Non-isocyanate Polyurethanes Research Articles

Design of 3D-Photoprintable, Bio-, and Hemocompatible Nonisocyanate Polyurethane Elastomers for Biomedical Implants.

Polyurethanes (PUs) have adjustable mechanical properties, making them suitable for a wide range of applications, including in the biomedical field. Historically, these PUs have been synthesized from isocyanates, which are toxic compounds to handle. This has encouraged the search for safer and more environmentally friendly synthetic routes, leading today to the production of nonisocyanate polyurethanes (NIPUs). Among these NIPUs, polyhydroxyurethanes (PHUs) bear additional hydroxyl groups, which are particularly attractive for derivatizing and adjusting their physicochemical properties. In this paper, polyether-based NIPU elastomers with variable stiffness are designed by functionalizing the hydroxyl groups of a poly(propylene glycol)-PHU by a cyclic carbonate carrying a pendant unsaturation, enabling them to be post-photo-cross-linked with polythiols (thiol-ene). Elastomers with remarkable mechanical properties whose stiffness can be adjusted are obtained. Thanks to the unique viscous properties of these PHU derivatives and their short gel times observed by rheology experiments, formulations for light-based three-dimensional (3D) printing have been developed. Objects were 3D-printed by digital light processing with a resolution down to the micrometer scale, demonstrating their ability to target various designs of prime importance for personalized medicine. In vitro biocompatibility tests have confirmed the noncytotoxicity of these materials for human fibroblasts. In vitro hemocompatibility tests have revealed that they do not induce hemolytic effects, they do not increase platelet adhesion, nor activate coagulation, demonstrating their potential for future applications in the cardiovascular field.

Antimicrobial Nonisocyanate Polyurethane Foam Derived from Lignin for Wound Healing.

Medical dressings, as a cover for wounds, can replace damaged skin in the wound healing process to play a temporary barrier role, avoid or control wound infection, and provide a favorable environment for wound healing. Therefore, there is an urgent need for medical antimicrobial dressings for the treatment of chronic wounds. Although traditional polyurethane foam has been widely used in medical dressings, conventional polyurethane foams are primarily prepared using nonbiocompatible isocyanate-based compounds, which are potentially hazardous for both operators and applications in the medical field. Here, we propose nonisocyanate polyurethane foams naturally derived from lignin by enzymatic lignin alkylation, cyclic carbonation modification, and polymerization with diamine and the addition of a blowing agent. Silver nanoparticle solution was added during foaming to confer antimicrobial properties. This lignin-based nonisocyanate polyurethane/silver composite foam (named NIPU foam-silver) using a green synthesis method has good mechanical properties, which can be used to manufacture polyurethane/silver foams, and thermal and antimicrobial properties. Notably, NIPU foam-Ag showed more than 95% bactericidal efficacy against both Escherichia coli and Staphylococcus aureus within 4 h. Evaluation of in vitro wounds in mice showed that this antimicrobial composite foam rapidly promotes wound healing and repairs damaged tissue. This suggests that this biobased biodegradable antimicrobial foam has significant scope for clinical applications in wound management.

Oxone in microemulsion for diastereoselective epoxidation of R-limonene to trans-limonene dioxide

Some catalytic processes developed for the synthesis of epoxy resins, polycarbonates or even non-isocyanate polyurethanes from cis/trans-limonene dioxide exhibit low or complete absence of reactivity of cis-limonene dioxide (cis-LDO). This study focuses on the development of a process for exclusively producing trans-LDO. The technique involves uses a chiral ketone as a catalyst that reacts with oxone to form the corresponding chiral dioxirane which epoxidises R-limonene. The effect of various organic solvents and the importance of the surfactant (for micelle formation) were evaluated. It was found that when epoxidation is performed using a chiral ketone in presence of a microemulsion, high conversion and diastereoselectivity was reached. The chiral ketone catalyst tested in this way gave an LDO yield close to 100%, consisting almost exclusively of trans-LDO (97%). When acetone catalyst was employed instead of the chiral ketone, a mixture of cis and trans-LDO was obtained with a selectivity to trans diastereoisomers of only 39%. The diastereoselective epoxidation process developed is easy to reproduce and could be considered ready for industrial implementation.

