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1.
Int J Biol Macromol ; 264(Pt 1): 130534, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38432276

RESUMEN

The objective was to utilize spent coffee grounds (SCG) as charring agent to combine with ammonium polyphosphate (APP) to prepare flame retardant poly(lactic acid) (PLA) composites with improved toughness. PLA/APP-SCG and PLA/APP-SCG/KH560 composites were prepared, and silane coupling agent KH560 was applied to improve particle-matrix interfacial compatibility. The particle-matrix interface, char formation, flame retardancy, mechanical properties and fracture morphology of PLA composites were studied. Results showed that PLA/APP-SCG5% and PLA/APP-SCG20% passed UL-94 V-0 rating, and increase in charred residues was favorable for improving flame retardancy. Improved toughness was also obtained compared to PLA, attributed to debonding of APP from matrix under external force as well as plasticization effect of coffee oil contained in SCG. PLA/APP-SCG5%/KH560 and PLA/APP-SCG20%/KH560 showed smaller elongation at break and impact strength compared to PLA/APP-SCG5% and PLA/APP-SCG20%, respectively. The improved interfacial compatibility was unfavorable for debonding of APP from matrix, and both APP and SCG played the role of enhancing strength, thus decreasing toughness. PLA/APP-SCG/KH560 counterparts were actually set as parallel samples to prove that PLA/APP-SCG composites showed improved toughness with weak interfacial compatibility. This study has provided a practical approach to utilize bio-derived wastes as charring agent to prepare flame retardant PLA composites with enhanced toughness.


Asunto(s)
Café , Retardadores de Llama , Poliésteres , Polifosfatos
2.
Int J Biol Macromol ; 265(Pt 1): 130648, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38460640

RESUMEN

The topic of biobased flame-retardant PLA has always been of great interest. In our study, we successfully synthesized a phosphorus-containing chitosan derivative (PCS) and combined it with aluminum hypophosphate (AP) to create an effective flame-retardant PLA system. PCS acted as an enhancer, enhancing the thermal performance, crystallinity, and toughness of PLA/AP. Compared to PLA modified with 12 wt% AP achieving UL-94 V-2 level and 24.3 % of limited oxygen index, PLA containing 3 wt% PCS and 9 wt% AP achieved UL-94 V-0 level and limited oxygen index of 28 %. The system testing studies such as CCT, Raman, XPS, and TG-IR results indicated that PLA/AP/PCS exhibited a dual flame-retardant mechanism of condensed and gas phases.


Asunto(s)
Quitosano , Retardadores de Llama , Cristalización , Poliésteres , Oxígeno , Fósforo
3.
Int J Biol Macromol ; 263(Pt 2): 130147, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38354942

RESUMEN

Green polymeric foams are an important research topic for sustainable development. In this study, a natural multifunctional flame-retardant additive based on food waste was developed and evaluated for its ability to replace the commercial additives tricresyl phosphate (TCP) and trioctyl phosphate (TOP) in a polylactide/poly(butylene adipate-co-terephthalate) (PLA/PBAT) foam. A series of blend foams with additives were prepared by melt extrusion. According to the results, the blend foam with 20 phr of TCP showed the best combination of impact toughness and flame retardancy. TCP, however, poses health and environmental risks. Therefore, natural flame retardants (NFRs) were used to partially replace the commercial flame retardant (CFR). A combination of TCP and soybean residue (SB) produced an impact toughened and flame-retardant blend foam. When compared to the neat PLA/PBAT foam, the impact toughness of the best sample was increased by about 256 %. The optimal foam showed excellent flame resistance with a V-0 UL-94 rating and a high LOI value (31.8 %). SB has the potential to partially replace TCP as flame retardant and could be used in a broad range of PLA/PBAT foam applications.


