Living Cationic Cyclopolymerization of Divinyl Ether with Bulky Substituents: Synthesis of High-Molecular-Weight Cyclopolymers and Star-Shaped Cyclopolymers

Living cationic cyclopolymerization of 1,2-bis(2-vinyloxyethoxy)-3,5-di-tert-butylbenzene (1) was investigated with the CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt initiating system in toluene at 0°C. All the reactions proceeded quantitatively to give gel-free polymers, soluble in organic solvents. The...

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Veröffentlicht in:KOBUNSHI RONBUNSHU 2019/05/25, Vol.76(3), pp.216-225
Hauptverfasser: NIWA, Takahiro, YAMAMOTO, Takafumi, HASHIMOTO, Tamotsu, URUSHISAKI, Michio, SAKAGUCHI, Toshikazu
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Sprache:jpn
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Zusammenfassung:Living cationic cyclopolymerization of 1,2-bis(2-vinyloxyethoxy)-3,5-di-tert-butylbenzene (1) was investigated with the CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt initiating system in toluene at 0°C. All the reactions proceeded quantitatively to give gel-free polymers, soluble in organic solvents. The number-average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that living cyclopolymerization of 1 occurred. The content of unreacted vinyl groups in the produced soluble polymers was less than ~2 mol%, and therefore, the degree of cyclization of the polymers was determined to be over ~98%. Preparation of high-molecular-weight cyclopoly(1) was achieved by sequential monomer addition to the living polymerization system and polymer linking reaction of living cyclopoly(1) leading to star-shaped polymers. Glass transition temperature (Tg) of linear cyclopoly(1) (Mn = 18,500) was 134°C and Tg of star-shaped cyclopoly(1) (Mn = 95,900) was 132°C, and thermal decomposition temperatures (Tds) of these cyclopoly(1) were over 350°C, indicating their high thermal stability.
ISSN:0386-2186
1881-5685
DOI:10.1295/koron.2019-0002