Biobased, reprocessable, self-blown non-isocyanate polyurethane foams: Influence of blowing agent structure and functionality

The ever-increasing scrutiny of polymer environmental issues calls for advancements in polymers derived from sustainable sources, which can include biobased precursors. However, biobased polymers often exhibit properties inferior to petrochemical-based materials. Here, we address this issue relevant in the development of polyhydroxyurethane (PHU) foams made from the tandem aminolysis-decarboxylation of dimer-acid-derived cyclic carbonates by probing the effects of thiol structure and functionality on foam properties. Incorporating difunctional, trifunctional, and tetrafunctional thiols, we observed that the foam morphology is independent of thiol structure. Using dynamic mechanical analysis, compressive testing, and hysteresis testing, we demonstrated enhancements of mechanical properties due to increase in cross-link density. Additionally, with the glass transition temperature well below room temperature, the foams are categorized as high-resiliency flexible foams. Then, we reprocessed the foams into bulk materials via hydroxyurethane dynamic chemistry, showing full recovery of cross-link density and demonstrating added sustainability and recyclability benefits of these materials. Moreover, the utility of the reprocessed films as dimensionally stable elastomers is demonstrated by the elevated-temperature creep arrest. Notably, cyclic carbonates derived from dimer acid also contain ester groups that can exchange during reprocessing. We performed stress relaxation experiments and demonstrated that transesterification plays a key role in tuning the relaxation phenomena. This study elucidates the modular control of PHU foam mechanical properties and demonstrates the tunable design and relaxation behaviors of biobased PHU foams.

Polylactide-Based Nonisocyanate Polyurethanes: Preparation, Properties Evaluation and Structure Analysis.

This study investigated the successful synthesis and characterization of nonisocyanate polyurethanes (NIPUs) based on polylactide. The NIPUs were synthesized by a condensation reaction of oligomers with hard segments (HSs) and synthesized carbamate-modified polylactic acid containing flexible segments (FSs). The oligomers with HSs were prepared from phenolsulfonic acid (PSA) or a mixture of PSA and hydroxynaphthalenesulfonic acid (HNSA), urea and formaldehyde. The mixing of oligomeric compounds with different amounts of formaldehyde was carried out at room temperature. Obtained NIPU samples with different hard segment content were tested for their mechanical and thermal properties. The tensile strength (TS) of all NIPU samples increased with an increasing amount of HSs, attaining the maximum value at an HS:FS ratio of 1:3. Samples prepared from PSA and HNSA showed higher tensile strength (TS) without significant change in elongation at break compared to the samples based only on PSA. Thermogravimetric analysis data indicated an absence of weight loss for all samples below 100 °C, which can be considered a safe temperature for using NIPU materials. Maximum degradation temperatures reached up to 385 °C. Fourier transform infrared spectroscopy results confirmed the existence of expected specific groups as well as the chemical structure of the prepared polyurethanes. DSC analysis showed the existence of two characteristic phase transitions attributed to the melting and crystallization of hard segments in the NIPU samples.

Preparation of mechanically tunable non-isocyanate polyurethane based on thiol-ene click reaction and amine structure

Preparation of mechanically tunable non-isocyanate polyurethane based on thiol-ene click reaction and amine structure

Direct ink writing of biocompatible chitosan/non-isocyanate polyurethane/cellulose nanofiber hydrogels for wound-healing applications

The demand for new biocompatible and 3D printable materials for biomedical applications is on the rise. Ideally, such materials should exhibit either biodegradability or recyclability, possess antibacterial properties, and demonstrate remarkable biocompatibility with no cytotoxic effects. In this research, we synthesized biocompatible and 3D printable hydrogels tailored for biomedical applications, such as wound healing films, by combining antibacterial double-quaternized chitosan (DQC) with cystamine-based non-isocyanate polyurethane (NIPU-Cys) - a material renowned for enhancing both the flexibility and mechanical properties of the hydrogels. To improve the rheological behavior, swelling attributes, and printability, cellulose nanofibrils were introduced into the matrix. We investigated the impact of DQC on degradability, swelling capacity, rheological behavior, printability, and cell biocompatibility. The slightly cytotoxic nature associated with quaternary chitosan was evaluated, and the optimal concentration of DQC in the hydrogel was determined to ensure biocompatibility. The resulting hydrogels were found to be suitable materials for 3D printing via a direct ink writing technique (DIW), producing porous, biocompatible hydrogels endowed with valuable attributes suitable for various wound-healing applications.

