R. Soc. open sci. 2018 , 5 ,180367..

Huang,C.;Zakharov,V.A.;Semikolenova,N.V.;Matsko,M.A.;Mahmood,Q.;Talsi,E.P.;Sun,W.H.Comparisonsbetweenhomogeneousandimmobilized1-(2,6-dibenzhydryl-4-nitrophenylimino)-2-mesityliminoacenaphthylnickelbromideasaprecatalystinethylenepolymerization. J. Catal. 2019 , 372 ,103−108..

Mahmood,Q.;Zeng,Y.;Wang,X.;Yang,S.;Sun,W.H.AdvancingpolyethylenepropertiesbyincorporatingNO 2 moietyin1,2-bis(arylimino)acenaphthylnickelprecatalysts:synthesis,characterizationandethylenepolymerization. Dalton Trans. 2017 , 46 ,6934−6947..

Zeng,Y.;Mahmood,Q.;Zhang,Q.;Sun,W.H.Highlythermo-stableandelectronicallycontrolledpalladiumprecatalystsforvinylhomo/co-polymerizationofnorbornene-ethylene. Eur. Polym. J. 2018 , 103 ,342−350..

Gao,J.;Zhang,L.;Zhong,L.;Du,C.;Liao,H.;Gao,H.;Wu,Q.Livingisomerizationpolymerizationsofalkenylcyclohexanewithcamphyl α -diiminenickelcatalysts. Polymer 2019 , 164 ,26−32..

Takeuchi,D.Synthesisandthermalpropertiesofpoly(oligomethylene-cycloalkylene)swithregulatedregio-andstereochemistry. Polym. J. 2018 , 50 ,573−578..

Takeuchi,D.;Watanabe,K.;Osakada,K.Synthesisofpolyketonescontainingsubstitutedsix-memberedrings via Pd-catalyzedcopolymerizationofmethylenecyclohexaneswithcarbonmonoxide. Macromolecules 2015 , 48 ,6745−6749..

Takeuchi,D.Preciseisomerizationpolymerizationofalkenylcyclohexanes:stereoregularpolymerscontainingsix-memberedringsalongthepolymerchain. J. Am. Chem. Soc. 2011 , 133 ,11106−11109..

Wang,F.;Tanaka,R.;Cai,Z.;Nakayama,Y.;Shiono,T.Precisionchain-walkingpolymerizationof trans- 4 - octenecatalyzedby α- diiminenickel(II)catalystsbearing ortho-sec- phenethylgroups. Macromol. Rapid Commun. 2016 , 37 ,1375−1381..

Wang,F.;Tanaka,R.;Li,Q.;Nakayama,Y.;Shiono,T.Chain-walkingpolymerizationoflinearinternaloctenescatalyzedby α- diiminenickelcomplexes. Organometallics 2018 , 37 ,1358−1367..

Wang,F.;Tanaka,R.;Cai,Z.;Nakayama,Y.;Shiono,T.Livingpolymerizationofhigher2-alkenewith α- diiminenickelcatalysts:synthesisandcharacterizationofhighmolecularweightpoly(2-alkene)s. Polymer 2017 , 127 ,88−100..

Wang,F.;Xu,G.;Li,Q.;Tanaka,R.;Nakayama,Y.;Shiono,T.Chain-walkingpolymerizationof3-heptenewithphenylsubstituted α- diiminenickelcatalysts. Polymer 2019 , 181 ,121801..

Alhan,H.B.E.;Jones,G.R.;Harth,E.Branchingregulationinolefinpolymerization via lewisacidtriggeredisomerizationofmonomers. Angew. Chem. Int. Ed. 2020 , 59 ,4743−4749..

Chen,M.;Chen,C.L.Directandtandemroutesforthecopolymerizationofethylenewithpolarfunctionalizedinternalolefins. Angew. Chem. Int. Ed. 2020 , 59 ,1206−1210..

Wang,Y.;Wang,C.;Hu,X.;Xia,Y.;Chi,Y.;Zhang,Y.;Jian,Z.Benzosuberylsubstituentsasa“sandwich-like”functioninolefinpolymerizationcatalysis. Chinese J. Polym. Sci. 2021 , 39 ,984−993..

Zou,C.;Si,G.;Chen,C.L.Ageneralstrategyforheterogenizingolefinpolymerizationcatalystsandthesynthesisofpolyolefinsandcomposites. Nat. Commun. 2022 , 13 ,1954..

