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1.
Materials (Basel) ; 17(13)2024 Jul 07.
Article in English | MEDLINE | ID: mdl-38998437

ABSTRACT

This paper presents the results of research on polyurethane viscoelastic foams (PUVFs) modified with biomaterials. This investigation looked at the effect of the biomaterials on the foaming processes, as well as the acoustical and selected physical-mechanical properties of the foams. Various types of rapeseed oil biopolyols and microcellulose were used to modify the materials. The analysis of properties covered a reference biopolyol-free sample and materials containing 10 wt.%, 20 wt.%, and 30 wt.% of different types of biopolyols in the mixture of polyol components. The biopolyols differed in terms of functionality and hydroxyl value (OHv). Next, a selected formulation was modified with various microcellulose biofillers in the amount of 0.5-2 wt.%. The PUVFs, with apparent densities of more than 210 kg/m3 and open-cell structures (more than 85% of open cells), showed a slow recovery to their original shape after deformation when the pressure force was removed. They were also characterized by a tensile strength in the range of 156-264 kPa, elongation at break of 310-510%, hardness of 8.1-23.1 kPa, and a high comfort factor of 3.1-7.1. The introduction of biopolyols into the polyurethane system resulted in changes in sound intensity levels of up to 31.45%, while the addition of fillers resulted in changes in sound intensity levels of up to 13.81%.

2.
Int J Biol Macromol ; : 133617, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38960219

ABSTRACT

Non-isocyanate polyurethanes (NIPUs) have attracted increasing attention as a sustainable alternative to conventional isocyanate-based polyurethanes. This study synthesized non-isocyanate hydroxyurethanes (NIHUs) through an addition reaction between propylene carbonate (PC) and 1,2-ethylenediamine (EDA). The resulting NIHU was then hybridized with carboxymethyl cellulose (CMC) to investigate its hybridization potential. Structural analysis through FTIR, NMR, and XRD confirmed the crystalline nature of NIHU, featuring urethane bonds and abundant hydroxyl groups. It was found that NIHU and CMC interacted by forming hydrogen bonds between hydroxyl groups of NIHU and carboxyl groups of CMC, resulting in a dense CMC/NIHU hybrid structure. NMR and XRD analyses revealed changes in the hybrids' chain mobility, the Young's modulus of the hybrid with 30 % NIHU content decreased from 1627 MPa to 502 MPa relative to CMC, and the elongation at break increased from 4.44 % to 17.2 %. Increasing the concentration of NIHU in CMC reduced the hydrophobicity, in terms of water contact angle, from 70° to 41.7°. The simplicity of the synthesis method for NIHU, coupled with the desirable structure, strength, and balanced flexibility of CMC/NIHU hybrids, is expected to facilitate the production of NIHU-rich hybrids and increase their application in packaging.

