Branched, aliphatic polyurethanes (PURs) were synthesized and compared to linear analogues. The influence of polycaprolactonetriol and synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments on structure, thermal and sorptive properties of PURs was determined. Using FTIR and Raman spectroscopies it was found that increasing the R,S-PHB amount in the structure of branched PURs reduced a tendency of urethane groups to hydrogen bonding. Melting enthalpies (on DSC thermograms) of both soft and hard segments of linear PURs were higher than branched PURs, suggesting that linear PURs were more crystalline. Oil sorption by samples of linear and branched PURs, containing only polycaprolactone chains in soft segments, was higher than in the case of samples with R,S-PHB in their structure. Branched PUR without R,S-PHB absorbed the highest amount of oil. Introducing R,S-PHB into the PUR structure increased water sorption. Thus, by operating the number of branching and the amount of poly([R,S]-3-hydroxybutyrate) in soft segments thermal and sorptive properties of aliphatic PURs could be controlled.

Materials science is an interdisciplinary area of studies. This science focuses on the influence of the physico-chemical properties of materials on their application in human everyday lives. The materials’ synthesis should be developed in accordance with sustainable development. Polyurethanes (PUR) represent a significant consumption of plastic in the world. Modification of PUR, e.g., with polysaccharide of natural origin (chitosan, Chit), should have a positive effect on their functional properties and degradability in the natural environment. The basic parameters affecting the scope and direction of changes are the size and quantity of the chitosan particles. The impact assessment of chitosan on the chemical structure, morphology, thermal properties, crystallinity, mechanical properties, flammability, water sorption, adsorption properties, degradability, and biological activity of PUR/Chit composites (without other additives) is discussed in this article. To the best of our knowledge, recent literature does not contain a study discussing the direct impact of the presence of chitosan in the structure of PUR/Chit composite on its properties, regardless of the intended uses. This paper provides an overview of publications, which presents the results of a study on the effect of adding chitosan in polyurethane/chitosan composites without other additives on the properties of polyurethane.

Polyurethanes are most often called “green” when they contain natural, renewable additives in their network or chemical structure, such as mono- and polysaccharides, oils (mainly vegetable oils), polyphenols (e.g., lignins, tannins), or various compounds derived from agro-waste white biotechnology (Principle 7). This usually results in these polyurethanes obtained from less hazardous substrates (Principle 4). Appropriate modification of polyurethanes makes them susceptible to degradation, and the use of appropriate processes allows for their recycling (Principle 10). However, this fulfilment of other principles also predisposes them to be green. As in the production of other polymer materials, the synthesis of polyurethanes is carried out with the use of catalysts (such as biocatalysts) (Principle 9) with full control of the course of the reaction (Principle 11), which allows maximization of the atomic economy (Principle 2) and an increase in energy efficiency (Principle 6) while minimizing the risk of production waste (Principle 1). Moreover, traditional substrates in the synthesis of polyurethanes can be replaced with less toxic ones (e.g., in non-isocyanate polyurethanes), which, at the same time, leads to a non-toxic product (Principle 3, Principle 5). In general, there is no need for blocking compounds to provide intermediates in the synthesis of polyurethanes (Principle 8). Reasonable storage of substrates, their transport, and the synthesis of polyurethanes guarantee the safety and the prevention of uncontrolled reactions (Principle 12). This publication is a summary of the achievements of scientists and technologists who are constantly working to create ideal polyurethanes that do not pollute the environment, and their synthesis and use are consistent with the principles of sustainable economy.

Polyether-esterurethanes containing synthetic poly[(R,S)-3-hydroxybutyrate] (R,S-PHB) and polyoxytetramethylenediol in soft segments and polyesterurethanes with poly(ε-caprolactone) and poly[(R,S)-3-hydroxybutyrate] were blended with poly([D,L]-lactide) (PLA). The products were tested in terms of their oil and water absorption. Oil sorption tests of polyether-esterurethane revealed their higher response in comparison to polyesterurethanes. Blending of polyether-esterurethanes with PLA caused the increase of oil sorption. The highest water sorption was observed for blends of polyether-esterurethane, obtained with 10% of R,S-PHB in soft segments. The samples mass of polyurethanes and their blends were almost not changed after incubation in phosphate buffer and trypsin and lipase solutions. Nevertheless the molecular weight of polymers was significantly reduced after degradation. It was especially visible in case of incubation of samples in phosphate buffer what suggested the chemical hydrolysis of polymer chains. The changes of surface of polyurethanes and their blends, after incubation in both enzymatic solutions, indicated on enzymatic degradation, which had been started despite the lack of mass lost. Polyurethanes and their blends, contained more R,S-PHB in soft segments, were degraded faster.

One of the methods of making traditional polymers more environmentally friendly is to modify them with natural materials or their biodegradable, synthetic equivalents. It was assumed that blends with polylactide (PLA), polysaccharides: chitosan (Ch) and starch (St) of branched polyurethane (PUR) based on synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) would degrade faster in the processes of hydrolysis and oxidation than pure PUR. For the sake of simplicity in the publication, all three modifiers: commercial PLA, Ch created by chemical modification of chitin and St are called bioadditives. The samples were incubated in a hydrolytic and oxidizing environment for 36 weeks and 11 weeks, respectively. The degradation process was assessed by observation of the chemical structure as well as the change in the mass of the samples, their molecular weight, surface morphology and thermal properties. It was found that the PUR samples with the highest amount of R,S-PHB and the lowest amount of polycaprolactone triol (PCL_triol) were degraded the most. Moreover, blending with St had the greatest impact on the susceptibility to degradation of PUR. However, the rate of weight loss of the samples was low, and after 36 weeks of incubation in the hydrolytic solution, it did not exceed 7% by weight. The weight loss of Ch and PLA blends was even smaller. However, a significant reduction in molecular weight, changes in morphology and changes in thermal properties indicated that the degradation of the samples should occur quickly after this time. Therefore, when using these polyurethanes and their blends, it should be taken into account that they should decompose slowly in their initial life. In summary, this process can be modified by changing the amount of R,S-PHB, the degree of cross-linking, and the type and amount of second blend component added (bioadditives).

The surface morphology and thermal properties of polyurethanes can be correlated to their chemical composition. The hydrophilicity, surface morphology, and thermal properties of polyurethanes (differed in soft segments and in linear/cross-linked structure) were investigated. The influence of poly([R,S]-3-hydroxybutyrate) presence in soft segments and blending of polyurethane with polylactide on surface topography were also estimated. The linear polyurethanes (partially crystalline) had the granular surface, whereas the surface of cross-linked polyurethanes (almost amorphous) was smooth. Round aggregates of polylactide un-uniformly distributed in matrix of polyurethane were clearly visible. It was concluded that some modification of soft segment (by mixing of poly([R,S]-3-hydroxybutyrate) with different polydiols and polytriol) and blending of polyurethanes with small amount of polylactide influence on crystallinity and surface topography of obtained polyurethanes.