Asunto(s)
Alquenos , Retardadores de Llama , Ácidos Ftálicos , Eliminación de Residuos , Fósforo , Alimento Perdido y Desperdiciado , Alimentos , Poliésteres , Adipatos , Poli A
4.
Int J Biol Macromol ; 262(Pt 2): 130144, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38360228

RESUMEN

The phosphoramide phosphorus ester phosphate ammonium (PPEPA) flame retardant was synthesized by phosphorus oxychloride and ethanolamine, and its structure was characterized by nuclear magnetic resonance and Fourier transform infrared spectroscopy (FTIR). Cotton textiles treated with 20 wt% PPEPA (CT-PPEPA3) would have high durability and flame retardance. The limiting oxygen index (LOI) of CT-PPEPA3 was found to be 46.5 %, while after undergoing 50 laundering cycles (LCs) following the AATCC 61-2013 3 A standard, the LOI only decreased to 31.4 %. Scanning electron microscopy and X-ray diffraction analyses suggested the penetration of PPEPA molecules into the interior of cotton fibers, resulting in a minor alteration of the cellulose crystal structure. The excellent durability, FTIR, and energy-dispersive X-ray of CT-PPEPA3 provided evidence for the formation of -N-P(=O)-O-C- and -O-P(=O)-O-C- covalent bonds between the PPEPA molecules and cellulose. The -N-P(=O)-O-C- bond exhibited a p-π conjugation effect, leading to enhanced stability and improved durability of the flame-retardant cotton textiles. Vertical flame, thermogravimetric, and cone calorimetry tests demonstrated that the CT-PPEPA3 underwent condensed-phase and synergistic flame retardation. Additionally, these finished cotton textiles retained adequate breaking strength and softness, making them suitable for various applications. In conclusion, the incorporation of the -N-P(=O)-ONH4 group into the phosphorus ester phosphate ammonium flame retardant demonstrated effective enhancement of the fire resistance and durability of treated cotton textiles.


Asunto(s)
Compuestos de Amonio , Retardadores de Llama , Fósforo , Fosfatos , Fosforamidas , Textiles , Fibra de Algodón , Celulosa
5.
Chemosphere ; 353: 141555, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38417497

RESUMEN

Dermal exposure to phosphorus flame retardants (PFRs) has received much attention as a major alternative exposure route in recent years. However, the information regarding dermal exposure via direct contact with a product is limited. In addition, in the commonly used dermal permeability test, the target substance is dissolved in a solvent, which is unrealistic. In this study, a dermal permeability test of PFRs in three car seats was performed using artificial skin. The PFR concentrations in the car seats are 0.12 wt% tris(2-chloroethyl) phosphate (TCEP), 0.030-0.25 wt% tris(2-chloroisopropyl) phosphate (TCPP), 0.15 wt% triphenyl phosphate (TPhP), 0.89 wt% cresyl diphenyl phosphate (CsDPhP), 0.074 wt% tricresyl phosphate (TCsP), and 0.46-4.7 wt% diethylene glycol bis [di (2-chloroisopropyl) phosphate (DEG-BDCIPP). The mean skin permeation rates for a contact time of 24 h are 14 (TCEP), 5.4-160 (TCPP), 0.67 (CsDPhP), 0.38 (TPhP), and 3.3-58 ng cm-2 h-1 (DEG-BDCIPP). The concentrations of TCsP in receptor liquid were lower than the limit of quantification at the contact time of 24 h. The skin permeation rates were significantly affected by the type of car seat (e.g., fabric or non-fabric). The potential dermal TCPP exposure rate for an adult via direct contact with the car seat during the average daily contact time (1.3 h), which was the highest value assessed in this study, was estimated to be 16,000 ng kg-1 day-1, which is higher than that related to inhalation and dust ingestion reported as significant exposure route of PFRs in previous studies. These facts reveal that dermal exposure associated with direct contact with the product might be an important exposure pathway for PFRs.