3.
Acta Biomater ; 183: 130-145, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38815684

ABSTRACT

Osteoarthritis (OA) poses significant therapeutic challenges, particularly OA that affects the hand. Currently available treatment strategies are often limited in terms of their efficacy in managing pain, regulating invasiveness, and restoring joint function. The APRICOTⓇ implant system developed by Aurora Medical Ltd (Chichester, UK) introduces a minimally invasive, bone-conserving approach for treating hand OA (https://apricot-project.eu/). By utilizing polycarbonate urethane (PCU), this implant incorporates a caterpillar track-inspired design to promote the restoration of natural movement to the joint. Surface modifications of PCU have been proposed for the biological fixation of the implant. This study investigated the biocompatibility of PCU alone or in combination with two surface modifications, namely dopamine-carboxymethylcellulose (dCMC) and calcium-phosphate (CaP) coatings. In a rat soft tissue model, native and CaP-coated PCU foils did not increase cellular migration or cytotoxicity at the implant-soft tissue interface after 3 d, showing gene expression of proinflammatory cytokines similar to that in non-implanted sham sites. However, dCMC induced an amplified initial inflammatory response that was characterized by increased chemotaxis and cytotoxicity, as well as pronounced gene activation of proinflammatory macrophages and neoangiogenesis. By 21 d, inflammation subsided in all the groups, allowing for implant encapsulation. In a rat bone model, 6 d and 28 d after release of the periosteum, all implant types were adapted to the bone surface with a surrounding fibrous capsule and no protracted inflammatory response was observed. These findings demonstrated the biocompatibility of native and CaP-coated PCU foils as components of APRICOTⓇ implants. STATEMENT OF SIGNIFICANCE: Hand osteoarthritis treatments require materials that minimize irritation of the delicate finger joints. Differing from existing treatments, the APRICOTⓇ implant leverages polycarbonate urethane (PCU) for minimally invasive joint replacement. This interdisciplinary, preclinical study investigated the biocompatibility of thin polycarbonate urethane (PCU) foils and their surface modifications with calcium-phosphate (CaP) or dopamine-carboxymethylcellulose (dCMC). Cellular and morphological analyses revealed that both native and Ca-P coated PCU elicit transient inflammation, similar to sham sites, and a thin fibrous encapsulation in soft tissues and on bone surfaces. However, dCMC surface modification amplified initial chemotaxis and cytotoxicity, with pronounced activation of proinflammatory and neoangiogenesis genes. Therefore, native and CaP-coated PCU possess sought-for biocompatible properties, crucial for patient safety and performance of APRICOTⓇ implant.


Subject(s)
Calcium Phosphates , Animals , Male , Rats , Calcium Phosphates/chemistry , Calcium Phosphates/pharmacology , Dopamine/metabolism , Dopamine/pharmacology , Coated Materials, Biocompatible/chemistry , Coated Materials, Biocompatible/pharmacology , Polycarboxylate Cement/chemistry , Joint Prosthesis , Carboxymethylcellulose Sodium/chemistry , Carboxymethylcellulose Sodium/pharmacology , Urethane/chemistry
4.
Angew Chem Int Ed Engl ; 63(28): e202404186, 2024 Jul 08.
Article in English | MEDLINE | ID: mdl-38691059

ABSTRACT

The introduction of nitrogen-containing functional groups to chiral polymer backbones enables the tailoring of physical properties and offers opportunities for further post-polymerization modification. However, the substrate scope of such polymers is extremely limited because monomers having nitrogen-containing groups can change coordination state with respect to the metal centers, thus decreasing the activity and enantioselectivity and even poisoning the catalyst completely. In this paper, we report our attempts to carry out the asymmetric copolymerization of meso-epoxide with highly reactive isocyanates. In particular, we found that biphenol-linked bimetallic Co(III) complexes with multiple chiral centers are very efficient in catalyzing this asymmetric copolymerization reaction, affording optically active polyurethanes with a completely alternating nature and a high enantioselectivity of up to 94 % ee. Crucially, we identified that the steric hindrance at the phenolate ortho position of the ligand strongly influences the catalytic activity and product enantioselectivity. In addition, density functional theory calculations revealed that the highly sterically bulky substituents change the mechanism from bimetallic to monometallic, and result in the unexpected inversion of the chiral induction direction. Moreover, the high stereoregularity of the produced polyurethanes enhances their thermal stability, and they can be selectively decomposed into oxazolidinones. This study offers a versatile methodology for the synthesis of chiral polymers containing nitrogen functionalities.

