Random Copolycarbonates Based on a Renewable Bicyclic Diol Derived from Citric Acid

Abstract

To address the poor thermal stability of isohexides while at the same time retain rigidity, we developed a novel bicyclic diol octahydro-2,5-pentalenediol (OPD) from naturally occurring citric acid in this study. Owing to the bicyclic skeleton composed of two fused cyclopentane rings, OPD is supposed to have perfect rigidity but higher thermal stability compared to isohexides. Herein, OPD was first converted to octahydro-2,5-pentalenediol bis­(methyl carbonate) (OPBMC) by reacting with dimethyl carbonate. The absolute stereochemistry of OPBMC was investigated by 2D 1H NMR and 13C NMR as well as single crystal X-ray diffraction. By polymerization of OPBMC with several aliphatic diols [1,8-octanediol (A8), 1,10-decanediol (A10), and 1,12-dodeacnediol (A12)] and alicyclic diols [1,4-cyclohexane­dimethanol (CHDM), 1,2,2-trimethyl­cyclopentane-1,3-dimethanol (TCDM), and octahydro-2,5-pentalenediol (OPD)], a series of bio-based copolycarbonates (co-PCs) with intriguing properties were synthesized. NMR spectra revealed that the stereochemistry of OPBMC was preserved after polymerization. Both differential scanning calorimetry and wide-angle X-ray diffraction analyses revealed that co-PCs made from A8, A10, A12, and OPD are semicrystalline, while co-PCs based on CHDM and TCDM are amorphous. A relatively high T 5% of 276 °C and outstanding high T g up to 80.4 °C were detected for fully OPD-based co-PC, confirming the excellent thermal stability and rigidity of OPD. This work addresses some critical needs for high performance polymers such as improving the sustainability of raw materials and achieving both high T g values and thermal stability.

Enzymatic Synthesis and Polymerization of Isosorbide-Based Monomethacrylates for High-Tg Plastics

“…7 However, the low reactivity of its secondary hydroxyl groups limits the use of isosorbide in polymerizations, and, in conjunction with high T g values, oligomeric or severely colored products are often formed. 8 this issue include the conversion of secondary hydroxyl groups into primary ones 9 and modification of the fused ring system, 10 which, unfortunately, usually lead to partial loss of polymer chain rigidity and reduction of T g . Isosorbide has in most cases been entirely included in the polymer backbone via engagement of both hydroxyl groups.…”

Robust Catechol Containing Cationic Waterborne Polyurethanes with Antibacterial, UV Protective, and Adhesive Properties

“…The main reason was that the incorporation of catechol structure in the molecular side chain of CWPUs provided more hydrogen bond interaction between polymer chains, and thus reduced the free volume and prevent close packing of molecular, leading to the enhancement in T g of the samples. [ 52 ]…”

“…The main reason was that the incorporation of catechol structure in the molecular side chain of CWPUs provided more hydrogen bond interaction between polymer chains, and thus reduced the free volume and prevent close packing of molecular, leading to the enhancement in T g of the samples. [52] The storage moduli (E′) of the CWPU films were studied by DMA. As shown in Figure 3h, the CWPUs displayed a typical behavior of crosslinked polymers with a sudden decrease in the E′ from −50 to −20 °C because of the motion of the soft segments of the polyurethane molecule.…”

Completely amorphous high thermal resistant copolyesters from bio‐based 2,5‐furandicarboxylic acid

“…To the best of our knowledge, incorporating the rigid cyclic diols is one of the most attractive methods to improve T g and modulus of polyesters. Therefore, varied cyclic diols, including isosorbide, [46][47][48][49] isomannide, 2,4:3,5-di-O-methylene-D-mannitol (Manx), 50,51 2,3:4,5-di-O-methylene-galactaric acid (Galx), 52 2,4:3,5-di-O-methylene-Dglucitol (Glux), 53 1,4-bis(hydroxymethyl)benzene, 54 octa hydro-2,5-pentalenediol (OPD), 55 and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) [56][57][58] have been tried as comonomers to enhance the polyester's chain stiffness and then improve their T g . The polyester synthesized from isosorbide and 1,4-cyclohexanedicarboxylic acid showed high T g up to 131 C. 46 However, the reactivity of isosorbide must be improved by acetic anhydride, which made the polycondensation more complicated.…”