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The prevention of chronic wound formation has already been a primary subject in wound management, particularly for deep wounds. The electrospun nanofiber membranes hold tremendous potential in the prevention of chronic wounds due to their micro/nano pore structures. Currently, many natural and synthetic materials have been utilized in the fabrication of nanofiber membranes. However, striking a balance between the structural stability and the biocompatibility remains challenging. It is necessary not only to ensure the long-term durability of nanofiber membranes but also to enhance their biocompatibility for alleviating patients' suffering. In this study, we reported a nanofiber membrane dressing with excellent biocompatibility and mechanical properties, which is potential for the treatment of deep wounds. The basal material chosen for the preparation of the nanofiber membrane was a co-polyester (NI-LPGD5) synthesized by non-isocyanate polyurethane (NIPU) and polyglycolic acid with a dihydroxy structure (LPGD-synthesized from glycolic acid and neopentyl glycol). Moreover, curcumin was also added as a bioactive substance to enhance the pro-healing effect of dressings. The physicochemical properties of the prepared nanofiber membranes were characterized through various physicochemical tools. Our results demonstrated that the NI-LPGD5 co-polymer can be electrospun into smooth fibers. Meanwhile, curcumin-loaded nanofiber membranes (Cur/NI-LPGD5) also exhibited a favorable microscopic morphology. The fabricated membranes exhibited suitable mechanical properties, outstanding hygroscopic-swelling rate and water vapor transmittance. Besides, in vitro cell culturing, the cells on the NI-LPGD5 membrane maintained their maximum viability. The potential of in vivo wound healing was further demonstrated through animal experiments. The experimental results showed that the nanofiber membranes effectively prevented chronic wounds from forming and promoted granulation tissue growth without replacing the dressing throughout the healing process. We also found that these nanofiber membranes could effectively promote the expression of related biomarkers to accelerate wound healing, particularly the Cur/NI-LPGD5 membrane. In conclusion, the fabricated membranes possess suitable physicochemical properties and promising bioactivity. As a result, it effectively prevented the formation of chronic wounds and demonstrated significant potential in reducing the frequency of dressing changes.

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This study presents the synthesis and characterization of non-isocyanate polyurethanes (NIPU) derived from the copolymerization of cyclic-carbonated soybean oil (CSBO) and cyclic carbonate (CC)-terminated poly(ether carbonate) (RCC). Using a double-metal cyanide catalyst, poly(ether carbonate) polyol was first synthesized through the copolymerization of carbon dioxide and propylene oxide. The terminal hydroxyl group was then subjected to a substitution reaction with a five-membered CC group using glycerol-1,2-carbonate and oxalyl chloride, yielding RCC. Attempts to prepare NIPU solely using RCC and diamine were unsuccessful, possibly due to the low CC functionality and the aminolysis of RCC's linear carbonate repeating units. However, when combined with CSBO, solid NIPUs were successfully obtained, exhibiting good thermal stability along with enhanced mechanical properties compared to conventional CSBO-based NIPU formulations. Overall, this study underscores the potential of leveraging renewable resources and carbon capture technologies to develop sustainable NIPUs with tailored properties, thereby expanding their range of applications.

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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.

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This paper describes the synthesis of NIPU by using cardanol as starting material. A cardanol formaldehyde oligomer was first prepared through the reaction of cardanol and formaldehyde, catalyzed by citric acid. The resulting oligomer was then subjected to epoxidation with m-chloroperbenzoic acid to obtain an epoxide compound, which was subsequently used to fix carbon dioxide (CO2) and form a cyclic carbonate. Using this cyclic carbonate, along with an amine, cardanol-based isocyanate polyurethane (NIPU) was prepared. Different characterization methods, such as Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and thermogravimetric analysis (TGA), were used to confirm the synthesis of the four intermediate products and NIPU in the reaction process. This study highlights the promise of bio-based NIPU as a sustainable alternative in a number of applications while offering insightful information on the synthesis and characterization of the material.