5.
Eur J Med Res ; 29(1): 264, 2024 May 03.
Article in English | MEDLINE | ID: mdl-38698476

ABSTRACT

BACKGROUND: The fundamental prerequisite for prognostically favorable postoperative results of peripheral nerve repair is stable neurorrhaphy without interruption and gap formation. METHODS: This study evaluates 60 neurorrhaphies on femoral chicken nerves in terms of the procedure and the biomechanical properties. Sutured neurorrhaphies (n = 15) served as control and three sutureless adhesive-based nerve repair techniques: Fibrin glue (n = 15), Histoacryl glue (n = 15), and the novel polyurethane adhesive VIVO (n = 15). Tensile and elongation tests of neurorrhaphies were performed on a tensile testing machine at a displacement rate of 20 mm/min until failure. The maximum tensile force and elongation were recorded. RESULTS: All adhesive-based neurorrhaphies were significant faster in preparation compared to sutured anastomoses (p < 0.001). Neurorrhaphies by sutured (102.8 [cN]; p < 0.001), Histoacryl (91.5 [cN]; p < 0.001) and VIVO (45.47 [cN]; p < 0.05) withstood significant higher longitudinal tensile forces compared to fibrin glue (10.55 [cN]). VIVO, with △L/L0 of 6.96 [%], showed significantly higher elongation (p < 0.001) compared to neurorrhaphy using fibrin glue. CONCLUSION: Within the limitations of an in vitro study the adhesive-based neurorrhaphy technique with VIVO and Histoacryl have the biomechanical potential to offer alternatives to sutured neuroanastomosis because of their stability, and faster handling. Further in vivo studies are required to evaluate functional outcomes and confirm safety.


Subject(s)
Anastomosis, Surgical , Chickens , Tensile Strength , Animals , Anastomosis, Surgical/methods , Biomechanical Phenomena , Tissue Adhesives/pharmacology , Fibrin Tissue Adhesive/pharmacology , Peripheral Nerves/surgery , Peripheral Nerves/physiology , Adhesives , Neurosurgical Procedures/methods
6.
Chemphyschem ; : e202400366, 2024 May 16.
Article in English | MEDLINE | ID: mdl-38753463

ABSTRACT

Polyurethanes are commodity materials used for multiple applications. In recent years, a new category of polyurethane material has emerged, characterized by the lack of polymer molar mass distribution, control of the monomer arrangement in the chain, and even full stereocontrol. Various multistep synthesis strategies have been developed to fabricate sequence-defined polyurethanes. However, synthesizing stereocontrolled polyurethanes with a controlled sequence is still a challenge. Polyurethanes with structural precision, as represented by biopolymers, i.e. proteins or nucleic acids, have opened new application directions for these groups of materials. It has been shown that polyurethanes can be used as biomimetics, information carriers, molecular tags, and materials with strictly controlled properties. Precise synthesis of macromolecules allows us to fine-tune the properties of polymers to specific needs. Therefore, it is essential to collect information on the sequence-structure relationship of polymers. In our work, we present synthetic pathways to make sequence and stereo-defined oligourethanes. We demonstrate that structural details, i.e., the monomer sequences and position of the stereocenter, have a tremendous effect on the thermal properties of model oligourethanes. We show that the introduction of chirality by constitutional isomerization can be used to program the thermal characteristics of polymers, which are key features for material applications.

7.
Int J Mol Sci ; 25(10)2024 May 18.
Article in English | MEDLINE | ID: mdl-38791552

ABSTRACT

Polyurethanes are among the most significant types of polymers in development; these materials are used to produce construction products intended for work in various conditions. Nowadays, it is important to develop methods for fire load reduction by using new kinds of additives or monomers containing elements responsible for materials' fire resistance. Currently, additive antipyrines or reactive flame retardants can be used during polyurethane material processing. The use of additives usually leads to the migration or volatilization of the additive to the surface of the material, which causes the loss of the resistance and aesthetic values of the product. Reactive flame retardants form compounds containing special functional groups that can be chemically bonded with monomers during polymerization, which can prevent volatilization or migration to the surface of the material. In this study, reactive flame retardants are compared. Their impacts on polyurethane flame retardancy, combustion mechanism, and environment are described.


Subject(s)
Flame Retardants , Polyurethanes , Flame Retardants/analysis , Polyurethanes/chemistry , Green Chemistry Technology/methods
8.
J Colloid Interface Sci ; 670: 223-233, 2024 Sep 15.
Article in English | MEDLINE | ID: mdl-38761575

ABSTRACT

Macrophages can kill bacteria and viruses by releasing free radicals, which provides a possible approach to construct antifouling coatings with dynamic surfaces that release free radicals if the breaking of dynamic covalent bonds is precisely regulated. Herein, inspired by the defensive behavior of macrophages of releasing free radicals to kill bacteria and viruses, a marine antifouling coating composed of polyurethane incorporating dimethylglyoxime (PUx-DMG) is prepared by precise regulation of dynamic oxime-urethane covalent bonds. The obtained alkyl radical (R·) derived from the cleavage of the oxime-urethane bonds manages to effectively suppress the attachment of marine biofouling. Moreover, the intrinsic dynamic surface makes it difficult for biofouling to adhere and ultimately achieves sustainable antifouling property. Notably, the PU50-DMG coating not only presents efficient antibacterial and antialgae properties, but also prevents macroorganisms from settling in the sea for up to 4 months. This provides a pioneer broad-spectrum strategy to explore the marine antifouling coatings.


