Dipalladium Catalyst for Olefin Polymerization: Introduction of Acrylate Units into the Main Chain of Branched Polyethylene

Takano, Shigenaga; Takeuchi, Daisuke; Osakada, Kohtaro; Akamatsu, Norihisa; Shishido, Atsushi

doi:10.1002/anie.201404339

Cited by 130 publications

(98 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Studies on Pd catalysts with aryl α‐diimines encompass the variation of the ligand skeleton, further enhancement of steric hindrance, and the use of dinuclear complexes …”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Ethylene/Methyl Acrylate Co‐Oligomerization: The Effect of a New Nonsymmetrical α‐Diimine with the 1,4‐Diazabutadiene Skeleton

et al. 2017

View full text Add to dashboard Cite

PdII complexes with a nonsymmetrical bis(aryl‐imino)diazabutadiene ligand (ArDAB) have been synthesized and characterized. The new ligand features one aryl ring substituted in the ortho positions with a methyl group and the other ring that bears a trifluoromethyl group on the meta positions, which leads to subtle steric and electronic differences at the two N donor atoms. This peculiar substitution makes the direct synthesis of the ligand unfeasible, and the relevant PdII complex, [Pd(CH3)Cl(ArDAB)], is obtained directly through a template reaction. The corresponding cationic complexes with either acetonitrile or DMSO were synthesized and characterized. The X‐ray crystal structure of a Pd complex with an α‐diimine and DMSO is reported. The monocationic complexes were tested as precatalysts in ethylene/methyl acrylate co‐oligomerization under mild reaction temperature and pressure conditions. A comparison of the catalytic behavior of the precatalysts with the corresponding nonsymmetrical aryl α‐diimines with an acenaphthene skeleton indicated that the active species with the new ligand is more productive and leads to the formation of ethylene oligomers and ethylene/methyl acrylate co‐oligomers.

show abstract

“…Studies on Pd catalysts with aryl α‐diimines encompass the variation of the ligand skeleton, further enhancement of steric hindrance, and the use of dinuclear complexes …”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Ethylene/Methyl Acrylate Co‐Oligomerization: The Effect of a New Nonsymmetrical α‐Diimine with the 1,4‐Diazabutadiene Skeleton

et al. 2017

View full text Add to dashboard Cite

show abstract

“…In contrast to the numerous studies focused on catalyst development, fewer studies concerning the material properties of polar‐functionalized polyolefins, such as density, viscosity, surface properties, dyeing properties, and mechanical properties, have been reported . Moreover, the polar polyolefins in these studies were limited to thermoplastic‐type materials.…”

Section: Introductionmentioning

confidence: 99%

“…[17][18][19][20][21][22][23] In contrast to the numerous studies focused on catalyst development, fewer studies concerning the material proper-ties of polar-functionalized polyolefins,s uch as density, viscosity,s urface properties,d yeing properties,a nd mechanical properties,have been reported. [24][25][26][27][28][29] Moreover,the polar polyolefins in these studies were limited to thermoplastic-type materials.I n2 014, Mecking and co-workers reported the synthesis of polyolefins bearing siloxanes/glycidyl/anhydride groups via phosphine-sulfonate palladium-catalyzed copolymerizations. [30] Crosslinking reactions of these reactive groups led to the formation of polar-functionalized elastomeric materials.H owever,t he presence of polar comonomers significantly reduced the copolymer molecular weights (M n < 10 000), which is detrimental to polymer mechanical properties.…”

Section: Introductionmentioning

confidence: 99%

Polar‐Functionalized, Crosslinkable, Self‐Healing, and Photoresponsive Polyolefins

Zou

Chen

2019

Angewandte Chemie

View full text Add to dashboard Cite

The nonpolar nature of polyolefins is one of their biggest limitations. Now, an efficient route to generate polar‐functionalized, crosslinkable, self‐healing, photoresponsive polyolefins with thermoplastic, elastomeric, and thermosetting properties is reported. Tunable amounts of carboxylic acid and a cyclic comonomer are installed onto polyolefins by palladium‐catalyzed terpolymerization reactions. The incorporated carboxylic acid unit can alter the surface properties of polyolefins. The subsequently introduced Fe3+/citric acid combination induces dynamic crosslinking and enables self‐healing. Under UV light irradiation, citric acid reduces Fe3+ to Fe2+ and decreases the crosslinking density. The Fe2+ moiety can be easily oxidized back to Fe3+, making the process reversible at the expense of citric acid. The incorporated cyclic comonomer modulates the crystallinity of polyolefins, provides elastic properties, and installs carbon–carbon double bonds for sulfur‐induced vulcanization.

show abstract

“…One of the most extensively studied late-transition-metal catalysts is the α-diimine-based Pd II and Ni II (Scheme 1, I). [1][2][3][4][5][6][7][8] The phosphine-sulfonate-based Pd II catalysts could copolymerize ethylene with many different polar monomers. [9][10][11][12][13][14][15] Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Redox Control in Olefin Polymerization Catalysis by Phosphine–Sulfonate Palladium and Nickel Complexes

2017

View full text Add to dashboard Cite

Two phosphine–sulfonate ligands, bearing both the ferrocene and the bi‐aryl units, were prepared and characterized. The corresponding palladium and nickel complexes are active in ethylene polymerization. In both the palladium and the nickel systems, the oxidation of the ferrocene unit leads to a decrease in catalytic activities and the polymer molecular masses. Interestingly, the neutral palladium catalyst is not active for norbornene polymerization, while the oxidized analogue shows good activity. As such, switchable polymerization could be achieved.

show abstract

Dipalladium Catalyst for Olefin Polymerization: Introduction of Acrylate Units into the Main Chain of Branched Polyethylene

Cited by 130 publications

References 39 publications

Palladium‐Catalyzed Ethylene/Methyl Acrylate Co‐Oligomerization: The Effect of a New Nonsymmetrical α‐Diimine with the 1,4‐Diazabutadiene Skeleton

Palladium‐Catalyzed Ethylene/Methyl Acrylate Co‐Oligomerization: The Effect of a New Nonsymmetrical α‐Diimine with the 1,4‐Diazabutadiene Skeleton

Polar‐Functionalized, Crosslinkable, Self‐Healing, and Photoresponsive Polyolefins

Redox Control in Olefin Polymerization Catalysis by Phosphine–Sulfonate Palladium and Nickel Complexes

Contact Info

Product

Resources

About