Ethylene–ethyl acrylate copolymers via ADMET polymerization: Effect of sequence distribution on thermal properties

Abstract

Copolymers of ethylene and ethyl acrylate have been widely used as commodity materials in many fields. In this article, a general synthetic strategy toward fine tuning the ethyl acrylate content and facile control over the monomer sequence regularity of this important type of copolymer via acyclic diene metathesis (ADMET) polymerization followed by hydrogenation is demonstrated. Three structurally symmetric diene monomers (M1–M3) were synthesized in good yields via a three‐step synthetic approach; each of the monomers contains two tail‐to‐tail linked ethyl acrylate units connected to the terminal alkenes by a methylene spacer with specific length. ADMET homopolymerization of M1–M3 and copolymerization of these monomers with 1,9‐decadiene were conducted, and after hydrogenation, a family of periodic and random copolymers of ethylene and ethyl acrylate were obtained. All the polymer samples were characterized by gel permeation chromatography and nuclear magnetic resonance, and the thermal properties of the saturated copolymers were investigated with thermal gravimetric analysis and differential scanning calorimetry. The glass transition and melting behaviors of this family of ethylene and ethyl acrylate copolymers were found to be dependent on the ethyl acrylate content and the primary structure regularity in copolymers. Copolymers with low ethyl acrylate content and periodic microstructures exhibited better crystallinity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2900–2909

Precisely designed perylene bisimide-substituted polyethylene with a high glass transition temperature and an ordered architecture

“…7a, Table 1), to be 263, 367, 295, and 385 C, respectively, indicating their highly thermal stability; these data are also similar to the T d values of previously reported PE polymers bearing periodically distributed single ethyl acrylate groups attached to PE carbons. 20 The unsaturated polymers P1a and P1d decomposed completely at 780 C, while 27% and 40% of the weights of the saturated polymers HP1a and HP1d, respectively, were still retained when they were heated to 800 C; these latter amounts of residue are obviously greater than that of the hydrogenated ethylene-ethyl acrylate copolymers, 21 and are indicative of the excellent thermal stability of PBI-containing PE.…”

Synthesis and characterization of precisely-defined ethylene-co-aryl ether polymers via ADMET polymerization

“…Typical polymerization strategies for the preparation of ether incorporated polyolefins could also include transition-metal-catalyzed coordination-insertion polymerization and free radical processes, but the oxophilicity of the transitionmetal polymerization catalysts which generally leads to poisoning by strong s-coordination of the Lewis basic moiety of a polar vinyl monomer or poor control over branching ratios, and distribution of the polar functional groups in the polymer chain. Alternatively, ring-opening metathesis polymerization (ROMP) of functionalized cyclooctenes [22e24] or acyclic diene metathesis (ADMET) of functionalized dienes [25e27] represents a potentially ideal method for the controlled synthesis of functional polyolefins in a single step, particularly, precisely control the identity and distribution of branches along the backbone of polyethylene, as well as functional groups incorporated in the main chain, including model copolymers of ethylene with acrylates [28], styrene [29], vinyl acetate [30], and vinyl halide [31], silicon-containing polymers [32] and chiral polymers [33] have been unprecedently achieved in the presence of Schrock' catalyst and Grubbs' series of catalysts.…”

Intrachain Cyclization via Postmodification of the Internal Alkenes of Periodic ADMET Copolymers: The Sequence Matters

“…P2 was obtained through exhaustive hydrogenation of P1 based on the method reported by Hahn et al 63 P3 and P4 were synthesized using G-I catalyst according to the previously reported synthetic procedures. 24 P5 was obtained via random copolymerization of 1,9-decadiene and monomer 1 at a feed molar ratio of 1:1.…”