Synthesis and surface modification of sunflower oil‐based non‐isocyanate polyurethane: Physicochemical and antibacterial properties

AbstractIn this work, non‐isocyanate polyurethane (NIPU) films are synthesized from sunflower oil (SFO) with the object of using a renewable resource and establishing a nonpolluting process. SFO also has the advantage of having a higher level of unsaturation than other commercial oils, which provides more reactive sites to be chemically modified. This feature enables a higher degree of conversion to the two monomers, cyclocarbonate, and polyamine‐polyol. NIPU is obtained from their mixture and further crosslinking at 90°C allows the films with suitable mechanical properties to be used in biomedical applications. However, NIPU does not show antibacterial activity, so the surface must be modified. Two methods are used: layer‐by‐layer coating of alginate‐chitosan, and immersion in tea tree oil (TTO), previously activating the surface with acrylic acid (AANIPU). Surface modifications are confirmed by increased hydrophilicity, thermochemical changes, and a drop in mechanical performance. TTO on NIPU films inhibits bacterial growth against S. aureus and E. Coli. NIPU and AANIPU can be accepted as noncytotoxic, while incorporation of the two agents can produce cytotoxicity. No previous reports of such modifications have been found on NIPU films, which appear as promising alternatives for biomedical applications.

A review on vegetable oil-based non isocyanate polyurethane: towards a greener and sustainable production route.

The transition from conventional polyurethane (PU) to non isocyanate polyurethane (NIPU) is driven mainly by safety concerns, environmental considerations, and sustainability issues associated with the current PU technology. NIPU has emerged as a promising alternative, addressing limitations related to traditional PU production. There has been increasing interest in bio-based NIPU aligning with the aspiration for green materials and processes. One important biomass resource for the development of bio-based NIPU is vegetable oil, an abundant, renewable, and relatively low cost feedstock. As such, this review aims to provide insight into the progression of NIPU derived from vegetable oils. This article highlights the synthetic and green approach to NIPU production, emphasizing the method involving the polyaddition reaction of cyclic carbonates and amines. The review includes case studies on vegetable oil-based NIPU and perspectives on their properties. Further, discussions on the potential applications and commercial importance of PU and NIPU are included. Finally, we offer perspectives on possible research directions and the future prospects of NIPU, contributing to the ongoing evolution of PU technology.

Design, manufacturing and testing of a green non-isocyanate polyurethane prosthetic heart valve.

The sole effective treatment for most patients with heart valve disease is valve replacement by implantation of mechanical or biological prostheses. However, mechanical valves represent high risk of thromboembolism, and biological prostheses are prone to early degeneration. In this work, we aim to determine the potential of novel environmentally-friendly non-isocyanate polyurethanes (NIPUs) for manufacturing synthetic prosthetic heart valves. Polyhydroxyurethane (PHU) NIPUs are synthesized via an isocyanate-free route, tested in vitro, and used to produce aortic valves. PHU elastomers reinforced with a polyester mesh show mechanical properties similar to native valve leaflets. These NIPUs do not cause hemolysis. Interestingly, both platelet adhesion and contact activation-induced coagulation are strongly reduced on NIPU surfaces, indicating low thrombogenicity. Fibroblasts and endothelial cells maintain normal growth and shape after indirect contact with NIPUs. Fluid-structure interaction (FSI) allows modeling of the ideal valve design, with minimal shear stress on the leaflets. Injection-molded valves are tested in a pulse duplicator and show ISO-compliant hydrodynamic performance, comparable to clinically-used bioprostheses. Poly(tetrahydrofuran) (PTHF)-NIPU patches do not show any evidence of calcification over a period of 8 weeks. NIPUs are promising sustainable biomaterials for the manufacturing of improved prosthetic valves with low thrombogenicity.

Lignin-derivable, thermoplastic, non-isocyanate polyurethanes with increased hydrogen-bonding content and toughness vs. petroleum-derived analogues.