Subject(s)
Anti-Bacterial Agents , Biofouling , Macrophages , Surface Properties , Biofouling/prevention & control , Macrophages/drug effects , Macrophages/metabolism , Animals , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Polyurethanes/chemistry , Polyurethanes/pharmacology , Mice , Oximes/chemistry , Oximes/pharmacology , RAW 264.7 Cells , Particle Size , Microbial Sensitivity Tests , Molecular Structure
9.
Sci Total Environ ; 934: 173250, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38761928

ABSTRACT

Isocyanides and isocyanates are some of the most reactive compounds in organic chemistry, making them perceived as compounds with high potential for use in both the laboratory and industry. With their high reactivity also comes several disadvantages, most notably their potentially high toxicity. The following article is a collection of information on the toxic effects of the isocyanide group on the human body and the environment. Information on the mechanism of how these harmful substances affect living tissues and the environment, worldwide information on how to protect against these chemicals, current regulations, and exposure limits for specific countries is compiled. The latest research on the application uses of isocyanates and isocyanides is also outlined, as well as the latest safer and greener methods and techniques to work with these compounds. Additionally, the presented article can serve as a brief guide to the organic toxicity of a group of isocyanates and isocyanates.


Subject(s)
Cyanides , Isocyanates , Isocyanates/toxicity , Cyanides/chemistry , Humans , Environmental Pollutants/toxicity , Environmental Exposure
10.
Polymers (Basel) ; 16(7)2024 Mar 29.
Article in English | MEDLINE | ID: mdl-38611200

ABSTRACT

The utilization of polyols derived from renewable sources presents an opportunity to enhance the sustainability of rigid polyurethane (PUR) foams, thereby contributing to the advancement of a circular bioeconomy. This study explores the development of PUR rigid foams exclusively using polyols sourced from second-generation renewable biomass feedstocks, specifically depolymerized birch bark suberin (suberinic acids) and tall oil fatty acids. The polyols achieved a total renewable material content as high as 74%, with a suberinic acid content of 37%. Response surface modeling was employed to determine the optimal bio-polyol, blowing agents, and catalyst content, hence, optimizing the bio-based foam formulations. In addition, response surface modeling was applied to rigid PUR foam formulations based on commercially available petroleum-based polyols for comparison. The results, including apparent density (~40-44 kg/m3), closed cell content (~95%), compression strength (>0.2 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), demonstrated that the suberinic acids-based rigid PUR foam exhibited competitive qualities in comparison to petroleum-based polyols. Remarkably, the bio-based rigid PUR foams comprised up to 29% renewable materials. These findings highlight the potential of suberinic acid-tall oil polyols as effective candidates for developing rigid PUR foams, offering promising solutions for sustainable insulation applications.

11.
J Pharm Bioallied Sci ; 16(Suppl 1): S93-S96, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38595485

ABSTRACT

Objective: This systematic review examines the efficacy and biocompatibility of orthodontic clear aligner tooth aligners constructed from polyethylene terephthalate glycol (PeT-G), polypropylene (PP), polycarbonate (PC), thermoplastic polyurethanes (TPUs), and ethylene-vinyl acetate (EVA). Materials and Methods: To find relevant papers published through September 2021, PubMed was searched extensively. Randomized clinical trials (RCTs) and observational studies assessing the effectiveness and biocompatibility of the aligner materials were included. Data were extracted independently, and the quality of included research was appraised using relevant procedures. The research variability necessitated a narrative synthesis. Results: Five studies were included for comparison. All materials were biocompatible; however, PeT-G and EVA aligners caused the least tissue irritation. Patients preferred TPU aligners for initial comfort and PeT-G aligners for transparency and endurance. Conclusion: Biocompatible PeT-G, PP, PC, TPU, and EVA tooth aligners fix malocclusions. Aligner materials should be chosen based on patient preferences, treatment goals, and material qualities. For stronger proof, a longer-term study is needed.

