01820nas a2200229 4500008004100000022001400041245010000055210006900155260006700224300000800291490000700299520096500306653002201271653003101293653002301324653002301347653001901370100002501389700002401414700002401438856012801462 2014 eng d a0887-624X00aPd-Phosphinesulfonate bravely battles the ``vinyl halide insertion copolymerization'' barricade0 aPdPhosphinesulfonate bravely battles the vinyl halide insertion  a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcJAN a1-60 v523 a

This overview provides insights into the current state-of-the-art solutions to insertion copolymerization of functional olefinic monomers. The challenges in insertion copolymerization of functional olefinic monomers, with a special emphasis on vinyl halides, are highlighted. The crucial design of the Pd-phosphinesulfonate [Pd(PO)] enables up to 3.6 mol % incorporation of vinyl fluoride (VF) in an ethylene-VF copolymerization reaction. In a significant development, insertion copolymerization of industrially relevant functional olefin, that is, vinyl chloride (VC), was unambiguously ascertained, and a detectable amount of VC (0.4 mol %) was incorporated (at the chain end). In a detailed investigation, the in situ existence of (PO)PdH species during the polymerization was revealed, and it was demonstrated that these are indeed responsible for VC incorporation. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1-6

10afunctional olefin10ainsertion copolymerization10apalladium catalyst10aphosphinesulfonate10avinyl chloride1 aGaikwad, Shahaji, R.1 aDeshmukh, Satej, S.1 aChikkali, Samir, H. uhttp://library.ncl.res.in/content/pd-phosphinesulfonate-bravely-battles-vinyl-halide-insertion-copolymerization-barricade-002036nas a2200289 4500008004100000022001400041245013000055210006900185260000800254300001400262490000700276520106100283653002601344653003101370653001201401653001401413653001701427100002501444700001701469700002401486700002101510700002701531700002401558700002101582700002401603856011901627 2020 eng d a2192-650600aPalladium-catalyzed insertion of ethylene and 1,1-disubstituted difunctional olefins: an experimental and computational study0 aPalladiumcatalyzed insertion of ethylene and 11disubstituted dif cJUN a1200-12090 v853 a

Insertion or coordination copolymerization of ethylene with di-substituted olefins is challenging and the choice of di-substituted mono-functional olefin versus di-substituted di-functional olefin (DDO) appears to be decisive. Here we show that DDO-inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2-acetamidoacrylic acid (AAA), methyl 2-acetamidoacrylate (MAAA), and ethyl 2-cyanoacrylate (ECA) were treated with palladium complex [{P perpendicular to O}PdMe(L)] (P perpendicular to O=kappa(2)-P,O-Ar2PC6H4SO2O with Ar=2-MeOC6H4; L=C2H6OS) and the existence of respective insertion intermediates in moderate yield (up to 37 %) was established. These intermediates were exposed to ethylene and corresponding ethylene-inserted products were isolated and characterized. A careful comparison with three model compounds confirmed ethylene insertion and polymerization. Thus, the combined experimental and computational investigations show that DDO-inserted species can undergo ethylene insertion and polymerization.

10aHomogeneous catalysis10ainsertion copolymerization10aOlefins10aPalladium10aPolyethylene1 aGaikwad, Shahaji, R.1 aPatel, Ketan1 aDeshmukh, Satej, S.1 aMote, Nilesh, R.1 aBirajdar, Rajkumar, S.1 aPandole, Satish, P.1 aChugh, Jeetender1 aChikkali, Samir, H. uhttp://library.ncl.res.in/content/palladium-catalyzed-insertion-ethylene-and-11-disubstituted-difunctional-olefins02147nas a2200265 4500008004100000022001400041245010600055210006900161260000900230300001100239490000800250520122800258653002901486653003101515653002401546653001701570653001001587100002601597700002201623700002401645700002401669700003301693700002401726856013101750 2020 eng d a0014-305700aRenewing polyethylene: insertion copolymerization of sugar derived hydrophilic monomers with ethylene0 aRenewing polyethylene insertion copolymerization of sugar derive cJUL  a1097750 v1343 a