Chu,Y.K.;Hu,X.Q.;Zhang,Y.;Liu,D.J.;Zhang,Y.X.;Jian,Z.B.Influenceofbackboneandaxialsubstituentofcatalyston α -imino-ketonenickelmediatedethylene(co)polymerization. Chinese J. Polym. Sci. 2022 , 40 ,469−477..

Wang,C.;Kang,X.;Dai,S.;Cui,F.;Li,Y.;Mu,H.;Mecking,S.;Jian,Z.Efficientsuppressionofchaintransferandbranching via Cs-typeshieldinginaneutralnickel(II)catalyst. Angew. Chem. Int. Ed. 2021 , 60 ,4018−4022..

Cheng,H.;Wang,H.;Li,Y.;Hu,Y.;Zhang,X.;Cai,Z.Structurallysimpledinuclearnickelcatalyzedolefincopolymerizationwithpolarmonomers. J. Catal. 2018 , 368 ,291−297..

Liang,T.;Goudari,S.;Chen,C.L.Asimpleandversatilenickelplatformforthegenerationofbranchedhighmolecularweightpolyolefins. Nat. Commun. 2020 , 11 ,1..

Peng,D.;Chen,C.L.Photoresponsivepalladiumandnickelcatalystsforethylenepolymerizationandcopolymerization. Angew. Chem. Int. Ed. 2021 , 60 ,22195−22200..

Zhang,H.;Zou,C.;Zhao,H.P.;Cai,Z.G.;Chen,C.L.Hydrogen-bonding-inducedheterogenizationofnickelandpalladiumcatalystsforcopolymerizationofethylenewithpolarmonomers. Angew. Chem. Int. Ed. 2021 , 60 ,17446−17451..

Tan,C.;Pang,W.;Chen,C.L.Aphenol-containing α -diimineligandfornickel-andpalladium-catalyzedethylenepolymerization. Chinese J. Polym. Sci. 2019 , 37 ,974−980..

Wang,G.;Peng,D.;Sun,Y.;Chen,C.L.Interplayofsupramolecularchemistryandphotochemistrywithpalladium-catalyzedethylenepolymerization. CCS Chem. 2020 , 3 ,2025−2034..

Zou,C.;Leatherman,M.D.;Daugulis,O.;Brookhart,M.Nickel-catalyzedcopolymerizationofethyleneandvinyltrialkoxysilanes:catalyticproductionofcross-linkablepolyethyleneandelucidationofthechain-growthmechanism. J. Am. Chem. Soc. 2017 , 139 ,16013−16022..

Na,Y.;Chen,C.L.Catechol-functionalizedpolyolefins. Angew. Chem. Int. Ed. 2020 , 59 ,7953−7959..

Xu,M.H.;Chen,C.L.Adisubstituted-norbornene-basedcomonomerstrategytoaddresspolarmonomerproblem. Sci. Bull. 2021 , 66 ,1429−1436..

Muhammad,Q.;Tan,C.;Chen,C.L.Concertedstericandelectroniceffectson α- diiminenickelandpalladium-catalyzedethylenepolymerizationandcopolymerization. Sci. Bull. 2020 , 65 ,300−307..

Tan,C.;Chen,C.L.Nickelcatalystsforthesynthesisofultrahighmolecularweightpolyethylene. Sci. Bull. 2020 , 65 ,1137−1138..

Kocen,A.L.;Brookhart,M.;Daugulis,O.AhighlyactiveNi(II)-triadamantylphosphinecatalystforultrahigh-molecular-weightpolyethylenesynthesis. Nat. Commun. 2019 , 10 ,438..

Wang,X.;Nozaki,K.Selectivechain-endfunctionalizationofpolarpolyethylenes:orthogonalreactivityofcarbeneandpolarvinylmonomersintheircopolymerizationwithethylene. J. Am. Chem. Soc. 2018 , 140 ,15635−15640..

Tan,C.;Zou,C.;Chen,C.L.Anionicclusterstrategyforperformanceimprovementsandproductmorphologycontrolinmetal-catalyzedolefin-polarmonomercopolymerization. J. Am. Chem. Soc. 2022 , 144 ,2245−2254..

