Random, Defect-Free Ethylene/Vinyl Halide Model Copolymers via Condensation Polymerization

• Published in: Macromolecules Vol. 41; no. 1; pp. 25 - 30
• Main Authors: Boz, Emine, Ghiviriga, Ion, Nemeth, Alexander J, Jeon, Keesu, Alamo, Rufina G, Wagener, Kenneth B
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 08.01.2008
• Subjects: Applied sciences; Copolymerization; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; Melting; Vinyl halide copolymer; Dienic compound; Experimental study; Complex catalyst copolymerization; Hydrogenation; Thermal stability; Saturated copolymer; Random copolymer; Chemical modification; Metathesis polymerization; Model compound; Preparation; Unsaturated copolymer; Methylene copolymer; Alkenamer copolymer; Halogen containing copolymer
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma071594u

The synthesis of ethylene vinyl halide (EVH) copolymers containing fluorine, chlorine, and bromine via the ADMET copolymerization of halogen containing α−ω-dienes with 1,9-decadiene is presented. The statistically random nature of the copolymers was established from their 13C NMR spectra. Thermal analysis via differential scanning calorimetry points to a distinct difference in the crystallization behavior of these random copolymers when compared to their compositionally matched precise analogues. In this case, sharp melting peaks typical of homopolymer-like crystallization of the precise analogues are no longer observed in Cl- and Br-based random copolymers and are replaced by broader peaks indicating a mechanism based on the selection of long crystallizable sequences. The results presented herein thus point to the utility of these random ADMET copolymers as suitable models for industrially relevant PE copolymers based on the perfectly linear, defect-free, and statistically random copolymer composition.