Biobased, Biodegradable, and Water-Soluble Amine-Functionalized Non-Isocyanate Polyurethanes for Potential Home Care Application

Abstract

Non-isocyanate polyurethanes (NIPUs) synthesized using bis–/poly­(cyclic carbonate) and di-/polyamine monomers provide a safer alternative to conventional polyurethanes (PUs) produced from highly toxic di-/polyisocyanates and di-/polyols. Water-based NIPUs could potentially substitute waterborne PUs, particularly, in applications where the presence of minute amounts of isocyanate impurity in the final PU product might cause severe consequences. Nevertheless, direct syntheses of water-soluble NIPUs are uncommon. Herein, we report a single-step synthesis of water-soluble and bio-derived linear amine-NIPUs by the polyaddition reaction of succinic bis­(cyclic carbonate) (SuBCC) with different commercial polyamines. These amine-NIPUs contain secondary (−NH−) or tertiary (−NR−) amine groups in their main chain imparting good water solubility/dispersibility. Consequently, the water-soluble amine-NIPUs were evaluated for their function as anti-soil/dirt redepositioning agents, one of the key ingredients present in laundry detergents used in home care applications. It is demonstrated that amine-NIPUs in this study are effective in retaining >90% whiteness (L*) of cotton and polyester cloths after model dirt deposition and wash cycle. Remarkably, these polymers were noncytotoxic when tested on human keratinocyte HaCaT cells and non-skin irritants by in vitro skin irritation assay using reconstructed human epidermis, which emphasizes their suitability for home care applications further. The amine-NIPUs were also found to degrade slowly (65% in 32 days) under hydrolytic conditions similar to that of seawater (pH 8.4 at 23 °C) and were biodegradable in activated sludge (up to 66% in 28 days), as determined by Zahn Wellens OECD-302-B assay. This work may pave the way toward the development and utilization of green, sustainable, and biodegradable NIPUs in home care and other applications, replacing the current toxic, nondegradable, and petroleum-based ingredients.

Phosphate functionalized nonisocyanate polyurethanes with bio-origin, water solubility and biodegradability

“…As a positive control, ethylene glycol demonstrated close to 80% biodegradability. These findings are highly promising, particularly considering that there are only limited studies 50,51 on water soluble and biodegradable NIPUs. The biodegradability of these NIPU phosphates might be facilitated by their water solubility and the presence of easily hydrolysable functionalities such as phosphate, urethane, and ester functionalities.…”

“…Matsukizono and Endo 66 reported a study where they reacted NIPU hydroxyl groups with succinic anhydride, followed by neutralization with sodium bicarbonate, resulting in the formation of water-soluble NIPUs containing the sodium carboxylate functionality. In a recent study conducted by our group, 50,51 we successfully synthesized bio-derived NIPUs with secondary (–NH–) or tertiary (–NR–) amine groups in their main chains, which endowed these polymers with excellent water solubility/dispersibility. These newly synthesized NIPUs were also explored for their potential applications in home care, specifically as anti-redepositioning agents, and were found to be promising.…”

Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels

“…However, li le a ention has been paid to NIPU/POSS physical blends, and even less a ention has been paid to determining the impact of POSS on the hydration properties of NIPUs, even though the high water absorption seems to be a dominant feature for this kind of material. Taking into account the biocompatibility of POSS [50,51] and the possible application of NIPUs in biomedical fields (e.g., in wound treatment) [52,53], shedding light on the influence of POSS on water-polymer interactions Subsequently, the type of POSS and the method of its introduction into the polymer matrix will influence the properties of the resultant hybrid composites. POSS may positively influence biocompatibility [38,39], flame retardancy [40,41], mechanical properties [37,38,42], etc.…”

“…However, little attention has been paid to NIPU/POSS physical blends, and even less attention has been paid to determining the impact of POSS on the hydration properties of NIPUs, even though the high water absorption seems to be a dominant feature for this kind of material. Taking into account the biocompatibility of POSS [ 50 , 51 ] and the possible application of NIPUs in biomedical fields (e.g., in wound treatment) [ 52 , 53 ], shedding light on the influence of POSS on water–polymer interactions in such systems is interesting from the point of view of polymer and material science. It should be noted that although water–polymer interactions attract a lot of attention due to their obvious significance in biotechnology [ 54 , 55 ], more often than not, the studies are performed in solutions, i.e., in an environment of abundant water.…”