Asunto(s)
Sistemas de Retención Infantil , Retardadores de Llama , Fosfinas , Piel Artificial , Tritolilfosfatos , Humanos , Adulto , Fósforo , Retardadores de Llama/análisis , Organofosfatos/análisis , Fosfatos , Polvo , Exposición a Riesgos Ambientales
6.
Int J Biol Macromol ; 260(Pt 2): 129293, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38199543

RESUMEN

A flame retardant (FR) hexachlorocyclotriphosphazene diethylenetriamine ammonium phosphoric acid (HDAPA) was synthesized. Vertical flammability test and limiting oxygen index (LOI) results showed that cotton samples finished with HDAPA solutions (15 % and 20 %) could pass vertical flame retardancy test, and LOIs reached 30.1 % and 35.4 % even after 50 laundering cycles according to AATCC 61-2013 3A washing standard (3A), performing flame retardancy and washing durability. Meanwhile, Fourier transform infrared and X-ray photoelectron spectroscopy analyses suggested that HDAPA was grafted on cotton fibers through -P(=O)-O-C covalent bond. Total heat release (1.98 MJ/m2) and char residue (16.2 %) of HDAPA treated cotton were much lower than those (4.26 MJ/m2, 3.2 %) of untreated cotton. Thermogravimetry results showed HDAPA changed thermal decomposition pathway of cotton fabric, which was further supported by thermogravimetric-Fourier infrared spectrometer results, revealing HDAPA performed a condensed phase flame retardancy mechanism. Scanning electron microscopy implied HDAPA entered amorphous region of cotton fibers to react with cellulose. Mechanical properties of HDAPA treated cotton decreased a little. Although the synthesis process used formaldehyde but no free formaldehyde released. In consequence, the aforementioned results indicated that the introduction of -N=P-(N)3- and -P(=O)(O-NH4+)2 groups to FR was an viable method to improve flame retardancy and durability.


Asunto(s)
Compuestos de Amonio , Retardadores de Llama , Ácidos Fosfóricos , Fósforo , Retardadores de Llama/análisis , Formaldehído
7.
Int J Biol Macromol ; 260(Pt 1): 129393, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38218301

RESUMEN

Lightweight, porous cellulose foam is an attractive alternative to traditional petroleum-based products, but the intrinsic flammability impedes its use in construction. Herein, an environmentally friendly strategy for scalable fabrication of flame-retardant bamboo pulp foam (BPF) using a foam-forming technique followed by low-cost ambient drying is reported. In the process, a hierarchical structure of halloysite nanotubes (HNT) was decorated onto bamboo pulp fibers through layer-by-layer assembling of chitosan (CS) and phytic acid (PA). This modification retained the highly porous microcellular structure of the resultant BPF (92 %-98 %). It improved its compressive strength by 228.01 % at 50 % strain, endowing this foam with desired thermal insulation properties and sound absorption coefficient comparable to commercial products. More importantly, this foam possessed exceptional flame retardancy (47.05 % reduction in the total heat release and 95.24 % reduction in the total smoke production) in cone calorimetry, and it showed excellent extinguishing performance, indicating considerably enhanced fire safety. These encouraging results suggest that the flame retardant BPF has the potential to serve as a renewable and cost-effective alternative to traditional foam for applications in acoustic and thermal insulation.


Asunto(s)
Quitosano , Retardadores de Llama , Nanotubos , Petróleo , Arcilla , Ácido Fítico , Sonido
8.
Int J Biol Macromol ; 259(Pt 2): 129237, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38191114

RESUMEN

The discharge of crude petroleum oils and their derivatives poses serious environmental challenges, which can be mitigated through oil/water separation. In this study, polyurethane (PU)/polydopamine (PDA)/chitosan-graft (g)-octanal foam was prepared by immersing of PU foam in PDA and chitosan-g-octanal solutions. The fabricated PU foam exhibited thermal stability, flame retardancy, and hydrophobicity/superoleophilicity. The coated PU foam can selectively absorb heavy and light oils from dynamic and static oil/water mixtures. The maximum sorption capacity for olive oil was found to be as high as 41.48 g/g. PU/PDA/chitosan-g-octanal foam also demonstrated excellent flame retardancy and the ability to quickly extinguish fire, as confirmed by the limiting oxygen index (LOI) test.


