Lipase catalysis was successfully employed to synthesize high molecular weight poly(butylene succinate) (PBS). Attempts to copolymerize succinic acid with 1,4-butanediol were unsuccessful due to phase separation of the reactants. To circumvent this problem, monophasic reaction mixtures were prepared from diethyl succinate and 1,4-butanediol. The reactions were studied in bulk as well as in solution. Of the organic solvents evaluated, diphenyl ether was preferred, giving higher molecular weight products. After 24 h in diphenyl ether, polymerizations at 60, 70, 80, and 90 degrees C yielded PBS with M(n) of 2000, 4000, 8000, and 7000, respectively. Further increase in reaction time to 72 h resulted in little or no further increase in M(n). However, increasing the reaction time produced PBS with extraordinarily low M(w)/M(n) due to the diffusion and reaction between low-molecular weight oligomers and chains that occurs at a greater frequency than interchain transesterification. Time-course studies and visual observation of polymerizations at 80 degrees C revealed PBS precipitates at 5 to 10 h, limiting the growth of chains. To maintain a monophasic reaction mixture, the polymerization temperature was increased from 80 to 95 degrees C after 21 h. The result was an increase in the PBS molecular weight to M(w) = 38 000 (M(w)/M(n) = 1.39). This work paves the way for the synthesis of PBS macromers and polymers that contain variable quantities of monomers with chemically sensitive moieties (e.g., silicone, epoxy, vinyl). Furthermore, this study established the feasibility of using lipase catalysis to prepare polyesters from alpha,omega-linear aliphatic diethyl ester/diol monomers with less than six carbons.

Candida antarctica Lipase B (CALB), a metal-free enzyme, was successfully employed as catalyst for ring-opening copolymerization of omega-pentadecalactone (PDL) with p-dioxanone (DO) under mild reaction conditions (<80 degrees C, atmospheric pressure). Poly(PDL-co-DO) with high molecular weight (Mw > 30 000) and a wide range of comonomer contents was synthesized using various PDL/DO feed ratios. During the copolymerization reaction, large ring PDL was found to be more reactive than its smaller counterpart DO, resulting in higher PDL/DO unit ratios in polymer chains than the corresponding PDL/DO monomer ratios in the feed. The copolymers were typically isolated in 50-90 wt % yields as the monomer conversion was limited by the equilibrium between monomers and copolymer. 1H and 13C NMR analysis on poly(PDL-co-DO) formed by CALB showed that the copolymers contain nearly random sequences of PDL and DO units with a slight tendency toward alternating arrangements. Copolymerization with PDL was found to remarkably enhance PDO thermal stability. Differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS) results demonstrate high crystallinity in all copolymers over the whole range of compositions. Depending on copolymer composition, the crystal lattice of either PDO or PPDL hosts units of the other comonomer, a behavior typical of an isodimorphic system. In poly(PDL-co-DO), both melting temperature and melting enthalpy display a minimum at 70 mol % DO, that is, at the pseudoeutectic composition. WAXS diffractograms show one crystal phase (that of either PPDL or PDO) on either side of the pseudoeutectic and coexistence of PPDL and PDO crystals at the pseudoeutectic.

The synthesis of silicone polyesteramides was successfully performed in bulk at 70 °C via a biocatalytic route. Immobilized Candida antartica Lipase B (Novozym 435, N435) was used as catalyst under mild conditions to perform the polycondensation reaction using various feed mole ratios of diethyl adipate (DEA), 1,8-octanediol (OD), and R,ω-(diaminopropyl)polydimethylsiloxane (Si-NH 2 ). The syntheses of poly(octamethylene adipate), POA, and poly(R,ω-(diaminopropyl)polydimethylsiloxane adipamide), PSiAA, were also performed by N435 catalysis in order to compare their properties with those of silicone polyesteramides. The microstructures of all polymers were studied by 1 H NMR spectroscopy, and calculated amide/ester ratios were in agreement with the monomer feed mole ratio. Formation of amide links (DEA-SiAA units) occurs more rapidly than ester repeats (DEA-OA units). This results in copolymers that tend toward a blocklike sequence distribution. Thermal stability of the polyesteramides, evaluated by TGA both in nitrogen and in air, increases with DEA-SiAA content (up to 50 mol %). The relative amount of amide and ester units along the polymer chain strongly affects the physical aspect of the polyesteramides. High content of DEA-OA units leads to hard solid materials containing a welldeveloped high melting POA-type crystal phase, whose melting temperature changes with composition. When DEA-SiAA units are the major component, the material acquires a sticky appearance.

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