Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers

Fei Wang; Li Pan; Vladislav A. Tuskaev; Svetlana Ch. Gagieva; Yue-Sheng Li

doi:10.1007/s10118-023-3044-x

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Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers

RESEARCH ARTICLE | Updated：2024-01-12

- Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers
- Chinese Journal of Polymer Science Vol. 42, Issue 2, Pages: 202-212(2024)
- Affiliations：
  
  a.Tianjin Key Lab of Composite & Functional Materials, School of Material Science and Engineering, Tianjin University, Tianjin 300072, China
  b.Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1, Moscow 119991, Russian Federation
  c.A N Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova st., 28, Moscow 119991, Russian Federation
- Author bio：
  
  lilypan@tju.edu.cn (L.P.)
  ysli@tju.edu.cn (Y.S.L.)
- Funds：
- DOI：10.1007/s10118-023-3044-x
  CLC：
- Received：13 July 2023，
  
  Revised：2023-8-1，
  
  Accepted：03 August 2023，
  
  Online First：15 September 2023，
  
  Published：01 February 2024
- Accepted：
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Wang, F.; Pan, L.; Tuskaev, V. A.; Gagieva, S. C.; Li, Y. S. Phosphine/benzocyclone-based neutral nickel catalysts for ethylene polymerization and copolymerization with polar monomers. Chinese J. Polym. Sci. 2024, 42, 202–212

Fei Wang, Li Pan, Vladislav A. Tuskaev, et al. Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers[J]. Chinese Journal of Polymer Science, 2024, 42(2): 202-212.
Wang, F.; Pan, L.; Tuskaev, V. A.; Gagieva, S. C.; Li, Y. S. Phosphine/benzocyclone-based neutral nickel catalysts for ethylene polymerization and copolymerization with polar monomers. Chinese J. Polym. Sci. 2024, 42, 202–212 DOI： 10.1007/s10118-023-3044-x.

Fei Wang, Li Pan, Vladislav A. Tuskaev, et al. Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers[J]. Chinese Journal of Polymer Science, 2024, 42(2): 202-212. DOI： 10.1007/s10118-023-3044-x.

摘要

A series of strategically designed neutral nickel catalysts with phosphine/benzocyclone-based ligand skeleton displayed high activity and thermal stability in ethylene polymerization to afford linear polyethylene. These bulky nickel catalysts also exhibited excellent tolerance towards acrylate functional groups and high incorporating capability

producing random copolymers with high molecular weights.

Abstract

The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution

three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts (

Ni1

: Ar = Ph;

Ni2

: Ar = 2-(C

;

Ni3

: Ar = 2-[2'

6'-(MeO)

-C

) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes

Ni2

and

Ni3

contributed to high catalytic activities (up to 7.24×10

and 9.04×10

g·mol

‒1

·h

‒1

respectively)

and produced high-molecular-weight polyethylene (

up to 545.7 kDa). Complex

Ni3

exhibited high activities for ethylene polymerization at the level of 10

g·mol

‒1

·h

‒1

across a wide range from 30 °C to 120 °C

exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate

ethyl acrylate

butyl acrylate and lauryl acrylate

producing copolymers with high molecular weights (

up to 80.5 kDa) and high polar monomer incorporation (up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.

关键词

Keywords

references

Dong,J.Y.;Hu,Y.L.Designandsynthesisofstructurallywell-definedfunctionalpolyolefins via transitionmetal-mediatedolefinpolymerizationchemistry. Coord. Chem. Rev. 2006 , 250 ,47–65..

Nakamura,A.;Anselment,T.M.;Claverie,J.;Goodall,B.;Jordan,R.F.;Mecking,S.;Rieger,B.;Sen,A.;vanLeeuwen,P.W.;Nozaki,K. Ortho -phosphinobenzenesulfonate:asuperbligandforpalladium-catalyzedcoordination-insertioncopolymerizationofpolarvinylmonomers. Acc. Chem. Res . 2013 , 46 ,1438–1449..

Chen,E.Y.X.Coordinationpolymerizationofpolarvinylmonomersbysingle-sitemetalcatalysts. Chem. Rev. 2009 , 109 ,5157–5214..

Chung,T.C.M.Functionalpolyolefinsforenergyapplications. Macromolecules 2013 , 46 ,6671–6698..

Tan,C.;Zou,C.;Chen,C.L.Materialpropertiesoffunctionalpolyethylenesfromtransition-metal-catalyzedethylene-polarmonomercopolymerization. Macromolecules 2022 , 55 ,1910–1922..