Although highly desirable, insertion copolymerization of renewable resource derived functional olefins with ethylene has been rarely investigated. Herein, we report insertion copolymerization of challenging sugar derived isohexide mono-enes with ethylene in the presence of Pd-phosphinesulfonate acetonitrile catalyst (C1). Thus, copolymerization of ethylene with isomannide mono-ene (2a), isosorbide mono-ene (2b'), isoidide mono-ene (2c) and methacryl-2,3,4,6-tetra-O-acetyl-D glucopyranoside (2d) afforded corresponding functionalized polyethylene (P2a-1 to P2d-1). High temperature proton NMR investigations revealed enchainment of 2a-2c in polyethylene backbone and the highest incorporation of 1.45% was observed for 2c. The high temperature proton NMR results were further corroborated by solid state C-13 NMR and IR spectroscopy. Gel permeation chromatography analysis displayed weight average molecular weight in the range of 13.0-27.2 x 10(3) g/mol. The thus prepared copolymers revealed melting temperature in the range of 117-126 degrees C. Relatively reduced melting temperature compared to neat polyethylene may suggest an irregular arrangement of pendant functional group on polyethylene main chain.

10aHydrophilic polyethylene10ainsertion copolymerization10aIsohexide mono-enes10aPolyethylene10aSugar1 aRajput, Bhausaheb, S.1 aPawal, Sandip, B.1 aBodkhe, Dnyaneshwar1 aRao, Nagamalleswara1 aSainath, Annadanam, V. Sesha1 aChikkali, Samir, H. uhttp://library.ncl.res.in/content/renewing-polyethylene-insertion-copolymerization-sugar-derived-hydrophilic-monomers-ethylene03063nas a2200229 4500008004100000022001400041245006500055210006300120260000900183300001100192490000800203520233200211653001302543653002802556653002702584653002902611653003102640653001702671100002702688700002402715856009402739 2021 eng d a0014-305700aInsertion copolymerization of functional olefins: Quo Vadis?0 aInsertion copolymerization of functional olefins Quo Vadis cJAN  a1101830 v1433 a

Functional polyethylene is a specialty polymer with unique set of properties and caters to a niche market. Currently, it is manufactured using high-pressure, high-temperature radical polymerization, or post-reactor (indirect) modification methods. Insertion copolymerization of functional olefins with ethylene provides a low pressure, direct route to prepare functional polyethylenes. However, insertion copolymerization of functional olefins with ethylene poses several impediments and requires special considerations. This review presents the current strategies, examines the progress, and attempts to gauge the commercial potential of direct synthesis of functional polyethylene. The performance of late transition metal catalysts derived from a-diimine, imine-phenolate, phosphine-sulfonate, bis-phosphine-mono-oxide, carbene-phenolate, phosphine-phenolate and their derivatives in the insertion copolymerization of functional olefins with ethylene is evaluated. While catalyst designing is crucial, incorporation of polar olefins that can serve an additional purpose is equally important. Therefore, we have organized the review in the following sections, polar alkenes with- acrylates, acrylic acids, acetates, nitriles, ethers, halides, two functional groups, cross-linking groups, dynamic interactions/self-healing properties, additional function/purpose, renewable functional olefins, and examine the progress. Among these, acrylates have been most intensively investigated and have been successfully incorporated in the polyethylene main-chain. Ethylene, methyl acrylate copolymers prepared by direct copolymerization reveal comparable melting temperature to that of LLDPE (at similar co-monomer content) and unfold the commercial potential of these materials. Recent developments on the insertion copolymerization of renewable functional olefins and di-functional olefins have elicited significant interest. This strategy is being viewed as a means of reducing environmental impact and enabling high functional group density at the same extent of incorporation. The overview thus offers a succinct account of insertion copolymerization of functional olefins, sheds light on the copolymer microstructure/material properties, and initiates a discussion on the commercial potential of functional polyethylene.

10aCatalyst10aFunctional polyethylene10afunctional polyolefins10aHydrophilic polyethylene10ainsertion copolymerization10aPolyethylene1 aBirajdar, Rajkumar, S.1 aChikkali, Samir, H. uhttp://library.ncl.res.in/content/insertion-copolymerization-functional-olefins-quo-vadis