Xia,J.;Kou,S.;Zhang,Y.;Jian,Z.Strategiescooperationondesigningnickelcatalyststoaccessultrahighmolecularweightpolyethylenes. Polymer 2022 , 240 ,124478..

Chen,S.;Pan,R.;Liu,Y.;Lu,X.Bulky o- phenylene-bridgedbimetallic α -diimineNi(II)andPd(II)catalystsinethylene(co)polymerization. Organometallics 2021 , 40 ,3703−3711..

Fu,X.;Zhang,L.;Tanaka,R.;Shiono,T.;Cai,Z.Highlyrobustnickelcatalystscontaininganilinonaphthoquinoneligandforcopolymerizationofethyleneandpolarmonomers. Macromolecules 2017 , 50 ,9216−9221..

Zhang,Y.;Kang,X.;Jian,Z.Selectivebranchformationinethylenepolymerizationtoaccesspreciseethylene-propylenecopolymers. Nat. Commun. 2022 , 13 ,725..

Wang,B.;Liu,H.;Zhang,C.;Tang,T.;Zhang,X.Propylenehomopolymerizationandcopolymerizationwithethylenebyacenaphthene-based α- diiminenickelcomplexestoaccessEPR-likeelastomers. Polym. Chem. 2021 , 12 ,6307−6318..

Chen,A.;Liao,D.;Chen,C.L.Promotingethylene(co)polymerizationinaliphatichydrocarbonsolventsusing tert- butylsubstitutednickelcatalysts. Chinese J. Chem. 2022 , 40 ,215−222..

Takeuchi,D.;Chiba,Y.;Takano,S.;Osakada,K.Doubledecker-typedinuclearnickelcatalystforolefinpolymerization:efficientincorporationoffunctionalcomonomers. Angew. Chem. Int. Ed. 2013 , 52 ,12536−12540..

Okada,M.;Nakayama,Y.;Ikeda,T.;Shiono,T.Synthesisofuniquelybranchedpolyethylenebyanilinonaphthoquinoneligatednickelcomplexactivatedwithtris(penta-fluorophenyl)borane. Macromol. Rapid Commun. 2006 , 27 ,1418−1423..

Zhu,L.;Fu,Z.S.;Pan,H.J.;Feng,W.;Chen,C.L.;Fan,Z.Q.Synthesisandapplicationofbinuclear α- diiminenickel/palladiumcatalystswithaconjugatedbackbone. Dalton Trans. 2014 , 43 ,2900−2906..

Gong,Y.F.;Li,S.K.;Gong,Q.;Zhang,S.J.;Liu,B.Y.;Dai,S.Y.Systematicinvestigationsofligandstericeffectson α- diiminenickelcatalyzedolefinpolymerizationandcopolymerization. Organometallics 2019 , 38 ,2919−2926..

Zhong,L.;Li,G.;Liang,G.;Gao,H.;Wu,Q.Enhancingthermalstabilityandlivingfashionin α- diimine-nickel-catalyzed(co)polymerizationofethyleneandpolarmonomerbyincreasingthestericbulkofligandbackbone. Macromolecules 2017 , 50 ,2675−2682..

Rhinehart,J.L.;Brown,L.A.;Long,B.K.ArobustNi(II) α- diiminecatalystforhightemperatureethylenepolymerization. J. Am. Chem. Soc. 2013 , 135 ,16316−16319..

Zhang,D.;Nadres,E.T.;Brookhart,M.;Daugulis,O.Synthesisofhighlybranchedpolyethyleneusing“sandwich”(8-p-tolylnaphthyl α- diimine)nickel(II)catalysts. Organometallics 2013 , 32 ,5136−5143..

Vaidya,T.;Klimovica,K.;LaPointe,A.M.;Keresztes,I.;Lobkovsky,E.B.;Daugulis,O.;Coates,G.W.Secondaryalkeneinsertionandprecisionchain-walking:anewroutetosemicrystalline“polyethylene”from α- olefinsbycombiningtworarecatalyticevents. J. Am. Chem. Soc. 2014 , 136 ,7213−7216..

Zhai,F.;Jordan,R.F.( α -Diimine)Nicomplexesthatcontainmenthylsubstituents:synthesis,conformationalbehaviorandolefinpolymerizationcatalysis. Organometallics 2017 , 36 ,2784−2799..