Huang,M.L.;Chen,J.Z.;Wang,B.H.;Huang,W.;Chen,H.B.;Gao,Y.S.;Marks,T.J.Polarisotacticandsyndiotacticpolypropylenesbyorganozirconium-catalyzedmasking-reagent-freepropyleneandamino-olefincopolymerization. Angew. Chem. Int. Ed. 2020 , 59 ,20522–20528..

Keyes,A.;BasbugAlhan,H.E.;Ordonez,E.;Ha,U.;Beezer,D.B.;Dau,H.;LiuY.S.;Tsogtgerel,E.;Jones,G.R.;Harth,E.Olefinsandvinylpolarmonomers:bridgingthegapfornextgenerationmaterials. Angew. Chem. Int. Ed. 2019 , 58 ,12370–12391..

Chen,J.Z.;Gao,Y.S.;Marks,T.J.Earlytransitionmetalcatalysisforolefin-polarmonomercopolymerization. Angew. Chem. Int. Ed. 2020 , 59 ,14726–14735..

Cui,D.M.Studiesonhomo-andco-polymerizationsofpolarandnon-polarmonomersusingrare-earthmetalcatalysts. Acta Polymerica Sinica (inChinese) 2020 , 51 ,12–29..

Ittel,S.D.;Johnson,L.K.;Brookhart,M.Late-metalcatalystsforethylenehomo-andcopolymerization. Chem. Rev. 2000 , 100 ,1169−1204..

Chen,Z.;Brookhart,M.Exploringethylene/polarvinylmonomercopolymerizationsusingNiandPda-diiminecatalysts. Acc. Chem. Res. 2018 , 51 ,1831–1839..

Nakamura,A.;Ito,S.;Nozaki,K.Coordination-insertioncopolymerizationoffundamentalpolarmonomers. Chem. Rev. 2009 , 109 ,5215–5244..

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,F.;Wang,X.L.;Pan,L.;Wang,B.;Li,Y.S.Efficientcopolymerizationofethylenewithpolardivinylmonomerbyphosphino-phenolatenickelcatalyst. Chin. J. Chem. 2023 , 41 ,1037–1044..

Cui,L.;Chu,Y.K.;Liu,D.J.;Han,Y.F.;Mu,H.L.;Jian,Z.B.Enhancementonhemilabilephosphine-amidepalladiumandnickelcatalystsforethylene(co)polymerizationwithpolarmonomersusingacyclizingstrategy. Chinese J. Polym. Sci. 2022 , 40 ,241–247..

Zhang,R.D.;Gao,R.;Gou,Q.Q.;Lai,J.J.;Li,X.Y.Recentadvancesinthecopolymerizationofethylenewithpolarcomonomersbynickelcatalysts. Polymers 2022 , 14 ,3809..

Karimi,M.;Arabi,H.;Sadjadi,S.Newadvancesinolefinhomoandcopolymerizationusingneutral,singlecomponentpalladium/nickelcomplexesligatedbyaphosphinesulfonate. J. Catal. 2022 , 412 ,59–70..

Wu,R.K.;KlinglerWuW.Y.;Stieglitz,L.;Gaan,S.;Rieger,B.;Heuberger,M.Recentadvancesona-diimineNiandPdcomplexesforcatalyzedethylene(co)polymerization:acomprehensivereview. Coord. Chem. Rev. 2023 , 474 ,214844..

Cui,L.;Chen,M.;Chen,C.L.;Liu,D.T.;Jian,Z.B.Systematicstudieson(co)polymerizationofpolarstyrenemonomerswithpalladiumcatalysts. Macromolecules 2019 , 52 ,7197–7206..

Liu,G.X.;Huang,Z.Recentadvancesincoordination-insertioncopolymerizationofethylenewithpolarfunctionalizedcomonomers. Chin. J. Chem. 2020 , 38 ,1445–1448..

Qasim,M.;Bashir,M.S.;Iqbal,S.;Mahmood,Q.Recentadvancementsin α -diimine-nickeland-palladiumcatalystsforethylenepolymerization. Eur. Polym. J. 2021 , 160 ,110783..

Odenwald,L.;Wimmer,F.P.;Mast,N.K.;Schußmann,M.G.;Wilhelm,M.;Mecking,S.Molecularlydefinedpolyolefinvitrimersfromcatalyticinsertionpolymerization. J. Am. Chem. Soc. 2022 , 144 ,13226–13233..

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

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

Johnson,L.K.;Mecking,S.,Brookhart,M.Copolymerizationofethyleneandpropylenewithfunctionalizedvinylmonomersbypalladium(II)catalysts. J. Am. Chem. Soc. 1996 , 118 ,267–268..