12.
J Dent ; 143: 104902, 2024 04.
Article in English | MEDLINE | ID: mdl-38432352

ABSTRACT

OBJECTIVE: To investigate the effect of tooth whitening on biomechanical properties of vacuum-formed retainers (VFRs). METHODS: Using a split-mouth, randomised controlled trial design, thirty participants were randomly allocated to receive whitening on either the upper or the lower arch, using 10 % carbamide peroxide for two weeks. Biomechanical properties such as hardness, tensile strength, and surface roughness were assessed two weeks after whitening was completed. RESULTS: Tensile strength of the whitening arch (mean ± SD: 40.93 ± 3.96 MPa) was significantly lower than that of the control (47.40 ± 5.03 MPa) (difference 6.47 MPa, 95 % CI 4.51 - 8.42, p < 0.001). Hardness and internal roughness of the whitening arch (VHN = 14.63 ± 2.29 N/mm2 and Ra = 1.33 ± 0.35 µm, respectively) were significantly greater than those of the control (12.22 ± 1.86 N/mm2 and 0.96 ± 0.29 µm, respectively) (differences 2.41 N/mm2, 95 % CI 1.56 - 3.25, p < 0.001 and 0.37 µm, 95 % CI 0.23 - 0.51, p < 0.001, respectively). The whitening arch showed greater tooth colour change (ΔE = 6.00 ± 3.32) than the control (ΔE = 2.50 ± 1.70) (difference = 3.50, 95 % CI 2.43 - 4.56, p < 0.001). CONCLUSIONS: Based on this short-term study, marked tooth colour change was achieved by whitening with VFRs as the whitening trays, but this changed the VFRs' biomechanical properties, including a decrease in tensile strength and an increase in hardness and internal roughness. CLINICAL SIGNIFICANCE: The application of carbamide peroxide in VFRs may compromise their mechanical properties.


Subject(s)
Tooth Bleaching Agents , Tooth Bleaching , Tooth , Humans , Carbamide Peroxide , Vacuum , Tooth Bleaching Agents/pharmacology , Urea , Peroxides/pharmacology , Hydrogen Peroxide/pharmacology , Drug Combinations
13.
Front Chem ; 12: 1378324, 2024.
Article in English | MEDLINE | ID: mdl-38476653

ABSTRACT

Nowadays, polyurethanes (PUs) stand out as a promising option for drug delivery owing to their versatile properties. PUs have garnered significant attention in the biomedical sector and are extensively employed in diverse forms, including bulk devices, coatings, particles, and micelles. PUs are crucial in delivering various therapeutic agents such as antibiotics, anti-cancer medications, dermal treatments, and intravaginal rings. Effective drug release management is essential to ensure the intended therapeutic impact of PUs. Commercially available PU-based drug delivery products exemplify the adaptability of PUs in drug delivery, enabling researchers to tailor the polymer properties for specific drug release patterns. This review primarily focuses on the preparation of PU nanoparticles and their physiochemical properties for drug delivery applications, emphasizing how the formation of PUs affects the efficiency of drug delivery systems. Additionally, cutting-edge applications in drug delivery using PU nanoparticle systems, micelles, targeted, activatable, and fluorescence imaging-guided drug delivery applications are explored. Finally, the role of artificial intelligence and machine learning in drug design and delivery is discussed. The review concludes by addressing the challenges and providing perspectives on the future of PUs in drug delivery, aiming to inspire the design of more innovative solutions in this field.