Liao,Y.;Zhang,Y.;Cui,L.;Mu,H.;Jian,Z.Pentiptycenylsubstituentsininsertionpolymerizationwith α- diiminenickelandpalladiumspecies. Organometallics 2019 , 38 ,2075−2083..

Long,B.K.;Eagan,J.M.;Mulzer,M.;Coates,G.W.Semi-crystallinepolarpolyethylene:ester-functionalizedlinearpolyolefinsenabledbyafunctional-group-tolerant,cationicnickelcatalyst. Angew. Chem. Int. Ed. 2016 , 55 ,7106−7110..

Yuan,J.;Wang,F.;Xu,W.;Mei,T.;Li,J.;Yuan,B.;Song,F.;Jia,Z.Chiralnaphthyl -α- diiminenickel(II)catalystsbearing sec- phenethylgroups:chain-walkingpolymerizationofethyleneathightemperatureandstereoselectivepolymerizationofmethylmethacrylateatlowtemperature. Organometallics 2013 , 32 ,3960−3968..

Wang,F.;Tanaka,R.;Li,Q.;Yuan,J.;Nakayama,Y.;Shiono,T.Synthesisandapplicationof α- diimineNi(II)andPd(II)complexeswithbulkystericgroupstopolymerizationofethyleneandmethylmethacrylate. J. Mol. Catal. A Chem. 2015 , 398 ,231−240..

Wang,F.;Yuan,J.;Li,Q.;Tanaka,R.;Nakayama,Y.;Shiono,T.Newnickel(II)diiminecomplexesbearingphenyland sec- phenethylgroups:synthesis,characterizationandethylenepolymerizationbehavior. Appl. Organometal. Chem. 2014 , 28 ,477−483..

Wang,F.;Tian,S.;Li,R.;Li,W.;Chen,C.L.Ligandstericeffectsonnaphthyl- α -diiminenickelcatalyzed α -olefinpolymerization. Chinese J. Polym. Sci. 2018 , 36 ,157−162..

Wang,F.;Tanaka,R.;Cai,Z.;Nakayama,Y.;Shiono,T.Synthesisofhighlybranchedpolyolefinsusingphenylsubstituted α -diimineNi(II)catalysts. Polymers 2016 , 8 ,160..

Li,P.;Li,X.;Behzadi,S.;Xu,M.;Yu,F.;Xu,G.;Wang,F.Livingchain-walking(co)polymerizationofpropyleneand1-decenebynickel α -diiminecatalysts. Polymers 2020 , 12 ,1988..

Liu,J.Y.;Li,Y.G.;Li,Y.S.;Hu,N.H.Ethylenepolymerizationby( α -diimine)nickel(II)complexesbearingdifferentsubstituentson para -positionofiminesactivatedwithMMAO. J. Appl. Polym. Sci. 2008 , 109 ,700−707..

Liu,F.;Hu,H.;Xu,Y.;Guo,L.H.;Zai,S.;Song,K.;Gao,H.;Zhang,L.;Zhu,F.;Wu,Q.Thermostable α- diiminenickel(II)catalystforethylenepolymerization:effectsofthesubstitutedbackbonestructureoncatalyticpropertiesandbranchingstructureofpolyethylene. Macromolecules 2009 , 42 ,7789−7796..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Preparation of Cyclic Olefin Copolymers with High Glass-transition Temperature via Ethylene/Dicyclopentadiene Copolymerization and Subsequent Hydrogenation

Concerted Steric and Electronic Strategy in Thermostable Salicylaldiminato Nickel Catalysts for Ethylene (Co)polymerization

Preparation and Chiral Recognition Ability of Crystalline Cellulose Phenylcarbamate

Silk Sericin-inspired Poly-β-homoserine for Protein Protection

pH-Responsive L-Cysteine-conjugated Polydopamine Nanocarriers for Controlled Release of Emamectin Benzoate against Pieris brassicae

Related Author

Shu-Nan Zhang

Ling-Yan Huang

Pan He

Chun-Ji Wu

Bao-Li Wang

Hong-Yu Ji

Hong-Liang Mu

Chun-Feng Tang

Related Institution

School of Material Science and Engineering, Changchun University of Science and Technology

School of Chemistry and Environmental Engineering, Changchun University of Science and Technology

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

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

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

⁰

Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations

DOI：10.1007/s10118-022-2875-1

摘要

Abstract

关键词

Keywords

references