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Three-dimensional (3D)-printed orthopedic surgical guides have the potential to provide personalized precision treatment. Non-isocyanate polyurethane (NIPU) is commonly used in the 3D printing of biomedical materials but its application in the orthopedic surgical guide is limited by poor mechanical properties and biocompatibility. In this study, we fabricated non-isocyanate polyurethane acrylate (NIPUA) photosensitive resin with superior biocompatibility and mechanical properties required for 3D-printed orthopedic surgical guides. NIPU prepolymer was synthesized by a ring-opening reaction and a ring acrylation reaction. NIPUA was further synthesized using polyethylene glycol diacrylate (PEGDA) as a modified material based on sustainable synthesis with reduced synthesis time. NIPUA showed the best tensile and flexural strengths when the PEGDA content reached 12 wt.%. NIPUA exhibited higher thermal stability, hemocompatibility, superior biocompatibility to ME3T3-E1 bone cells and C1C12 muscle cells, and non-immunogenic effect toward macrophages compared with commercial photosensitive resins. Commercial resins triggered a severe inflammatory response during in vivo implantation, but this effect was not observed during NIPUA implantation. Transcriptome analysis showed downregulation of cell death and cell cycle disruption-related genes, such as CDK2, CDKN1a, and GADD45a, and upregulation of autophagy and anti-tumor activity-related genes, such as MYC, PLK1, and BUB1b, in NIPUA-treated MC3T3-E1 cells compared with commercial resin-treated MC3T3-E1 cells. In conclusion, NIPUA resin showed excellent mechanical and thermal properties as well as good biocompatibility toward bone cells, muscle cells, and macrophages, suggesting its possible application in the 3D printing of customized orthopedic surgical guides.

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Flexible hard coatings with strong adhesion are critical requirements for several foldable devices and marine applications; however, only a few such coatings have been reported. Herein, we report a non-isocyanate polyurethane (NIPU) coating prepared by the epoxy-oligosiloxane nanocluster-amine curing reaction and cyclic carbonate-amine polyaddition, where the former provides the coating with ceramic-like hardness and polymer-like flexibility while the latter polymerization results in NIPU with strong substrate adhesion. The coating is transparent (>92% transmittance), hard (5-7 H), and flexible (2 mm bending diameter). It has strong adhesion to various substrates including aluminum alloy, titanium, steel, glass, ceramic, epoxy, and polyethylene terephthalate (2-8 MPa), which can be attributed to the high density of polar groups in NIPU. Moreover, we can facilely endow the coating with anti-icing, self-cleaning, and anti-smudge capabilities by incorporating amine-terminated low-surface-tension polydimethylsiloxane (PDMS) to replace a part of the amine curing agent. Particularly, the mechanical properties of NIPU coatings are only slightly affected by the introduction of low-content PDMS since it intends to enrich on the surface. The novel coating has promising future for use in fields of foldable devices and marine applications.

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This article focuses on the synthesis of polyhydroxyurethane (PHU) materials containing novel phosphorus flame retardants (FR). Four different phosphorus compounds were grafted onto cyclic carbonate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diethyl phosphite (DEP), diphenyl phosphite (DPP) and dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO). Thus, three novel phosphorus reactive cyclic carbonates which have never been reported so far were synthetized. Phosphorus FR containing PHU materials were characterized by FTIR to evidence the total conversion of the cyclic carbonate. Moreover, the gel contents up to 80% confirmed the formation of the polymer network. Then, the thermal stability and the flame-retardant properties were investigated by thermogravimetric analyses, cone calorimeter and pyrolysis combustion flow calorimeter. The mode of action of phosphorus compounds, depending on the oxidation state, was especially highlighted. Phosphonate (+III) provided better action in a condensed phase than phosphinate thanks to a more efficient char formation. Among phosphonates, differences were observed in terms of char-formation rate and expansion. DEP provided the best flame-retardant properties, with a reduction of 76% of pHRR with 2 wt% of phosphorus in cone calorimeter analysis. Therefore, this article highlighted the different modes of action of phosphorus flame retardants, depending on the oxidation state of phosphorus, in PHU materials.

