The NSF funded Center for Polymeric Interfaces and Macromolecular Assemblies (CPIMA) under cooperative agreement DMR-9400354 The Swedish-American Foundation BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
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The polymerization of ε-caprolactone (and/or TOSUO) was initiated with bis-MPA or its derivatives using a catalytic amount of Sn(Oct)2. The polymerizations were carried out in the melt at 100°C (20 h). The polymers were then dissolved in THF and precipitated in cold methanol.
1H-NMR spectra were recorded with a Bruker AM 250 (250 MHz) spectrometer. The number average molecular weights were calculated from the intensity ratios of the -OCH2- methylene proton signals (δ = 3.65) in the 1H-NMR spectra. Size-exclusion chromatography was carried out on a Waters chromatograph connected to a Waters 410 differential refractometer. Four 5 μm Waters columns (300 × 7.7 mm) connected in series in order of increasing pore size (100, 1000, 105, and 106 Å) were used with THF as solvent. Glass transition temperatures (Tg) were recorded on a Perkin-Elmer DSC 7.
A general procedure for the preparation of AB2 functional α-carboxylic-ω-dihydroxy poly(ε-caprolactone) (3-n). Pd/C (0.40 g) was added to a solution of 1-20 (4.00 g) in THF (10 mL) and EtOAc (40 mL). The flask was evacuated and put under H2(g) atmosphere. The reaction was stopped after 24 h, the Pd/C was filtered off and the clear solution was precipitated into cold methanol. The obtained macromonomer was a white crystalline powder. Yield: 3.00 g.
Polymerization of α-carboxylic-ω-dihydroxy poly(ε-caprolactone) (1-20). The macromonomer 1-20 (1.00 g, 0.33 mmol) was dissolved in CH2Cl2 (3 mL) in a previously flamed flask, into which a solution of DPTS (16.0 mg, 0.05 mmol) in THF and then DCC (0.10 g, 0.50 mmol) was added. After 48 h the reaction mixture was precipitated into methanol and then filtered to yield 0.87 g (87%) of hyperbranched polymer 4-c.
Deacetalization of TOSUO containing copolymers: ε-CL/TOSUO block copolymer (2.4 mmol of TOSUO) and triphenylcarbenium tetrafluoroborate (2.5 mmol) were dissolved under stirring for 30 min in 100 mL of dichloromethane (3 wt % copolymer). The copolyester was recovered by precipitation in cold methanol. Reduction of ketone pendent groups into hydroxyl groups: Copolyester A (1.2 mmol of ketone) and sodium borohydride (1.45 mmol) were dissolved under stirring in a CH2Cl2/ ethanol (5/2 v/v) mixture (ca. 1.0 wt % copolymer for min. The polymer was isolated by precipitation in cold methanol.
