Pd–phosphinesulfonate bravely battles the “vinyl halide insertion copolymerization” barricade

Gaikwad, Shahaji R.; Deshmukh, Satej S.; Chikkali, Samir H.

doi:10.1002/pola.26968

Cited by 13 publications

(5 citation statements)

References 37 publications

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“…Coordination–insertion polymerization of ethylene and propylene is one of the most well-established transformations, and roughly 145 million tons of polyolefins are produced annually using this process. − Polyolefins are inherently nonpolar, which limits their application in adhesives, paints, binders, and printing inks, among others. Introducing even a few percent of functional groups on the nonpolar polyolefins is anticipated to significantly enhance material properties of these polymers. − Despite the tremendous progress of olefin polymerization, insertion (co)polymerization of functional olefins is a highly sought-after area of research, in both academia and industry. − The following three features associated with this transformation inhibit the insertion of polar monomers and make it a demanding target . (A) One of the major hurdles has been coordination of the functional group installed on the polar monomer to the metal to form σ-complex (Figure , A ).…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Gaikwad¹,

Deshmukh²,

Koshti³

et al. 2017

Macromolecules

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A comprehensive picture of insertion of 1,1disubstituted difunctional olefins, their ability to double the functional group density at the same level of incorporation as that of monofunctional olefin, and copolymerization with ethylene has been demonstrated. Exposure of a palladium complex [{P∧O}PdMe(L)] (P∧O = κ 2 -P,O−Ar 2 PC 6 H 4 SO 2 O with Ar = 2-MeOC 6 H 4 ; L = C 2 H 6 OS) to methyl 2acetamidoacrylate (MAAA) revealed slight preference for 1,2insertion over 2,1-insertion (1.0:0.7). In contrast, insertion of electron-deficient 2-(trifluoromethyl)acrylic acid (TFMAA) unveiled selective 2,1-insertion {via [(P∧O)PdC 5 H 6 F 3 O 2 ] (11)}. The unstable intermediate 11 undergoes β-hydride and β-fluoride elimination to produce subsequent insertion and elimination products. The identity of elimination products (E/Z)-2-trifluoromethyl)but-2-enoic acid [17(E/Z)] and 2-(difluoromethylene)butanoic acid (13) was fully established by 1−2D NMR spectroscopy. These insertion experiments, taken together with insertion rates, suggest that MAAA and TFMAA are amenable to insertion. Polymerization of ethylene with MAAA, TFMAA, acetamidoacrylic acid, 2-bromoacrylic acid, dimethyl allylmalonate, and allylmalonic acid was catalyzed by [{P∧O}PdMe(L)] (L = C 2 H 3 N) (5.ACN), and the highest incorporation of 11.8% was observed for dimethyl allylmalonate (DMAM). The changes in the surface properties of the copolymers after incorporation of difunctional olefins were evaluated by measuring the water contact angle. Copolymer with highest (11.8% of DMAM) incorporation revealed a reduced water contact angle of 76°. These findings demonstrate that 1,1-disubstituted difunctional olefins are amenable to polymerization, and incorporation of difunctional olefins in polyethylene backbone leads to the production of relatively hydrophilic polyethylene copolymers.

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Section: Introductionmentioning

confidence: 99%

Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Gaikwad¹,

Deshmukh²,

Koshti³

et al. 2017

Macromolecules

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“…[3] An ethylene dimerization Pd-phosphine-sulfonatec atalyst can be tweaked to yield high molecular weight PE. [5][6][7] Figure 1( D = Lewis base or ad onor atom/solvent) depicts some of the representative catalysts employedi nt he ethylene polymerization reaction. [5][6][7] Figure 1( D = Lewis base or ad onor atom/solvent) depicts some of the representative catalysts employedi nt he ethylene polymerization reaction.…”

Section: Introductionmentioning

confidence: 99%

“…[4] Thus, ligands dominate the outcomeo fa ne thylene oligomerization or polymerization reaction. [5][6][7] Figure 1( D = Lewis base or ad onor atom/solvent) depicts some of the representative catalysts employedi nt he ethylene polymerization reaction. As evident, nitrogen and phosphorus containing ligandsh ave been quite frequently used to prepare these catalysts.…”