Behzadi,S.;Zou,C.;Yang,B.P.;Tan,C.;Chen,C.L.Styrene-containingphosphine-sulfonateligandsfornickel-andpalladium-catalyzedethylenepolymerization. Chinese J. Polym. Sci. 2021 , 39 ,447–454..

Mecking,S.;Schnitte,M.Neutralnickel(II)catalysts:fromhyperbranchedoligomerstonanocrystal-basedmaterials. Acc. Chem. Res. 2020 , 53 ,2738–2752..

Mu,H.L.;Pan,L.;Song,D.P.;Li,Y.S.Neutralnickelcatalystsforolefinhomo-andcopolymerization:relationshipsbetweencatalyststructuresandcatalyticproperties. Chem. Rev . 2015 , 115 ,12091−12137..

Mu,H.L.;Zhou,G.L.;Hu,X.Q.;Jian,Z.B.Recentadvancesinnickelmediatedcopolymerizationofolefinwithpolarmonomers. Coord. Chem. Rev. 2021 , 435 ,213802..

Yang,B.P.;Xiong,S.Y.;Chen,C.L.Manipulationofpolymerbranchingdensityinphosphine-sulfonatepalladiumandnickelcatalyzedethylenepolymerization. Polym. Chem. 2017 , 8 ,6272–6276..

Xia,J.;Zhang,Y.X.;Zhang,J.F.;Jian,Z.B.High-performanceneutralphosphinesulfonatenickel(II)catalystsforefficientethylenepolymerizationandcopolymerizationwithpolarmonomers. Organometallics 2019 , 38 ,1118–1126..

Xia,J.;Han,Y.F.;Kou,S.Q.;Zhang,Y.X.;Jian,Z.B.Exploringstericeffectofelectron-donatinggroupinpalladiumandnickelmediatedethylenepolymerizationandcopolymerizationwithpolarmonomers. Eur. Polym. J. 2021 , 160 ,110781..

Tao,W.J.;Nakano,R.;Ito,S.;Nozaki,K.CopolymerizationofethyleneandpolarmonomersbyusingNi/IzQOcatalysts. Angew. Chem. Int. Ed. 2016 , 55 ,2835–2839..

Younkin,T.R.;Connor,E.F.;Henderson,J.I.;Friedrich,S.K.;Grubbs,R.H.;Bansleben,D.A.Neutral,single-componentnickel(II)polyolefincatalyststhattolerateheteroatoms. Science 2000 , 287 ,460–462..

Cheng,H.L.;Wang,H.J.;Li,Y.Q.;Hu,Y.M.;Zhang,X.Q.;Cai,Z.G.Structurallysimpledinuclearnickelcatalyzedolefincopolymerizationwithpolarmonomers. J. Catal. 2018 , 368 ,291–297..

Cheng,H.L.;Cai,Z.G.(Anilino)anthraquinonenickel-catalyzedrandomcopolymerizationofnorborneneandethylene. ChemCatChem 2018 , 10 ,497–500..

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

Jung,J.;Yasuda,H.;Nozaki,K.Copolymerizationofnonpolarolefinsandallylacetateusingnickelcatalystsbearingamethylene-bridgedbisphosphinemonoxideligand. Macromolecules 2020 , 53 ,2547–2556..

Cao,L.X.;Cai,Z.G.;Li,M.Y.Phosphinobenzenaminenickelcatalyzedefficientcopolymerizationofmethylacrylatewithethyleneandnorbornene. Macromolecules 2022 , 55 ,3513–3521..

Ji,G.;Chen,Z.;Wang,X.Y.;Ning,X.S.;Xu,C.J.;Zhang,X.M.;Tao,W.J.;Li,J.F.;Gao,Y.S;Shen,Q.;Sun,X.L.;Wang,H.Y.;Zhao,J.B.;Zhang,B.;Guo,Y.L.;Zhao,Y.N.;Sun,J.J.;Luo,Y.;Tang,Y.DirectcopolymerizationofethylenewithproticcomonomersenabledbymultinuclearNicatalysts. Nat. Commun. 2021 , 12 ,6283..

Li,Y.Q.;Cheng,H.L.;Xiao,R.;Cai,Z.G.RationaldesignofnickelcatalystscontainingN-acylatedimidazoline-2-imineligandforethylenecopolymerizationwithpolarmonomer. J. Catal. 2020 , 383 ,117–123..

Song,D.P.;Wang,Y.X.;Mu,H.L.;Li,B.X.;Li,Y.S.Observationsandmechanisticinsightsonunusualstabilityofneutralnickelcomplexeswithastericallycrowdedmetalcenter. Organometallics 2011 , 30 ,925–934..