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Polyurethane foams (PUFs) are a significant group of polymeric foam materials. Thanks to their outstanding mechanical, chemical, and physical properties, they are implemented successfully in a wide range of applications. Conventionally, PUFs are obtained in polyaddition reactions between polyols, diisoycyanate, and water to get a CO2 foaming agent. The toxicity of isocyanate has attracted considerable attention from both scientists and industry professionals to explore cleaner synthesis routes for polyurethanes excluding the use of isocyanate. The polyaddition of cyclic carbonates (CCs) and polyfunctional amines in the presence of an external blowing agent or by self-blowing appears to be the most promising route to substitute the conventional PUFs process and to produce isocyanate-free polyurethane foams (NIPUFs). Especially for polyhydroxyurethane foams (PHUFs), the use of a blowing agent is essential to regenerate the gas responsible for the creation of the cells that are the basis of the foam. In this review, we report on the use of different blowing agents, such as Poly(methylhydrogensiloxane) (PHMS) and liquid fluorohydrocarbons for the preparation of NIPUFs. Furthermore, the preparation of NIPUFs using the self-blowing technique to produce gas without external blowing agents is assessed. Finally, various biologically derived NIPUFs are presented, including self-blown NIPUFs and NIPUFs with an external blowing agent.

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Polyurethanes (PUs) are versatile and widespread, particularly as flexible and rigid foams. To avoid isocyanates and other toxic reagents required for synthesis, such as phosgene, alternative synthetic routes have been utilized to produce non-isocyanate polyurethanes (NIPUs). A thermally and flame-resistant rigid NIPU was produced from environmentally benign and bio-sourced ingredients, requiring no catalyst or solvents. A foamed structure was obtained by the addition of glutaraldehyde and four different carboxylic acids: malic acid, maleic acid, citric acid, and aconitic acid. The resulting morphology, thermal degradation, and flame resistance of each foam were compared. The properties vary with each carboxylic acid used, but in each case, peak thermal degradation and peak heat release are postponed by >100 °C compared to commercial rigid PU foam. Furthermore, in a butane torch test, NIPU foams exhibit an 80% higher remaining mass and a 75% reduction in afterburn time, compared to commercial polyurethane. This bio-based polyurethane eliminates the hazards of traditional PUs, while imparting inherent thermal stability and flame resistance uncharacteristic of conventional foams.

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For 80 years, polyisocyanates and polyols were central building blocks for the industrial fabrication of polyurethane (PU) foams. By their partial hydrolysis, isocyanates release CO2 that expands the PU network. Substituting this toxic isocyanate-based chemistry by a more sustainable variant-that in situ forms CO2 by hydrolysis of a comonomer-is urgently needed for producing greener cellular materials. Herein, we report a facile, up-scalable process, potentially compatible to existing infrastructures, to rapidly prepare water-induced self-blown non-isocyanate polyurethane (NIPU) foams. We show that formulations composed of poly(cyclic carbonate)s and polyamines furnish rigid or flexible NIPU foams by partial hydrolysis of cyclic carbonates in the presence of a catalyst. By utilizing readily available low cost starting materials, this simple but robust process gives access to greener PU foams, expectedly responding to the sustainability demands of many sectors.

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Poly(hydroxyurethanes) (PHUs) have been suggested as isocyanate-free, low-toxicity alternatives to polyurethanes (PUs). However, PHUs present low mechanical properties due to the presence of side reactions that limit the production of high-molar mass polymers. Here, we present the synthesis under mild conditions and atmospheric pressure of bi-cyclic carbonate monomer for the production of PHU nanocomposites with good physical properties. The kinetics of the bi-cyclic carbonate synthesis and its complete conversion to urethane were followed by FTIR. The addition of functionalized boron nitrate (f-BN) with sucrose crystals improved the thermal degradation temperature as well as the glass transition by approximately 20 °C and 10 °C, respectively. The storage modulus of PHU films gradually increases with the concentration of f-BN in the composite.