Section: Introductionmentioning

confidence: 99%

Pd‐Iminocarboxylate Complexes and Their Behavior in Ethylene Polymerization

Deshmukh

Gaikwad

Gonnade

et al. 2020

Chemistry An Asian Journal

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Designingc o-catalyst-free late transition metal complexes for ethylene polymerization is ac hallenging task at the interface of organometallic and polymerc hemistry. Herein, as et of new,co-catalyst-free,s ingle-component catalytic systemsf or ethylene polymerizationh ave been unraveled. Treatmento fa nthranilica cid with various aldehydes produced four iminocarboxylate ligands (L1-L4)i nv ery good to excellent yield (75-92 %). The existence of 2-((2-methoxybenzylidene)amino) benzoica cid (L1)h as been unambiguously demonstrated using NMR spectroscopy,M Sa nd single-crystal X-ray diffraction. An eutralP d-iminocarboxylate complex [{N O}PdMe(L1)] (N O = k 2 -N,O-ArCHNC 6 H 4 CO 2 with Ar = 2-MeOC 6 H 4 ) C1 was prepared by treating stoichiometric amount of L1.Na with palladium precursor.T he identity of C1 was confirmed by 1-2D NMR spectroscopy and singlecrystal X-ray diffraction studies. Along the same lines,p alladium complexes C2-C4 were prepared from ligands L2-L4 respectively.I n-situ high-pressure NMR investigations revealed that these Pd complexes are amenable to ethylene insertiona nd undergo facile b-H elimination to produce propylene. These palladium complexes were then evaluated in ethylene polymerizationr eaction and various reactionp arameters were screened. When C1-C4 were exposed to ethylene pressures of 10-50bar,f ormationo fl ow-molecularweightpolyethylene wasobserved.

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“…1−4 The deep understanding of the classical ZN-type catalysts inspired academics to develop homogeneous congeners for olefin polymerization and olefin copolymerization with functional groups. 5−7 The late metal α-diimine Ni or Pd catalysts developed by Brookhart produce highly branched polyethylene. 8 Detailed investigations reveal that α-diimine Ni or Pd catalysts are susceptible to chain-walking, a phenomenon that yields highly branched polyethylene.…”

Section: Introductionmentioning

confidence: 99%

“…Insertion polymerization of olefins to the corresponding polyolefins is known for several decades, and the world today produces about 180 million tons of polyolefins every year using the well-known Ziegler–Natta (ZN) process. − The deep understanding of the classical ZN-type catalysts inspired academics to develop homogeneous congeners for olefin polymerization and olefin copolymerization with functional groups. − The late metal α-diimine Ni or Pd catalysts developed by Brookhart produce highly branched polyethylene . Detailed investigations reveal that α-diimine Ni or Pd catalysts are susceptible to chain-walking, a phenomenon that yields highly branched polyethylene. , However, recent modification to the famous α-diimine Brookhart system has enabled the polymerization of ethylene to high-molecular-weight polyethylene .…”

Section: Introductionmentioning

confidence: 99%

Neutral Imino-Methyl Benzenesulfonate-Ligated Pd(II) Complexes and Implications in Ethylene Polymerization

et al. 2019

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A reaction between sodium 2-formylbenzenesulfonate and aniline revealed the near-quantitative (91%) formation of sodium-2-((phenylimino)methyl)benzenesulfonate L1 . The identity of L1 was unambiguously ascertained using spectroscopic and analytical methods. The scope of this methodology was widened and various electron-donating amines were treated with sodium 2-formylbenzenesulfonate, and a small library of 6 imine ligands L2–L6 was generated. When L2 was treated with [(COD)PdMeCl], instead of the anticipated [ L2 PdMe(DMSO)] complex, the formation of [(DMSO) 2 Pd 2 Cl 2 Me 2 ] Pd-Dim was observed. Nevertheless, the desired imino-methyl benzenesulfonate-ligated palladium complex [ L2 PdMe(Lu)] C1 was obtained by in situ abstraction of chloride and addition of bulky 2,6-lutidine as the donor group. The observation of characteristic Pd–Me protons at 0.06 ppm and the corresponding carbon at −8.1 ppm indicated the formation of C1 . These 1D NMR observations were corroborated by 2D C–H correlation spectra and mass analysis, and the existence of C1 was unambiguously ascertained. Along the same lines, L4 and L5 were treated with a palladium precursor to produce [ L4/5 PdMe(Lu)]-type complexes C2–C3 in 55–84% yield, and their identity was established by using a combination of spectroscopic tools, analytical methods, and single-crystal X-ray diffraction. The synthetic utility of C1–C3 has been demonstrated by utilizing these complexes in the insertion polymerization of ethylene to polyethylene.

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Pd–phosphinesulfonate bravely battles the “vinyl halide insertion copolymerization” barricade

Cited by 13 publications

References 37 publications

Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Pd‐Iminocarboxylate Complexes and Their Behavior in Ethylene Polymerization

Neutral Imino-Methyl Benzenesulfonate-Ligated Pd(II) Complexes and Implications in Ethylene Polymerization

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