Bio-based Thermoplastic Polyhydroxyurethanes Synthesized from the Terpolymerization of a Dicarbonate and Two Diamines: Design, Rheology, and Application in Melt Blending

Abstract

The terpolymerization of bio-based diglycerol dicarbonate (DGC) and Priamine 1074 is conducted with aminopropyl terminated polydimethylsiloxane (M n = 1000 g/ mol, PDMS) or 1,10-diaminodecane (DAD). Depending on DGC contents and PDMS/Priamine 1074 ratios, the resulting amorphous thermoplastic polyhydroxyurethanes (TPHUs) present random or block copolymer-like segmented structures. These TPHUs exhibit nanophase separation of small interdomain spacing (3−3.5 nm) mainly caused by DGC. As for DAD, it introduces crystallinity (8%) and chain ordering into the TPHU structure as observed from X-ray measurements. Some PDMS-based TPHUs are blended with PLA, and the blends are found to be partially miscible as they exhibit two T g 's, and their estimated relative energy differences (RED), calculated from Hoftyzer−Van Krevelen's group contribution method, are nearly unity. Based on the type of hydrogen bonding interactions and the extent of immiscibility (RED) of each of the blends, the TPHUs find potential applications as toughening agents and/or plasticizers for PLA.

Sugar-Based Thermoplastic Polyhydroxyurethanes: Effects of Sorbitol and Mannitol Diastereomers on Polymer Properties and Applications in Melt Blending

“…Diglycerol dicarbonate (DGC) is derived from glycerol, which is a byproduct obtained from the hydrolysis of biomass wastes, the methanolysis of triglycerides, and the production of biodiesel, whereas sorbitol and mannitol biscarbonates (SBC and MBC, respectively) are acquired from sugars obtained from glucose processing . While DGC was extensively explored in the literature for different PHU formulations, − SBC and MBC were not, − and that could be related to the low melting point of DGC (65 °C), , which allows it to react with diamines in bulk and at moderate conditions, compared to the high melting points of SBC and MBC (214–216 °C and 181–183 °C, respectively) …”

Effects of Poly(propylene glycol)‐Based Triamine on the Sol/Gel Curing and Properties of Hybrid Non‐Isocyanate Polyurethanes

“…[ 4,10,18–41 ] Of the multitude of viable renewable NIPU precursors, glycerol remains an attractive choice as it is produced as a by‐product of the biodiesel industry, allowing it to be an inexpensive, renewable, and safe precursor to cyclic dicarbonates. [ 28,31,37,38,42–47 ] Indeed, the price of crude glycerol in 2019 was around $US 170 per ton, [ 48 ] leading glycerol to be a very inexpensive pathway to renewable bio‐based NIPUs. Further, use of glycerol avoids ester cleavage issues [ 3,21,26,42 ] which plague some other NIPU feedstocks such as vegetable oils.…”

“…[ 49 ] Many researchers have synthesized NIPU thermoplastics, hybrid thermosets, and waterborne systems from glycerol derivatives, namely, diglycerol dicarbonate (DGC). [ 31,37–39,42–44,46,47 ] Younes et al. synthesized cheaper linear DGC‐based NIPUs using a poly(propylene glycol) diamine, Jeffamine D‐2000 (Huntsman), herein referred to as Jeffamine, which could be subsequently functionalized with amino (N‐2‐aminoethyl‐3‐aminopropyltrimethoxysilane, Dynasylan DAMO) or epoxy (3‐glycidyloxypropyltrimethoxysilane, Dynasylan GLYMO) terminated trimethoxysilane end‐cappers to yield moisture‐curable hybrid NIPUs that could be potentially used as adhesives and sealants.…”

“…[49] Many researchers have synthesized NIPU thermoplastics, hybrid thermosets, and waterborne systems from glycerol derivatives, namely, diglycerol dicarbonate (DGC). [31,[37][38][39][42][43][44]46,47] Younes et al synthesized cheaper linear DGC-based NIPUs using a poly(propylene glycol) diamine, Jeffamine D-2000 (Huntsman), herein referred to as Jeffamine, which could be subsequently functionalized with amino (N-2-aminoethyl-3-aminopropyltrimethoxysilane, Dynasylan DAMO) or epoxy (3-glycidyloxypropyltrimethoxysilane, Dynasylan GLYMO) terminated trimethoxysilane end-cappers to yield moisture-curable hybrid NIPUs that could be potentially used as adhesives and sealants. [39] While these novel glycerolbased poly(hydroxy urethanes) (PHUs) show promise, they exhibited some of the common pitfalls of hybrid NIPUs in such applications, namely inadequate tensile properties and water swelling behavior, [39] presenting an obstacle to wider adoption.…”

Tuning the Catalytic Activity of Recyclable Heterogeneous Catalysts for the Direct Etherification Reaction of Glycerol Using Antagonistic Additives

“…Polyglycerol, a product of the conversion of glycerol by etherification, has tremendous potential in a variety of fields including polymers, cosmetics, food, dispersants, pharmaceutical industry, lubricants, biomedical, or pharmaceutical delivery systems [1][2][3][4]. In particular, diglycerol (DG) and triglycerol (TG) are converted into derivatives such as fatty acid esters, which can be used as multifunctional additives for pharmaceuticals, cosmetics, foods, and polyurethans [1,2,[5][6][7][8][9][10]. DG and TG can also be used as water-soluble plasticizers and emulsions.…”