High Thermal Stability of Bio-Based Polycarbonates Containing Cyclic Ketal Moieties

Abstract

Bio-based polycarbonates containing cyclic ketal moieties were designed, and the bio-based diol monomer was synthesized by CQ with glycerol to improve their thermal properties and replace BPA in polymer industry. The molecular structure of the novel bio-based diol monomer 2,2:3,3-bis(4′-hydroxymethylethylenedioxy)-1,7,7-trimethylbicyclo[2.2.1]heptane (abbreviated as CaG) was analyzed by 1 H, 13 C, and 2D-COSY NMR techniques. GPC results show that CaG was reacted successfully and led to the high molecular weights for homopolycarbonate (M w = 18 652) abbreviated as PCaGC and for copolycarbonate (M w = 78 482) as PCaG 20 BPA 80 C. The high thermal stability (T d value above 350°C) and glass transition temperature (T g value from 128 to 151°C) of PCaGCs and PCaG x BPA y Cs were studied by TGA and DSC, respectively. Given the sufficient reactivity and high thermal stability, CaG is a promising renewable building block for applicable polymers.

Synthesis of isosorbide-based polycarbonates via melt polycondensation catalyzed by quaternary ammonium ionic liquids

“…The resulting material was dissolved in dichloromethane to precipitate a small quantity of silver dicyanamide, which was filtered off, following which the filtrate was evaporated to dryness. The TEAD was then dried under vacuum over 2 d. Yield: 1.90 g (97%); 1 Tetraethylammonium lactate (TEAL) was synthesized by the acid-base neutralization method. Lactic acid (0.90 g, 0.01 mol) was added dropwise to a 100 mL single-necked flask containing TEAH (1.47 g, 0.01 mol), after which the mixture was stirred for approximately 5 h at room temperature.…”

“…Polycarbonate (PC) is an excellent engineering plastic widely used for various industrial applications owing to its unique properties, including high tensile strength, impact resistance, and good transparency [1,2]. Currently, one of the most important and widely commercialized PCs is bisphenol A PC (BPAPC) [3,4].…”

Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid

“…In addition, Suh and coworkers synthesized a PC by polycondensation of DPC and the bis(glycerol) ketal of camphorquinone, and reported Đ = 2.25 (M n = 8.3 kg mol −1 ). 24 Characterization by 1 H and 13 C NMR spectroscopy confirmed the structure of the PCs (see Fig. 3 and Fig.…”

“…Recently, the biobased diketones camphorquinone and 1,4-cyclohexanedione were combined with glycerol to obtain stiff spiro-diols. 24 The corresponding PCs showed good mechanical properties, high thermal stability and high T g values. However, the isolation of these diol monomers required chromatographic purification, which makes them less attractive on larger scales.…”

A rigid spirocyclic diol from fructose-based 5-hydroxymethylfurfural: synthesis, life-cycle assessment, and polymerization for renewable polyesters and poly(urethane-urea)s

“…polyesters, polyurethanes and polycarbonates) have been reported based on a variety of biomass resources. [25][26][27][28][29][30][31]107 Sugar-based rigid building blocks have also been intensively investigated. For example, isosorbide (a bicyclic sugarbased diol) was reported to produce diversified polymer structures with increased T g .…”