Macromolecules
Article
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(13) Free radical polymerization of divinyl formal and related
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Ethylene and Alkyl Vinyl Ethers by a (Phosphine-sulfonate)PdMe
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(10) (a) Schuster, N.; Runzi, T.; Mecking, S. Reactivity of
̈
Functionalized Vinyl Monomers in Insertion Copolymerization.
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Negele, C.; Krumova, M.; Mecking, S. Nanocomposites of
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Ethylene and 3,3,3-Trifluoropropene Using (Phosphine-sulfonate)Pd-
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Influence of Alkylphosphine−Sulfonate Ligands on Polymerization,
Leading to High-Molecular-Weight Copolymers of Ethylene and Polar
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Mikes, F.; Koike, Y.; Okamoto, Y. Synthesis and Properties of Partially
Fluorinated Amorphous Ring Containing Polymers: Poly[bis(2,2-
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Gottker-Schnetmann, I.; Mecking, S. Incorporation of Vinyl Chloride
̈
in Insertion Polymerization. Angew. Chem., Int. Ed. 2013, 52, 3963.
(i) Neuwald, B.; Falivene, L.; Caporaso, L.; Cavallo, L.; Mecking, S.
Exploring Electronic and Steric Effects on the Insertion and
Polymerization Reactivity of Phosphinesulfonato PdII Catalysts.
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Functional Polyethylenes by Catalytic Copolymerization. Macro-
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Copolymerization of Allyl Monomers with Ethylene. J. Am. Chem.
Soc. 2011, 133, 1232. (n) Shen, Z.; Jordan, R. F. Copolymerization of
Ethylene and Vinyl Fluoride by (Phosphine-bis(arenesulfonate))-
PdMe(pyridine) Catalysts: Insights into Inhibition Mechanisms.
(14) In IR spectra of the copolymer (Figure 2a), very strong peaks at
2916 and 2848 cm−1 are mostly attributed to the C−H asymmetric
and symmetric stretching vibrations of − CH2− groups of the
polyethylene backbone. Weak peaks in this frequency range are also
found in the products of free-radical and cationic polymerizations
(Figure 2, parts b and c), these are reasonably assigned to the C−H
asymmetric and symmetric stretching vibrations of − CH2− groups
derived from poly(divinyl formal).
(15) The copolymerization of ethylene-d4 and DVF was performed
with catalyst precursor 1 under 2.5 bar of ethylene-d4 pressure and 1.2
mol L−1 of DVF in 10 mL of toluene at 95 °C for 5 h in a 20 mL
pressure reactor.
(16) As a model compound for the initiating chain end trans-II units,
trans-4-butyl-2,2,5-trimethyl-1,3-dioxolane features the following key
1
NMR resonances: H(13C) at δ = 3.70(76.7) and 3.50(82.4) (CH),
1.24(17.6) ppm (CH3). Note that cis-4-butyl-2,2,5-trimethyl-1,3-
1
dioxolane features distinctly different key resonances H(13C) at δ =
Macromolecules 2010, 43, 8706. (o) Runzi, T.; Frohlich, D.;
Mecking, S. Direct Synthesis of Ethylene−Acrylic Acid Copolymers
by Insertion Polymerization. J. Am. Chem. Soc. 2010, 132, 17690.
4.22(73.6) and 4.02(77.9) (CH), 1.14(15.5) ppm (CH3). See: Vyvyan,
J. R.; Meyer, J. A.; Meyer, K. D. Conversion of Epoxides to 1,3-
Dioxolanes Catalyzed by Tin(II) Chloride. J. Org. Chem. 2003, 68,
9144.
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(p) Bouilhac, C.; Runzi, T.; Mecking, S. Catalytic Copolymerization of
̈
Ethylene with Vinyl Sulfones. Macromolecules 2010, 43, 3589.
(17) As a model for the initiating chain end cis-III units, cis-6-hexyl-4-
methyl-2-(l-methylethyl)-1,3-dioxane features the following key NMR
resonances: 1H(13C) at δ = 3.74−3.56(72.3) and 3.55−3.42(76.2)
(CH), 1.85−1.68(39.1) (cyclic CH2), 1.19(21.7) ppm (CH3). Note
that trans-6-hexyl-4-methyl-2-(l-methylethyl)-1,3-dioxane features dis-
(q) Guironnet, D.; Roesle, P.; Runzi, T.; Gottker-Schnetmann, I.;
̈
̈
Mecking, S. Insertion Polymerization of Acrylate. J. Am. Chem. Soc.
2009, 131, 422. (r) Ito, S.; Munakata, K.; Nakamura, A.; Nozaki, K.
Copolymerization of Vinyl Acetate with Ethylene by Palladium/
Alkylphosphine−Sulfonate Catalysts. J. Am. Chem. Soc. 2009, 131,
14606. (s) Skupov, K. M.; Piche, L.; Claverie, J. P. Linear Polyethylene
with Tunable Surface Properties by Catalytic Copolymerization of
Ethylene with N-Vinyl-2-pyrrolidinone and N-Isopropylacrylamide.
Macromolecules 2008, 41, 2309. (t) Skupov, K. M.; Marella, P. R.;
1
tinctly different key resonances: H(13C) at δ = 4.25(67.6) and 3.75−
3.63(71.2) (CH), 1.82−1.58(36.1) (cyclic CH2), 1.29(17.1) ppm
(CH3). See: Rychnovsky, S. D.; Skalitzky, D. J. A Practical Preparation
of.alpha.-Alkoxylithium Reagents: Synthesis of Syn or Anti 1,3-Diols. J.
Org. Chem. 1992, 57, 4336.
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Macromolecules 2016, 49, 4395−4403