Highly Active and Thermally Robust Nickel Enolate Catalysts for the Synthesis of Ethylene‐Acrylate Copolymers

Xiong, Shuoyan; Hong, Alexandria; Bailey, Brad C.; Spinney, Heather A.; Senecal, Todd D.; Bailey, Hannah; Agapie, Theodor

doi:10.1002/anie.202206637

Cited by 19 publications

(31 citation statements)

References 120 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In comparison to other thermally stable nickel catalysts reported in the literature (Table S16), our nickel–cesium complexes stand out due to their ability to achieve extremely high productivity (>1 × 10 4 kg/mol of Ni) while maintaining a moderate polymer molecular weight ( M n = up to 1.85 × 10 2 kg/mol) at 90 °C. In contrast, other nickel complexes with P , O - ( Cat5 , Cat6 , Cat8 ), N , O - ( Cat7 ), and C , N -donating ( Cat9 ) ligands exhibit significantly lower productivity (<1 × 10 3 kg/mol of Ni) and PE molecular weight ( M n = <1 × 10 1 kg/mol) at high temperature. Although nickel(α-iminoketone) Cat3 and nickel(diimine) Cat4 produce polymers with M n up to 1 × 10 3 kg/mol, their productivity is at least 19× lower than that of the Ni1 –Cs/ Ni2 –Cs catalysts.…”

Section: Resultsmentioning

confidence: 96%

Customizing Polymers by Controlling Cation Switching Dynamics in Non-Living Polymerization

et al. 2022

View full text Add to dashboard Cite

Controlling the chain growth process in non-living polymerization reactions is difficult because chain termination typically occurs faster than the time it takes to apply an external trigger. To overcome this limitation, we have developed a strategy to regulate non-living polymerizations by exploiting the chemical equilibria between a metal catalyst and secondary metal cations. We have prepared two nickel phenoxyphosphine–polyethylene glycol variants, one with 2-methoxyphenyl (Ni1) and another with 2,6-dimethoxyphenyl (Ni2) phosphine substituents. Ethylene polymerization studies using these complexes in the presence of alkali salts revealed that chain growth is strongly dependent on electronic effects, whereas chain termination is dependent on both steric and electronic effects. By adjusting the solvent polarity, we can favor polymerizations via non-switching or dynamic switching modes. For example, in a 100:0.2 mixture of toluene/diethyl ether, reactions of Ni1 and both Li+ and Na+ cations in the presence of ethylene yielded bimodal polymers with different relative fractions depending on the Li+/Na+ ratio used. In a 98:2 mixture of toluene/diethyl ether, reactions of Ni2 and Cs+ in the presence of ethylene generated monomodal polyethylene with dispersity <2.0 and increasing molecular weight as the amount of Cs+ added increased. Solution studies by NMR spectroscopy showed that cation exchange between the nickel complexes and alkali cations in 98:2 toluene/diethyl ether is fast on the NMR time scale, which supports our proposed dynamic switching mechanism.

show abstract

Section: Resultsmentioning

confidence: 96%

Customizing Polymers by Controlling Cation Switching Dynamics in Non-Living Polymerization

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Because of the low activity and poor heat stability of the catalysts, the insertion copolymerization of polar olefins and ethylene still presents considerable difficulties. Quite recently Agapie group [60] has reported highly robust nickel‐enolate catalysts for ethylene copolymerization with acrylate. They have presented an approach for overcoming these barriers by designing the ligands.…”

Section: Copolymerization Of Ethylene With Polar Monomermentioning

confidence: 99%

Recent Advances in Transition Metal‐Based Catalysts for Ethylene Copolymerization with Polar Comonomer

Khan

Mazhar

Shehzad

et al. 2023

The Chemical Record

View full text Add to dashboard Cite

The synthesis of polar functionalized polyolefin (PFP) offers improvement in mixing properties, polymer surface, and rheological properties with the potential of upgraded polyolefins for modern and ingenious applications. The synthesis of PFP from metal-based catalyzed olefin (non-polar in nature) copolymerization with polar comonomers embodies energy-efficient, atomefficient, and apparently an upfront methodology. Despite their outstanding success during conventional polymerization of olefin, 3 rd and 4 th group (early transition metal)-based catalysts, owing to their electrophilic nature, face challenges mainly due to Lewis basic sites of the polar monomers. On the contrary, late transition metal-based catalysts have also made progress, in recent years, for PFP synthesis. The recent past has also witnessed several advancements in the development of dominating palladium-based catalysts while their lower resistance towards ligand functional groups has limited the practical application of abundant and cheaper nickel-based catalysts. However, the relentless efforts of the scientific community, during the past half-decade, have indicated rigorous progress in the development of nickel-based catalysts for PFP synthesis. In this review, we have abridged the recent research trends in both early as well as late transition metal-based catalyst development. Furthermore, we have highlighted the role of transition metalbased catalysts in influencing the polymer properties.

show abstract

“…2–5 Late transition metal-catalyzed copolymerization of olefins with polar copolymer monomers is an efficient and alluring method of introducing functional groups that can enhance the properties of polyolefins and widen the application range of functionalized polyolefins. 6–24 For example, recently, the copolymerization of ethylene with various polar copolymer monomers has been extensively explored using phosphine sulfonates and related palladium catalysts, and a series of properties (such as viscosity, surface properties, and dyeing and mechanical properties) of polar functionalized polyolefin materials have been studied on this basis (Scheme 1a). 25–33…”

Section: Introductionmentioning

confidence: 99%

“…[2][3][4][5] Late transition metal-catalyzed copolymerization of olefins with polar copolymer monomers is an efficient and alluring method of introducing functional groups that can enhance the properties of polyolefins and widen the application range of functionalized polyolefins. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] For example, recently, the copolymerization of ethylene with various polar copolymer monomers has been extensively explored using phosphine sulfonates and related palladium catalysts, and a series of properties (such as viscosity, surface properties, and dyeing and mechanical properties) of polar functionalized polyolefin materials have been studied on this basis (Scheme 1a). [25][26][27][28][29][30][31][32][33] However, most of these monomers used to prepare functional polyolefin materials come from non-renewable petroleum resources, 34 and only a few biomass converted monomers are used for olefin polymerization.…”

Section: Introductionmentioning

confidence: 99%

Palladium-catalyzed synthesis of oil-based functionalized polyolefins

et al. 2023

View full text Add to dashboard Cite

show abstract

Highly Active and Thermally Robust Nickel Enolate Catalysts for the Synthesis of Ethylene‐Acrylate Copolymers

Cited by 19 publications

References 120 publications

Customizing Polymers by Controlling Cation Switching Dynamics in Non-Living Polymerization

Customizing Polymers by Controlling Cation Switching Dynamics in Non-Living Polymerization

Recent Advances in Transition Metal‐Based Catalysts for Ethylene Copolymerization with Polar Comonomer

Palladium-catalyzed synthesis of oil-based functionalized polyolefins

Contact Info

Product

Resources

About