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Plastic pollution is recognized as a major environmental problem in many countries. Over the last decade, academics have embraced research on bioplastics to discover newer high-end green materials. However, the end-of-life environmental fate of such materials is not adequately understood. Non-isocyanate polyhydroxyurethanes (PHUs) are green engineering materials with huge potential to replace traditional polyurethanes. Despite this immense potential, a number of questions about their environmental fate remain unanswered. The present study investigated the extent and mechanisms underlying soil biodegradation of PHUs and determined whether the deterioration of PHUs within starch bioplastics (ST) can improve the biodegradation of starch (ST)-PHU hybrids. Soil microbiomes managed to effectively and quickly digest not only PHUs but also ST-PHU hybrids. All ST-PHU hybrids were characterized by exceptional biodegradability with mass losses of up to ~88% following a soil burial time of only 120 days. The biodegradation of ST-alone bioplastics was 69% under identical conditions. The presence of cellulose nanocrystals (CNC) reduced the potential for the soil microbial community to degrade nanohybrids (ST-PHU-CNC). Microbially digested bioplastics with PHU presented less stages of thermal degradation, and reduced intensities of FTIR, NMR and XPS signals compared to the original films, indicating improvement of the biodegradation mechanism. These findings suggested the positive environmental implications of PHU in improving the bioplastic's degradation and their potential for future applications.

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Carbonation of epoxidized linseed oil (CELO) containing five-membered cyclic carbonate (CC5) groups has been optimized to 95% by reacting epoxidized linseed oil (ELO) with carbon dioxide (CO2) and tetrabutylammonium bromide (TBAB) as catalysts. The effect of reaction variables (temperature, CO2 pressure, and catalyst concentration) on the reaction parameters (conversion, carbonation and selectivity) in an autoclave system was investigated. The reactions were monitored, and the products were characterized by Fourier Transform Infrared Spectroscopy (FT-IR), carbon-13 nuclear magnetic resonance (13C-NMR) and proton nuclear magnetic resonance (1H-NMR) spectroscopies. The results showed that when carrying out the reaction at high temperature (from 90 °C to 120 °C) and CO2 pressure (60-120 psi), the reaction's conversion improves; however, the selectivity of the reaction decreases due to the promotion of side reactions. Regarding the catalyst, increasing the TBAB concentration from 2.0 to 5.0 w/w% favors selectivity. The presence of a secondary mechanism is based on the formation of a carboxylate ion, which was formed due to the interaction of CO2 with the catalyst and was demonstrated through 13C-NMR and FT-IR. The combination of these factors makes it possible to obtain the largest conversion (96%), carbonation (95%), and selectivity (99%) values reported until now, which are obtained at low temperature (90 °C), low pressure (60 psi) and high catalyst concentration (5.0% TBAB).

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In this work, a straightforward and efficient synthesis approach to renewable non-isocyanate polyurethanes (NIPUs) is described. For this purpose, suitable and renewable carbamate monomers, possessing two double bonds, are synthesized from hydroxamic fatty acid derivatives via the Lossen rearrangement in a one-step synthesis, and sustainable dithiols are synthesized from dialkenes derived from renewable feedstock (i.e., limonene and 1,4-cyclohexadiene). Subsequently, the comonomers are polymerized with the highly efficient thiol-ene reaction to produce NIPUs with Mn values up to 26 kg mol-1 bearing thioether linkages. The main side product of the Lossen rearrangement, a symmetric urea, can also be polymerized in the same fashion. Important in the view of sustainability, the monomer mixture can also be used directly, without separation. The obtained polymers are characterized by NMR, attenuated total reflection-infrared spectroscopy, differential scanning calorimetry, and size exclusion chromatography.

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Developing degradable and self-healable elastomers composed of reusable resources is of great value but is rarely reported because of the undegradable molecular chains. Herein, we report a class of degradable and self-healable vitrimers based on non-isocyanate polyurethane elastomer. Such vitrimers are fabricated by copolymerizing bis(6-membered cyclic carbonate) and amino-terminated liquid nitrile rubber. The networks topologies can rearrange by transcarbonation exchange reactions between hydroxyl and carbonate groups at elevated temperatures; as such, vitrimers after reprocessing can recover 82.9-95.6% of initial tensile strength and 59-131% of initial storage modulus. Interestingly, the networks can be hydrolyzed and decarbonated in the strong acid solution to recover 75% of the pure di(trimethylolpropane) monomer. Additionally, the elastomer exhibits excellent self-healing efficiency (~88%) and fracture strain (~1,200%) by tuning the monomer feeding ratio. Therefore, this work provides a novel strategy to fabricate the sustainable elastomers with minimum environmental impact.

