Ring Opening Metathesis Polymerization (ROMP) of cis- and trans-3,4-Bis(acetyloxymethyl)cyclobut-1-enes and Synthesis of Block Copolymers

✍ Scribed by Vincent Lapinte; Pierre de Frémont; Véronique Montembault; Laurent Fontaine

• Book ID: 102486611
• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 174 KB
• Volume: 205
• Category: Article
• ISSN: 1022-1352
• DOI: 10.1002/macp.200300224

✦ Synopsis

Abstract

Summary: The synthesis and living ring opening metathesis polymerization (ROMP) of diacetate functionalized cyclobutene derivatives cis‐3,4‐bis(acetyloxymethyl)cyclobutene (2) and trans‐3,4‐bis(acetyloxymethyl)cyclobutene (3) were investigated with the functional group tolerant initiators (PCy~3~)~2~(Cl)~2~RuCHPh (I) and (SIMes)(PCy~3~)(Cl)~2~RuCHPh (II) (SIMes: 1,3‐dimesityl‐4,5‐dihydroimidazol‐2‐ylidene). The kinetic parameters of the ROMP initiated by the ruthenium alkylidene complexes I and II were determined and correlated to monomer stereochemistry. The cis isomer 2 was found to be more reactive than the trans isomer 3 and to generate functional polymers of narrow molecular weight distribution especially with the classical “first generation Grubbs catalyst” I. Block copolymers containing 2 and cyclooctadiene (COD) or norbornene (NBE) were synthesized. Block copolymer poly(2‐b‐COD) was hydrolyzed and converted to a material with a block bearing hydrophilic alcohol functional groups and hydrophobic block.

SEC elution profiles: poly(2) prepolymer and block copolymer poly(2‐b‐COD).

magnified imageSEC elution profiles: poly(2) prepolymer and block copolymer poly(2‐b‐COD).