14.
Macromol Rapid Commun ; : e2300724, 2024 Mar 14.
Article in English | MEDLINE | ID: mdl-38485136

ABSTRACT

Luminescent solar concentrators (LSCs) are spectral conversion devices offering interesting opportunities for the integration of photovoltaics into the built environment and portable systems. The Förster-resonance energy transfer (FRET) process can boost the optical response of LSCs by reducing energy losses typically associated to non-radiative processes occurring within the device under operation. In this work, a new class of FRET-based thin-film LSC devices is presented, in which the synthetic versatility of linear polyurethanes (PU) is exploited to control the photophysical properties and the device performance of the resulting LSCs. A series of luminescent linear PUs are synthesized in the presence of two novel bis-hydroxyl-functionalized luminophores of suitable optical properties, used as chain extenders during the step-growth polyaddition reaction for the formation of the linear macromolecular network. By synthetically tuning their composition, the obtained luminescent PUs can achieve a high energy transfer efficiency (≈90%) between the covalently linked luminophores. The corresponding LSC devices exhibit excellent photonic response, with external and internal photon efficiencies as high as ≈4% and ≈37%, respectively. Furthermore, their optimized power conversion efficiency combined with their enhanced average visible-light transmittance highlight their suitability for potential use as transparent solar energy devices.

15.
Adv Colloid Interface Sci ; 325: 103100, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38330882

ABSTRACT

Synthetic polymers, particularly polyurethanes (PUs), have revolutionized bioengineering and biomedical devices due to their customizable mechanical properties and long-term stability. However, the inherent hydrophobic nature of PU surfaces arises common issues such as high friction, strong protein adsorption, and thrombosis, especially in the physiological environment of blood contact. To overcome these issues, researchers have explored various modification techniques to improve the surface biofunctionality of PUs. In this review, we have systematically summarized several typical surface modification methods including surface plasma modification, surface oxidation-induced grafting polymerization, isocyanate-based chemistry coupling, UV-induced surface grafting polymerization, adhesives-assisted attachment strategy, small molecules-bridge grafting, solvent evaporation technique, and hydrogen bonding interaction. Correspondingly, the advantages, limitations, and future prospects of these surface modification methods were discussed. This review provides an important guidance or tool for developing surface functionalized PUs in the fields of bioengineering and medical devices.

16.
J Biomed Mater Res B Appl Biomater ; 112(2): e35381, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38348489

ABSTRACT

Recent studies show good osteoinductive properties of polyurethanes modified with polyhedral oligomeric silsesquioxanes (POSS). In this work, three types of POSS; propanediolisobutyl-POSS (PHI-POSS), disilanolisobutyl-POSS (DSI-POSS), and octahydroxybutyl-POSS (OCTA-POSS) were chemically incorporated into linear polyurethane based on an aliphatic isocyanate, hexamethylene diisocyanate (HDI), to obtain new nanohybrid PU-POSS materials. The full conversion of POSS was confirmed by Fourier transform infrared spectroscopy (FTIR-ATR) spectra of the model reactions with pure HDI. The materials obtained were investigated by FTIR, SEM-EDS, and DSC. The DSC studies showed the thermoplasticity of the obtained materials and apparently good recovery. 30-day immersion in SBF (simulated body fluid) revealed an increase in the rate of deposition of hydroxyapatite (HAp) for the highest POSS loadings, resulting in thick layers of hydroxyapatite (~60-40 µm), and the Ca/P ratio 1.67 (even 1.785). The structure and properties of the inorganic layer depend on the type of POSS, the number of hard segments, and those containing POSS, which can be tailored by changing the HDI/poly(tetramethylene glycol) (PTMG) ratio. Furthermore, the obtained composites revealed good biocompatibility, as confirmed by cytotoxicity tests conducted on two cell lines; normal human dermal fibroblasts (NHDF) and primary human osteoblasts (HOB). Adherent cells seeded on the tested materials showed viability even after a 48-h incubation. After this time, the population of viable, and proliferating cells exceeded 90%. Bioimaging studies have shown the fibroblast and osteoblast cells were well attached to the surface of the tested materials.