Asunto(s)
Aldehídos , Quitosano , Retardadores de Llama , Indoles , Petróleo , Polímeros , Poliuretanos , Aceite de Oliva
9.
Int J Biol Macromol ; 258(Pt 2): 129007, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38151082

RESUMEN

The excellent comprehensive properties of microfiber synthetic leathers have led to their wide application in various aspects of our lives. However, the issue of flammability remains a significant challenge that needs to be addressed. Nowadays, the bio-based chemicals used in the flame-retardant materials have extremely grabbed our eyes. Herein, we developed an ecologically friendly flame-retardant microfiber synthetic leather using phosphorus-free layer-by-layer assembly technology (LBL) based on natural polysaccharide alginate (SA) coupled with polyethyleneimine (PEI) and 3-aminopropyltriethoxysilane (APTES). The effect of different LBL coating systems on the flame retardancy of microfiber synthetic leather was investigated. The results demonstrated that the introduction of APTES can completely inhibit the melt-dripping by enhancing char formation through silica elements. Furthermore, the trinary coating system consisting of SA/APTES/PEI exhibited excellent flame retardancy by combining gas-phase action from PEI and condensed-phase function from APTES. This modified microfiber synthetic leather showed a significantly higher limiting oxygen index (LOI) value of 33.0 % with no molten droplet. Additionally, the SA-based coating slightly suppressed the heat release, resulting in a 20 % reduction in total heat release during the combustion test. Overall, this work presents a facile and environmentally-friendly approach for achieving flame-retardant and anti-dripping microfiber synthetic leather.


Asunto(s)
Alginatos , Retardadores de Llama , Propilaminas , Silanos , Epidermis , Ojo , Fósforo , Polietileneimina
10.
Chemosphere ; 344: 140371, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37820874

RESUMEN

Unsaturated polyester resins (UPR) are composed of prepolymers and styrene diluents, while the former are produced by co-polycondensation between diol, unsaturated diacid and saturated diacid. In this work, bio-based UPR prepolymers were synthesized from bio-based oxalic acid, itaconic acid, and ethylene glycol, which were then diluted with bio-based isosorbide methacrylate (MI). Meanwhile, the phenylphosphonate were introduced into the molecular chains of prepolymers to achieve intrinsic flame retardancy of bio-based UPR. The potential of the reactive MI diluents as substitutes of volatile styrene, was also assessed through the volatility test, curing kinetics and gel contents analysis. For UPR materials with styrene diluents, the UPR materials can achieve UL-94 V0 level and the 28% of limiting oxygen index (LOI) with 2.63 wt% of phosphorus contents. By contrast, the UPR materials with MI diluents can reach UL-94 V0 level with only 2.14 wt% of phosphorus contents. As the phosphorus contents were further increased to 2.63 wt%, UPR materials can achieve highest 29%, while the peak of heat release rate (PHRR) and total heat release (THR) were decreased by 68.01% and 48.62%, respectively. The Flame Retardancy Index (FRI) was also used to comprehensively evaluate the flame retardant performance of UPR composites. Compared with neat UPR, the composites with MI diluents and phosphorus containing structures increased from 1.00 to 6.46. The mechanism for improved flame retardancy was analyzed from gaseous and condensed phase. Additionally, the tensile strengths of bio-based UPR materials with styrene and MI diluents were studied. This work provides an effective method to prepared high-performance and fully bio-based UPR materials with improved flame retardant properties and safety application of reactive diluents.


Asunto(s)
Retardadores de Llama , Poliésteres , Excipientes , Isosorbida , Ácido Oxálico , Fósforo , Estirenos
11.
Chemosphere ; 342: 140184, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37716559

