Highly Isospecific Polymerization of Silyl‐Protected ω‐Alkenols Using an [OSSO]‐Type Bis(phenolato) Dichloro Zirconium(IV) Precatalyst. Issue 12 (6th May 2016)

• Record Type: Journal Article
• Authors: Saito, Yusuke; Nakata, Norio; Ishii, Akihiko
• Is Part Of: Macromolecular rapid communications. Volume 37:Issue 12(2016)
• Page Start: 969
• Page End: 974
• Publication Date: 2016-05-06
• Subjects: isospecific polymerization -- [OSSO]‐type ligands -- polar monomers -- post‐metallocene -- zirconium; Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.201600123
• Languages: English
• ISSNs: 1022-1336

Abstract

Abstract : The coordination polymerization of silyl‐protected ω‐alkenols such as ω‐alken‐α‐oxytriisopropylsilanes1 provides poly(ω‐alkenyl‐α‐oxytriisopropylsilalne)s with a highly isospecific microstructure ([ mmmm ] > 95%) when a combination of [OSSO]‐type bis(phenolato) dichloro zirconium(IV) complex2 and dried methylaluminoxane is used as the precatalyst and activator, respectively. The resulting siloxy‐substituted polymers could be efficiently transformed into the corresponding functionalized polyolefins, which contained up to 90% acetyl groups and ≈7% hydroxy groups in the terminal side chains. Abstract : The dichloro zirconium(IV) complex bearing an [OSSO]‐type bis(phenolate) ligand activated by an excess amount of dried methylaluminoxane polymerizes several silyl‐protected ω‐alkenols isospecifically ([ mmmm ] > 95%). Subsequently, the obtained terminal siloxy‐substituted isotactic polymer could be readily transformed by a macromolecular desilylation/acetylation reaction sequence to afford the corresponding terminal acetyl‐enriched polymer.