Development of bio-based thermoplastic polyurethanes formulations using corn-derived chain extender for reactive rotational molding

Abstract

Abstract. Partly bio-based segmented thermoplastic polyurethane (TPU) formulations were developed to fulfill the requirements of the reactive rotational molding process. They were obtained by one-shot bulk polymerization between an aliphatic diisocyanate (1,6-hexamethylene diisocyanate), a polyether polyol as macrodiol (polyethylene glycol) and a biobased corn-derived 1,3-propanediol as chain extender (CE), in presence of a catalyst, at an initial temperature of 45°C. Equivalent TPU formulations with classical petroleum-based 1,3-propanediol were also prepared for a purpose of comparison. TPU with different soft to hard segment (SS/HS) ratios were synthesized by varying the macrodiol and CE concentrations in the formulations. For each formulation, the evolution of the reaction temperature as a function of time was monitored and the kinetics of polymerization was studied by Fourier Transform infrared spectroscopy in attenuated total reflection mode (FTIR-ATR). The morphology, thermal properties, solubility in different solvents and tensile properties of the final products were analyzed. All synthesized polyurethanes are 100% linear polymers and the extent of microphase separation, as well as the thermal and mechanical properties highly depends on the HS content, and glass transition temperature and Young modulus can be tuned by adjustment of the SS/HS ratio. All results indicate that petrochemical CE can be replaced by its recently available corn-derived homologue, without sacrificing any use properties of the final polyurethanes.

Synthesis of Bio-Based Hydrogel From Epoxidized Palm Oil Catalyzed by Fluoroantimonic Acid Hexahydrate

“…From the graph, the melting temperature, T m for PEPO was observed to be at 10 °C while HPEPO has higher in a range between 45 to 60 °C . As related to previous findings reported by Zhang et al [13] and Rashmi et al [14], bio-based polyols are typically have low melting temperature due the domain that consists of soft segments that crosslink to each other. According to Wang and Schuman [15], the composition of the polymer within the cross linked structure plays an important role in thermal behavior, with the inherently flexible structure of fatty acid chain in PEPO reducing the crosslink density to form a less compact crosslinked structure compared to HPEPO.…”

Effect of carbon nanotube dispersion and network formation on thermal conductivity of thermoplastic polyurethane/carbon nanotube nanocomposites

“…NAH and C@O hydrogen bonded and nonhydrogen bonded stretching vibrations observed at $3320, $1700, and $1725 cm 21 clearly indicate formation of the urethane group. The lack of an isocyanate peak at 2270 cm 21 and presence of the amine and carbonyl peaks indicate a complete conversion of monomers to urethane [19,42,43].…”

Synthesis, structure and properties of poly(ester-urethane)s obtained using bio-based and petrochemical 1,3-propanediol and 1,4-butanediol

“…The actual trends of green chemistry are connected with the replacing of petrochemical-based chemicals by bio-based and renewable feedstock. The increasing interest in the area of bio-based substances (e.g., polyols [1,2,15,16], chain extenders [17][18][19][20] and diisocyanates [21,22]) used as a components in the synthesis of polyurethanes is observed. According to the literature, the non-isocyanates polyurethanes synthesized using natural resources (e.g., vegetable oils, bio-based diamines, fatty acids and glycerol) are also known [23,24].…”

“…Susterra Ò is a completely bio-based diol obtained by biotechnological process from corn sugar. Rashmi et al [18] demonstrated that the replacement of petroleum-based chain extenders by biobased one like Susterra Ò was not reduced the properties of obtained materials, e.g., solubility, thermal and mechanical properties. Another bio-derived propanediol produced by DuPont Tate & Lyle BioProducts is Zemea Ò , which is also obtained in the fermentation process of the corn glucose.…”

“…Over the past few years, novel bio-glycols obtained from natural feedstocks were proposed as components for the synthesis of polymers, for example Zemea Ò propanediol (DuPont Tate & Lyle BioProducts) [28,29], Susterra Ò propanediol (DuPont Tate & Lyle BioProducts) [18,[29][30][31]], 1,3-propanediol from sorghum [32], bio-butanediol from bio-succinic acid [33], 1,4-butanediol realized by using Genomatica's GENO BDO TM process [34], 1,4-butanediol from glucose syrup [35], 1,3-propanediol from crude glycerol [36] and others.…”