RESUMEN

A novel approach for improving the flame retardancy, smoke suppression and mechanical properties of epoxy resins (EPs) has been proposed by incorporating functionalized hollow mesoporous silica microcapsules (SHP) loaded with phosphorous silane flame retardants (SCA) and coated with polydopamine (PDA) and transition metals. The proposed approach involves a multi-level structure that combines several mechanisms to enhance the flame-retardant properties of EP. The physical barrier provided by silica serves to impede heat and mass transfer during combustion, while the catalytic carbonization effect of phosphorus and transition metals promotes the formation of a protective char layer, which acts as a barrier to further flame propagation. Incorporating a low loading amount of 3 wt% SHP into the epoxy matrix resulted in EP/SHP-3 composites with significantly improved flame retardancy, as evidenced by a limiting oxygen index of 31.5% and a V-1 rating, in contrast to the values obtained for unmodified EP, which were 23.8% and no rating, respectively. In addition, cone calorimeter test (CCT) results indicated that the total heat release, peak heat release rate and total smoke production of EP/SHP-3 decreased by 18.2%, 25.2% and 18.4%, respectively. Moreover, the improved interfacial compatibility facilitated by polydopamine assists in the dispersion and compatibility of the SHP with the epoxy matrix, leading to better mechanical properties. Herein, the addition of 1 wt% SHP to EP significantly improved its mechanical performance, with a 16.7% increase in tensile strength and a 19.2% increase in impact strength. The design of the multi-level structural approach has the potential to provide new ideas for the simultaneous improvement of fire safety as well as mechanical properties of polymers.


Asunto(s)
Resinas Epoxi , Retardadores de Llama , Dióxido de Silicio , Cápsulas , Catálisis , Fósforo
12.
Ecotoxicol Environ Saf ; 264: 115396, 2023 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-37625336

RESUMEN

Organophosphorus flame retardants (OPFRs), including 2-ethylhexyl diphenyl phosphate (EHDPHP), are prevalent in everyday life due to their broad usage in fields such as healthcare, electronics, industry, and sports. These compounds, added to polymers through physical mixing, can leach into the environment, posing a risk to humans through direct contact or the food chain. Despite known associations with health issues like endocrine disruption, neurotoxicity, and reproductive toxicity, the implications of perinatal EHDPHP exposure on both mothers and offspring are still unclear. This study aimed to investigate the neuroinflammatory effects of EHDPHP and the potential mitigating role of inulin. Pregnant C57 mice were administered either a corn oil control or an EHDPHP solution (300 µg/kg bw/d) from gestation day 7 (GD7) to postnatal day 21 (PND21). Concurrently, mice were provided either regular drinking water or water supplemented with 1% inulin. We found that EHDPHP significantly increased the serum levels of IL-1ß, IL-6, and MDA, but decreased SOD levels in both mothers and pups. These effects were reversed by inulin supplementation. RNA-sequencing revealed that EHDPHP induced inflammation and oxidative stress through the TLR4/NF-κB pathway, which was mitigated by inulin. In conclusion, inulin ameliorated EHDPHP-induced neuroinflammation and oxidative stress in both mothers and offspring, highlighting its potential therapeutic role.


Asunto(s)
Retardadores de Llama , Fosfatos , Embarazo , Ratones , Humanos , Femenino , Animales , Organofosfatos/toxicidad , Inulina , Enfermedades Neuroinflamatorias , Estrés Oxidativo , Retardadores de Llama/toxicidad
13.
Molecules ; 28(13)2023 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-37446723

RESUMEN

The usage of flame retardants in flammable polymers has been an effective way to protect both lives and material goods from accidental fires. Phosphorus flame retardants have the potential to be follow-on flame retardants after halogenated variants, because of their low toxicity, high efficiency and compatibility. Recently, the emerging allotrope of phosphorus, two-dimensional black phosphorus, as a flame retardant has been developed. To further understand its performance in flame-retardant efficiency among phosphorus flame retardants, in this work, we built model materials to compare the flame-retardant performances of few-layer black phosphorus, red phosphorus nanoparticles, and triphenyl phosphate as flame-retardant additives in cellulose and polyacrylonitrile. Aside from the superior flame retardancy in polyacrylonitrile, few-layer black phosphorus in cellulose showed the superior flame-retardant efficiency in self-extinguishing, ~1.8 and ~4.4 times that of red phosphorus nanoparticles and triphenyl phosphate with similar lateral size and mass load (2.5~4.8 wt%), respectively. The char layer in cellulose coated with the few-layer black phosphorus after combustion was more continuous and smoother than that with red phosphorus nanoparticles, triphenyl phosphate and blank, and the amount of residues of cellulose coated with the few-layer black phosphorus in thermogravimetric analysis were 10 wt%, 14 wt% and 14 wt% more than that with red phosphorus nanoparticles, triphenyl phosphate and blank, respectively. In addition, although exothermic reactions, the combustion enthalpy changes in the few-layer black phosphorus (-127.1 kJ mol-1) are one third of that of red phosphorus nanoparticles (-381.3 kJ mol-1). Based on a joint thermodynamic, spectroscopic, and microscopic analysis, the superior flame retardancy of the few-layer black phosphorus was attributed to superior combustion reaction suppression from the two-dimensional structure and thermal nature of the few-layer black phosphorus.