The functionality inherent in lignin-derivable bisguaiacols/bissyringols can improve the processability and performance of the resulting polymers. Herein, non-isocyanate polyurethanes (NIPUs) were synthesized from bisguaiacols/bissyringols with varying degrees of methoxy substitution and differing bridging groups. Notably, the presence of increasing numbers of methoxy groups (0, 2, and 4) in bisphenol F (BPF)-, bisguaiacol F (BGF)-, and bissyringol F (BSF)-NIPUs led to higher percentages of hydrogen-bonded -OH/-NH groups (i.e., ∼65%, ∼85%, ∼95%, respectively). Increased hydrogen bonding between chains improved the elongation-at-break (εbreak) and toughness of lignin-derivable NIPUs over their petroleum counterparts without a reduction in Young's moduli and tensile strengths. For example, BSF-NIPU exhibited the highest εbreak ∼210% and toughness ∼62 MJ m-3, followed by BGF-NIPU (εbreak ∼185% and toughness ∼58 MJ m-3), and then BPF-NIPU (εbreak ∼140% and toughness ∼42 MJ m-3). Similar trends were found in the dimethyl-substituted analogues, particularly for the bisphenol A-NIPU and bisguaiacol A-NIPU. Importantly, the melt rheology of the lignin-derivable NIPUs was comparable to that of the petroleum-derived analogues, with a slightly lower viscosity (i.e., improved melt flow) for the bio-derivable NIPUs. These findings suggested that the added functionalities (methoxy groups) derived from lignin precursors improved thermomechanical stability while also offering increased processability. Altogether, the structure-property-processing relationships described in this work can help facilitate the development of sustainable, performance-advantaged polymers.

Correction: CO2-derived non-isocyanate polyurethanes (NIPUs) and their potential applications

Correction for ‘CO2-derived non-isocyanate polyurethanes (NIPUs) and their potential applications’ by Rita Turnaturi et al., Green Chem., 2023, 25, 9574–9602, https://doi.org/10.1039/D3GC02796A.

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

Water-soluble/dispersible, bio-derived, non-toxic and biodegradable nonisocyanate polyurethane (NIPU) phosphate monoesters were synthesized by applying green chemistry principles. Potential applications include personal care and cosmetic products.

Biorenewable vegetable oil based nonisocyanate polyurethanes and nanocomposites; formulation, characterisation, biodegradation, anticorrosion and antifouling coatings

Castor oil cyclic carbonate chosen as sustainable precursor to afford biodegradable NIPU via polyaddition of aliphatic diamine and NIPU nanocomposites by functionalized Fe3O4 via covalent incorporation, used as anticorrosion and antifouling coating.

Fast carbon dioxide–epoxide cycloaddition catalyzed by metal and metal-free ionic liquids for designing non-isocyanate polyurethanes

Imidazolium-based ionic liquids are applied as all-in-one catalysts for the supercritical carbon dioxide–epoxide cycloaddition to produce β-hydroxyurethanes under mild conditions.

Turning waste into resources. Efficient synthesis of biopolyurethanes from used cooking oils and CO2

The coupling reaction of carbon dioxide and highly-substituted epoxides derived from renewable resources such as fatty acids and waste vegetable oils (cooking oils derived from olive and sunflower) leads to the synthesis of new bio-derived cyclic carbonates using efficient metal-free bifunctional organocatalysts under mild and solvent-free reaction conditions. Once cyclic carbonates derived from biobased sources were synthesized, the design of non-isocyanate polyurethanes (NIPUs) with different chemical structures was investigated by their reaction with a broad substrate scope of diamines. The NIPUs materials were characterized by spectroscopic techniques (NMR and IR) and their molecular weights and polydispersities were determined by GPC studies. Finally, thermal properties of the polymers were studied by DSC and TGA analyses.

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations.

For decades, self-blown polyurethane foams─found in an impressive range of materials─are produced by the toxic isocyanate chemistry and are difficult to recycle. Producing them in existing production plants by a rapid isocyanate-free self-blowing process from room temperature (RT) formulations is a long-lasting challenge. The recent water-induced self-blowing of nonisocyanate polyurethane (NIPU) formulations composed of a CO2-based tricyclic carbonate, diamine, water, and a catalyst successfully addressed the isocyanate issue, however failed to provide foams at RT. Herein, we elaborate a practical solution to empower the NIPU foam formation in record timeframes from RT formulations. We generate cascade exotherms by the addition of a highly reactive triamine and an epoxide to the formulation of the water-induced self-foaming process. These exotherms, combined to a fast cross-linking imparted by the triamine and epoxide, rapidly raise the temperature to the foaming threshold and deliver hybrid NIPU foams in 5 min with KOH as a catalyst. Careful selection of the monomers enables producing foams with a wide range of properties, as well as with an unprecedented high biobased content up to 90 wt %. Moreover, foams can be upcycled into polymer films by hot pressing, offering them a facile reuse scenario. This robust cheap process opens huge perspectives for greener foams of high biobased contents, expectedly responding to the sustainability demands of the foam sector. It is potentially compatible to the retrofitting of industrial foaming infrastructures, which is of paramount importance to accommodate existing foam production plants and address the huge foam market demands.