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A partially biobased self-blowing and self-hardening polyurethane foam from glucose-based non-isocyanate polyurethanes (g-NIPU) was prepared by reaction of glucose with dimethyl carbonate and hexamethylene diamine. However, these foam types generally require a high foaming temperature. In this paper, a self-blowing foam based on g-NIPU was prepared at room temperature by using maleic acid as an initiator and glutaraldehyde as a crosslinker. Water absorption, compression resistance, and fire resistance were tested. Scanning electron microscopy (SEM) was used to observe the foam cells structure. Middle infrared (ATR FT-MIR) and Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF) mass spectrometry were used to help to analyze the reactions during the foaming process. The results obtained showed that self- blowing rigid foams have good compression, this being directly proportional to the foam density. Increasing the amount of glutaraldehyde or reducing maleic acid thickens the cell walls and increases the density of the foams. MALDI-TOF analysis showed that g-NIPU reacts with both maleic acid and glutaraldehyde. The foams presented poor fire resistance indicating that, as for isocyanate based polyurethane foams, addition of a fire retardant would be necessary.

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Dimer acid cyclocarbonate (DACC) is synthesized from glycerol carbonate (GC) and Sapium sebiferum oil-derived dimer acid (DA, 9-[(Z)-non-3-enyl]-10-octylnonadecanedioic acid). Meanwhile, DACC can be used for synthetic materials of bio-based non-isocyanate polyurethane (bio-NIPU). In this study, DACC was synthesized by the esterification of dimer acid and glycerol carbonate using Novozym 435 (Candida antarctica lipase B) as the biocatalyst. Via the optimizing reaction conditions, the highest yield of 76.00% and the lowest acid value of 43.82 mg KOH/g were obtained. The product was confirmed and characterized by Fourier transform-infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). Then, the synthetic DACC was further used to synthesize bio-NIPU, which was examined by FTIR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC), indicating that it possesses very good physio-chemical properties and unique material quality with a potential prospect in applications.

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Non-isocyanate polyurethane (NIPU) was prepared from Jatropha curcas oil (JCO) and its alkyd resin via curing with different diamines. The isocyanate-free approach is a green chemistry route, wherein carbon dioxide conversion plays a major role in NIPU preparation. Catalytic carbon dioxide fixation can be achieved through carbonation of epoxidized derivatives of JCO. In this study, 1,3-diaminopropane (DM) and isophorone diamine (IPDA) were used as curing agents separately. Cyclic carbonate conversion was catalyzed by tetrabutylammonium bromide. After epoxy conversion, carbonated JCO (CJCO) and carbonated alkyd resin (CC-AR) with carbonate contents of 24.9 and 20.2 wt %, respectively, were obtained. The molecular weight of CJCO and CC-AR were determined by gel permeation chromatography. JCO carbonates were cured with different amine contents. CJCO was blended with different weight ratios of CC-AR to improve its characteristics. The cured NIPU film was characterized by spectroscopic techniques, differential scanning calorimetry, and a universal testing machine. Field emission scanning electron microscopy was used to analyze the morphology of the NIPU film before and after solvent treatment. The solvent effects on the NIPU film interfacial surface were investigated with water, 30% ethanol, methyl ethyl ketone, 10% HCl, 10% NaCl, and 5% NaOH. NIPU based on CCJO and CC-AR (ratio of 1:3) with IPDA crosslink exhibits high glass transition temperature (44 °C), better solvent and chemical resistance, and Young's modulus (680 MPa) compared with the blend crosslinked with DM. Thus, this study showed that the presence of CC-AR in CJCO-based NIPU can improve the thermomechanical and chemical resistance performance of the NIPU film via a green technology approach.