Branched Poly(1,4-Butylene Carbonate-co-Terephthalate)s: LDPE-Like Semicrystalline Thermoplastics

Branched poly[1,4-butylene carbonate-co-terephthalate]s (PBCTs) have been synthesized by the addition of a small amount of glycerol propoxylate (1) or pentaerythritol (2) in the polycondensation of 1,4-butanediol, dimethyl carbonate, and dimethyl terephthalate. To avoid gel formation, the feed amount of 1 or 2 was carefully controlled at below 0.5 mol % for 1 and below 0.3 mol % for 2. When feed of 1 or 2 was used, a high-molecular weight melt state (M-w approximate to 180,000 g/mol) was reached in a total reaction time of 5.5 to 6.5 h with a yield higher than 90%. The generated PBCTs were a semicrystalline polymer (T-g approximate to 5 degrees C and T-m approximate to 120 degrees C) when the terephthalate content (F-[TPA]) was 45 to 50 mol %. The crystallization rate increased with increasing F-[TPA] and branch content (F-[1 (or) (2])); PBCT composed of F-[TPA]=49 mol % and F-[1]=0.44 mol % was crystallized completely in a short time, approximate to 3 min, at a crystallization temperature of 50 degrees C. The branched PBCT exhibited more pronounced toughness in tensile test while providing the advantage of processibility at high shear rates due to the pronounced shear thinning in melt. It was also found that the branched PBCTs were biodegradable. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 914-923