Preparation and fire resistance modification on tannin-based non-isocyanate polyurethane (NIPU) rigid foams

Non-isocyanate polyurethane (NIPU) as a new type of polyurethane material has become a hot research topic in the polyurethane industry due to its no utilization of toxic isocyanates during the synthesis process. And the developing on recyclable biomass materials has also much attention in the industrial sector, hence the preparation and application of bio-based NIPU has also become a very meaningful study work. So, in this paper, tannin as a biomass material was used to synthesize tannin based non-isocyanate polyurethanes (TNIPU) resin, and then successfully prepared a self-blowing TNIPU foam at room temperature by using formic acid as initiator and glutaraldehyde as cross-linking agent. The compressive strength of this foam as high as 0.8 MPa, which is an excellent compressive performance. Meanwhile it will return to the state before compression when removing the pressure. This indicating that the foam has good toughness. In addition, formic acid can react with the amino groups in TNIPU to form amide substances, and generated enough heat to initiate the foaming process. Glutaraldehyde, as a crosslinking agent, reacts with the amino group in TNIPU to form a network structure system. By scanning electron microscope (SEM) observation of the cell shapes, it can be seen that the foam cells were uniform in size and shape, and the cell pores showed open and closed cells. The limiting oxygen index (LOI) tested value of this TNIPU foam is 24.45 % without any flame retardant added, but compared to the LOI value of polyurethane foam (17 %–19 %), TNIPU foam reveal a better fire resistance. It has a wider application prospect.

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

Non-isocyanate polyurethane (NIPU) networks physically modified with octa(3-hydroxy-3-methylbutyldimethylsiloxy)POSS (8OHPOSS, 0-10 wt%) were conditioned in environments of different relative humidities (up to 97%) to study water-polymer interactions. The equilibrium sorption isotherms are of Brunauer type III in a water activity range of 0-0.97 and are discussed in terms of the Guggenheim (GAB) sorption model. The study shows that the introduction of 8OHPOSS, even in a large amount (10 wt%), does not hinder the water affinity of the NIPU network despite the hydrophobic nature of POSS; this is attributable to the homogenous dispersion of POSS in the polymer matrix. The shift in the urethane-derived carbonyl bands toward lower wavenumbers with a simultaneous shift in the urethane N-H bending bands toward higher wavenumbers exposes the breakage of polymer-polymer hydrogen bonds upon water uptake due to the formation of stronger water-polymer hydrogen bonds. Upon water absorption, a notable decrease in the glass transition temperature (Tg) is observed for all studied materials. The progressive reduction in Tg with water uptake is driven by plasticization and slaving mechanisms. POSS moieties are thought to impact slaving indirectly by slightly affecting water uptake at very high hydration levels.

Preparation and properties of multi-responsive self-healing non-isocyanate polyurethane gel coating

ABSTRACT Traditional polyurethane coating is prepared by combining isocyanate and polyol, but isocyanate is toxic, which is not conducive to the sustainable development of ecological environment. In this paper, dibutyltin dilaurate (DBTDL) was used as catalyst to synthesize dicyclic carbonate from four different acids and glycerol carbonates. Then, it was gradually polymerized with isophorone diamine (IPDA) and 4,4’-diaminodiphenyl disulfide ether to synthesize self-healing non-isocyanate polyurethane (NIPU). The effects of different acid types on coating forming and self-healing properties of NIPU were studied. Then, polypyrrole modified carbon nanotubes were prepared and physically blended with NIPU to obtain a responsive NIPU gel coating. The results show that NIPU has excellent scratch repair performance at 70°C by optical microscopy; Through the dissolution and re-formation of NIPU by N, N-dimethylformamide, it is proved that the material has repeatable processability and is conducive to the sustainable development of ecological environment; The high precision multimeter proved that NIPU has the responsiveness under different chemical environment of acid, alkali, oxidation and reduction. The coating has broad application prospects in biomimetic technology, biology, electronics and other fields.