Subject(s)
Durapatite , Isocyanates , Polyurethanes , Humans , Polyurethanes/pharmacology , Polyurethanes/chemistry , Spectroscopy, Fourier Transform Infrared , Osteoblasts , Cell Line
17.
Adv Mater ; 36(16): e2311992, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38183353

ABSTRACT

Advances in modern industrial technology continue to place stricter demands on engineering polymeric materials, but simultaneously possessing superior strength and toughness remains a daunting challenge. Herein, a pioneering flexible cage-reinforced supramolecular elastomer (CSE) is reported that exhibits superb robustness, tear resistance, anti-fatigue, and shape memory properties, achieved by innovatively introducing organic imide cages (OICs) into supramolecular networks. Intriguingly, extremely small amounts of OICs make the elastomer stronger, significantly improving mechanical strength (85.0 MPa; ≈10-fold increase) and toughness (418.4 MJ m-3; ≈7-fold increase). Significantly, the cooperative effect of gradient hydrogen bonds and OICs is experimentally and theoretically demonstrated as flexible nodes, enabling more robust supramolecular networks. In short, the proposed strengthening strategy of adding flexible cages effectively balances the inherent conflict between material strength and toughness, and the prepared CSEs are anticipated to be served in large-scale devices such as TBMs in the future.

18.
Polymers (Basel) ; 16(2)2024 Jan 16.
Article in English | MEDLINE | ID: mdl-38257051

ABSTRACT

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.

19.
Polymers (Basel) ; 16(2)2024 Jan 16.
Article in English | MEDLINE | ID: mdl-38257057

ABSTRACT

In this work, biobased rigid polyurethane foams (PUFs) were developed with the aim of achieving thermal and fireproofing properties that can compete with those of the commercially available products. First, the synthesis of a biopolyol from a wood residue by means of a scaled-up process with suitable yield and reaction conditions was carried out. This biopolyol was able to substitute completely the synthetic polyols that are typically employed within a polyurethane formulation. Different formulations were developed to assess the effect of two flame retardants, namely, polyhedral oligomeric silsesquioxane (POSS) and amino polyphosphate (APP), in terms of their thermal properties and degradation and their fireproofing mechanism. The structure and the thermal degradation of the different formulations was evaluated via Fourier Transformed Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Likewise, the performance of the different PUF formulations was studied and compared to that of an industrial PUF. From these results, it can be highlighted that the addition of the flame retardants into the formulation showed an improvement in the results of the UL-94 vertical burning test and the LOI. Moreover, the fireproofing performance of the biobased formulations was comparable to that of the industrial one. In addition to that, it can be remarked that the biobased formulations displayed an excellent performance as thermal insulators (0.02371-0.02149 W·m-1·K-1), which was even slightly higher than that of the industrial one.

20.
Biodegradation ; 35(3): 315-327, 2024 Jun.
Article in English | MEDLINE | ID: mdl-37987936

ABSTRACT

In this article, the degradability by Aspergillus niger and Aspergillus clavatus of three bio-based polyurethane (PU) foams is compared to previous degradability studies involving a Pseudomonas sp. bacterium and similar initial materials (Spontón et al. in Int. Biodet. Biodeg. 85:85-94, 2013, https://doi.org/10.1016/j.ibiod.2013.05.019 ). First, three new polyester-polyurethane foams were prepared from mixtures of castor oil (CO), maleated castor oil (MACO), toluene diisocyanate (TDI), and water. Then, their degradation tests were carried out in an aqueous medium, and employing the two mentioned fungi, after their isolation from the environment. From the degradation tests, the following was observed: (a) the insoluble (and slightly collapsed) foams exhibited free hydroxyl, carboxyl, and amine moieties; and (b) the water soluble (and low molar mass) compounds contained amines, carboxylic acids, and glycerol. The most degraded foam contained the highest amount of MACO, and therefore the highest concentration of hydrolytic bonds. A basic biodegradation mechanism was proposed that involves hydrolysis and oxidation reactions.


Subject(s)
Aspergillus , Polyesters , Polyurethanes , Polyurethanes/chemistry , Polyurethanes/metabolism , Polyesters/metabolism , Aspergillus niger/metabolism , Castor Oil/chemistry , Water
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