Zou,C.;Zhang,H.;Tan,C.;Cai,Z.G.Polyolefinswithintrinsicantimicrobialproperties. Macromolecules 2021 , 54 ,64–70..

Tan,C.;Qasim,M.;Pang,W.M.;Chen,C.L.Ligand-metalsecondaryinteractionsinphosphine-sulfonatepalladiumandnickelcatalyzedethylene(co)polymerization. Polym. Chem. 2020 , 11 ,411–416..

Wang,Q.;Wang,W.B.;Qu,W.C.;Pang,W.M.;Qasim,M.;Zou,C.Ethylenehomoandcopolymerizationbyphosphorus-benzoquinonebasedhomogeneousandheterogeneousnickelcatalysts. J. Polym. Sci. 2022 , 61 ,115–122..

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

Baur,M.;Mecking,S.Polyethyleneswithcombinedin-chainandside-chainfunctionalgroupsfromcatalyticterpolymerizationofcarbonmonoxideandacrylate. ACS Macro Lett. 2022 , 11 ,1207−1211..

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

Baur,M.;Lin,F.;Morgen,T.O.;Odenwald,L.;Mecking,S.Polyethylenematerialswithin-chainketonesfromnonalternatingcatalyticcopolymerization. Science 2021 , 374 ,604–607..

Xiong,S.Y.;Shoshani,M.M.;Zhang,X.L.;Spinney,H.A.;Nett,A.J.;Henderson,B.H.;Miller,T.F.;Agapie,T.EfficientcopolymerizationofacrylateandethylenewithneutralP,O-chelatednickelcatalysts:mechanisticinvestigationsofmonomerinsertionandchelateformation. J. Am. Chem. Soc. 2021 , 143 ,6516–6527..

Lin,F.;Morgen,T.O.;Mecking,S.LivingaqueousmicroemulsionpolymerizationofethylenewithrobustNi(II)phosphinophenolatocatalysts. J. Am. Chem. Soc. 2021 , 143 ,20605−20608..

Zhang,Y.P.;Mu,H.L.;Pan,L.;Wang,X.L.;Li,Y.S.Robustbulky[P,O]neutralnickelcatalystsforcopolymerizationofethylenewithpolarvinylmonomers. ACS Catal. 2018 , 8 ,5963−5976..

Zhang,Y.P.;Mu,H.L.;Wang,X.;Pan,L.;Li,Y.S.Elaboratetuninginligandmakesabigdifferenceincatalyticperformance:bulkynickelcatalystsfor(co)polymerizationofethylenewithpromisingvinylpolarmonomers. ChemCatChem 2019 , 11 ,2329−2340..

Xin,B.S.;Sato,N.;Tanna,A.;Oishi,Y.;Konishi,Y.;Shimizu,F.Nickelcatalyzedcopolymerizationofethyleneandalkylacrylates. J. Am. Chem. Soc. 2017 , 139 ,3611−3614..

Wang,X.L.;Zhang,Y.P.;Wang,F.;Pan,L.;Wang,B.;LiY.S.Robustandreactiveneutralnickelcatalystsforethylenepolymerizationandcopolymerizationwithachallenging1,1-disubstituteddifunctionalpolarmonomer. ACS Catal. 2021 , 11 ,2902–2911..

Wang,X.L.;Zhang,Y.P.;Pan,L.;Wang,F.;Luo,S.;Li,Y.S.Reactivityofphosphino-naphtholatenickelcomplexesandtheircatalysisofcopolymerizationwithpolarmonomers. ChemCatChem 2022 , 14 ,e202101736..

Tanemura,K.;Suzuki,T.;Nishida,Y.;Satsumabayashi,K.;Horaguchi,T.Amildandefficientprocedurefor α -brominationofketonesusingN-bromosuccinimidecatalysedbyammoniumacetate. Chem. Commun . 2004 ,470–471..

Nakamura,A.;Anselment,T.M.J.;Claverie,J.;Goodall,B.;Jordan,R.F.;Mecking,S.;Rieger,B.;Sen,A.;vanLeeuwen,P.W.N.M.;Nozaki,K. Ortho -phosphinobenzenesulfonate:Asuperbligandforpalladium-catalyzedcoordination-insertioncopolymerizationofpolarvinylmonomers. Acc. Chem. Res. 2013 , 46 ,1438−1449..

Drent,E.;vanDijk,R.;vanGinkel,R.;vanOort,B.;Pugh,R.I.Palladiumcatalysedcopolymerisationofethenewithalkylacrylates:polarcomonomerbuiltintothelinearpolymerchain. Chem. Commun . 2002 ,744−745..

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