Molecularly defined caprolactone oligomers and polymers: synthesis and characterization.
The synthesis of molecularly defined epsilon-caprolactone oligomers and polymers up to the 64-mer, via an exponential growth strategy, is described. By careful selection of orthogonal protecting groups, t-butyldimethylsilyl (TBDMS) ether for the hydroxyl group and benzyl (Bn) ester for the carboxylic acid group, a highly efficient synthetic strategy was developed with yields for both deprotection steps being essentially quantitative and for the coupling reactions using 1,3-dicyclohexylcarbodiimide (DCC), yields of 80-95% were obtained even at high molecular weights. This allows monodisperse dimers, tetramers, octamers, 16-mers, 32-mers and 64-mers to be prepared in gram quantities and fully characterized using mass spectroscopy, size exclusion chromatography (SEC), and IR and NMR spectroscopy. Thermal and physical properties were measured using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS). These results conclusively show a distinct structure/property relationship with a close correlation between the number of repeat units and physical properties. In addition, a number of marked differences were observed on comparison with the parent poly(caprolactone) polymer.
Takizawa
Kenichi
K
Materials Research Laboratory and Department of Materials, University of California, Santa Barbara, California 93106, USA.
Tang
Chuanbing
C
Hawker
Craig J
CJ
D002152:Calorimetry, Differential Scanning; D002208:Caproates / Q000138:chemical synthesis* / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D018625:Microscopy, Atomic Force; D015394:Molecular Structure; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
D002208:Caproates; D007783:Lactones; D011108:Polymers; C121056:caprolactone