title: Controlled ROP of β-butyrolactone simply mediated by amidine, guanidine, and phosphazene organocatalysts.
abstract: Basic organocatalysts of the guanidine (1,5,7-triazabicyclo[4.4.0]dec-5-ene, TBD), amidine (1,8-diazabicyclo[5.4.0]-undec-7-ene, DBU), and phosphazene (2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2diazaphosphorine, BEMP) type do effectively polymerize β-butyrolactone (BL). Poly(3-hydroxybutyrate)s (PHBs) with controlled molecular features, that is, controlled molar masses, narrow molar mass distributions, and well-defined functional end groups are thus formed at 60 °C from bulk monomer, with M(n,NMR) up to 21 500 g mol(-1). The formation of α,ω-guanidine/amidine/phosphazene,crotonate functionalized PHBs, as demonstrated by NMR, SEC, and MALDI-ToF mass spectrometry analyses, mechanistically suggests the formation of N-acyl-α,β-unsaturated propagating species that originate from 1:1 guanidine/amidine/phosphazene:BL adducts.
authors.affiliation: Institut des Sciences Chimiques de Rennes, Organometallics, Materials and Catalysis, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France.
authors.forename: Cédric G
authors.initials: CG
authors.lastname: Jaffredo
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Carpentier
authors.forename: Sophie M
authors.initials: SM
authors.lastname: Guillaume
mesh_terms: D015107:4-Butyrolactone / Q000031:analogs & derivatives* / Q000737:chemistry; D053961:Azabicyclo Compounds / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D002384:Catalysis; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry*; D006885:Hydroxybutyrates / Q000737:chemistry; D009943:Organophosphorus Compounds / Q000737:chemistry*; D011091:Polyesters / Q000737:chemistry; D058105:Polymerization; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D000094122:Polyhydroxybutyrates
chemical_list: D015107:4-Butyrolactone; D053961:Azabicyclo Compounds; D019086:Bridged Bicyclo Compounds, Heterocyclic; D006573:Heterocyclic Compounds, 1-Ring; D006885:Hydroxybutyrates; D009943:Organophosphorus Compounds; D011091:Polyesters; C526482:triazabicyclodecene; C003182:poly-beta-hydroxybutyrate; D000094122:Polyhydroxybutyrates; C013426:beta-butyrolactone; C116638:BEMP phosphazene; C031033:1,8-diazabicyclo(5.4.0)undec-7-ene