High Bio-Content Thermoplastic Polyurethanes from Azelaic Acid

Abstract

To realize the commercialization of sustainable materials, new polymers must be generated and systematically evaluated for material characteristics and end-of-life treatment. Polyester polyols made from renewable monomers have found limited adoption in thermoplastic polyurethane (TPU) applications, and their broad adoption in manufacturing may be possible with a more detailed understanding of their structure and properties. To this end, we prepared a series of bio-based crystalline and amorphous polyester polyols utilizing azelaic acid and varying branched or non-branched diols. The prepared polyols showed viscosities in the range of 504–781 cP at 70 °C, with resulting TPUs that displayed excellent thermal and mechanical properties. TPUs prepared from crystalline azelate polyester polyol exhibited excellent mechanical properties compared to TPUs prepared from amorphous polyols. These were used to demonstrate prototype products, such as watch bands and cup-shaped forms. Importantly, the prepared TPUs had up to 85% bio-carbon content. Studies such as these will be important for the development of renewable materials that display mechanical properties suitable for commercially viable, sustainable products.

Synthesis and characterization of improved bio‐based carbon content thermoplastic polyurethane with bio‐aliphatic and petro‐aromatic diisocyanate

“…The second stage, which is most prominent between 380 and 420°C, originates from the dissociation of ester bonds. The third stage, which appears as a shoulder peak between 440 and 450°C, is related to hydrocarbon chain decomposition 54 …”

“…The third stage, which appears as a shoulder peak between 440 and 450 C, is related to hydrocarbon chain decomposition. 54 Generally, the temperature of 5 wt% weight loss (T 5% ) is considered the decomposition onset temperature. It can be seen that the TPUs with PDI or MDI have a higher T 5% than the TPUs composed of the PDI/MDI mixture, indicating that the decomposition starts at higher temperatures.…”

Biodegradable waterborne polyurethane‐urea dispersion adhesives with high biocontent

“…While the bio‐sourced content of TPUs has been reported in excess of 85%, PUDs have lagged behind due to the need for water‐stabilizing agents 27,28 . Vegetable oil‐based PUDs have reported biobased content up to 75%, but they contained monomers not currently used in industrial PUD production 29 .…”

“…While the bio-sourced content of TPUs has been reported in excess of 85%, PUDs have lagged behind due to the need for water-stabilizing agents. 27,28 Vegetable oil-based PUDs have reported biobased content up to 75%, but they contained monomers not currently used in industrial PUD production. 29 Fortunately, the PUDs prepared are synthesized from commercially available monomers and offer a drop-in replacement with current S C H E M E 1 Reaction route for PUD 5 and 6.…”

Determination of Residual Diisocyanates and Related Diamines in Biodegradable Mulch Films Using N-Ethoxycarbonylation Derivatization and GC-MS

“…Generally, 2, 6-TDI and 2, 4-TDI are the predominant diisocyanates in the global market, but have toxicity with acute or chronic effects and potential carcinogenicity. Safer aliphatic biocompatible diisocyanates (HDA and DAB) are suitable alternatives in recent years [ 41 , 42 ]. As a result, diisocyanates and related diamines need to be effectively analyzed for assessing the safety in different biodegradable mulch films.…”