02658nas a2200205   4500008004100000245010100041210006900142260000800211300001400219490000700233520190800240100002502148700002402173700002202197700002002219700002402239700003502263700002402298856013002322       2017                        eng d00aReactivity of difunctional polar monomers and ethylene copolymerization: a comprehensive account0 aReactivity of difunctional polar monomers and ethylene copolymer  cAUG  a5748-57580 v503 aA comprehensive picture of insertion of 1,1-disubstituted 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 boolean AND O}PdMe(L)] (P boolean AND O = kappa(2)-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4.; L = C2H6OS) to methyl 2-acetamidoacrylate (MAAA) revealed slight preference for 1,2-insertion 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 boolean AND O)PdC5H6F3O2] (11)1. The unstable intermediate 11 undergoes beta-hydride and beta-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 boolean AND O}PdMe(L)] (L = C2H3N) (S.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 degrees. 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.1 aGaikwad, Shahaji, R.1 aDeshmukh, Satej, S.1 aKoshti, Vijay, S.1 aPoddar, Suparna1 aGonnade, Rajesh, G.1 aRajamohanan, Pattuparambil, R.1 aChikkali, Samir, H.  uhttps://library.ncl.res.in/content/reactivity-difunctional-polar-monomers-and-ethylene-copolymerization-comprehensive-account