Asunto(s)
Retardadores de Llama , Fósforo/química , Celulosa/química , Polímeros/química
14.
Int J Biol Macromol ; 247: 125834, 2023 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-37453641

RESUMEN

Three kinds of divalent metal ions (Ca2+, Cu2+, Zn2+) alginate/silver phosphate (MAlg/Ag3PO4) hybrid materials were prepared via an in-situ method, and the composites were characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Fourier transform infrared spectrum (FTIR). To investigate their flame-retardant properties and phosphorus-polymetallic flame-retardant effects, the combustion behavior and flammability of the composites were assessed by using the thermogravimetric analysis (TGA), limiting oxygen index (LOI) and micro-calorimeter tests (MCC). The results show that the three composites were thermally stable, among which the LOI of CaAlg/Ag3PO4, CuAlg/Ag3PO4 and ZnAlg/Ag3PO4 were 62.6 %, 46.5 % and 79.8 %, respectively, which were much higher than the prescribed flame retardants which was 27 %. According to the TGA, the thermal stability was ZnAlg/Ag3PO4 > CaAlg/Ag3PO4 > CuAlg/Ag3PO4. The heat release capacity (HRC) of the above three materials was 49 J/(g·K), 69 J/(g·K), 41 J/(g·K), respectively, and the fire safety performance was also in the same order as the thermal stability. By using the thermogravimetric analysis coupled with Fourier transform infrared analysis (TG-FTIR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS), the flame retarding mechanism of MAlg/Ag3PO4 and the synergistic effect of Ag3PO4 and divalent metal ions were proposed based on the experimental data.


Asunto(s)
Retardadores de Llama , Fósforo , Alginatos , Iones , Oxígeno
15.
Environ Int ; 177: 108010, 2023 07.
Artículo en Inglés | MEDLINE | ID: mdl-37307603

RESUMEN

Organophosphate esters (OPEs) are widely used as plasticizers in plastic food packaging; however, the migration of OPEs from plastic to food is largely unstudied. We do not even know the specific number of OPEs that exist in the plastic food packaging. Herein, an integrated target, suspect, and nontarget strategy for screening OPEs was optimized using ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS). The strategy was used to analyze 106 samples of plastic food packaging collected in Nanjing city, China, in 2020. HRMS allowed full or tentative identification of 42 OPEs, of which seven were reported for the first time. Further, oxidation products of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (AO626) in plastics were identified, implying that the oxidation of organophosphite antioxidants (OPAs) could be an important indirect source of OPEs in plastics. The migration of OPEs was examined with four simulated foods. Twenty-six out of 42 OPEs were detected in at least one of the four simulants, particularly isooctane, in which diverse OPEs were detected at elevated concentrations. Overall, the study supplements the list of OPEs that humans could ingest as well as provides essential information regarding the migration of OPEs from plastic food packaging to food.


Asunto(s)
Retardadores de Llama , Plásticos , Humanos , Plásticos/análisis , Embalaje de Alimentos , Ésteres/análisis , Retardadores de Llama/análisis , Monitoreo del Ambiente , Organofosfatos/análisis , China , Suplementos Dietéticos/análisis
16.
Macromol Rapid Commun ; 44(12): e2300071, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-37083036

RESUMEN

Two kinds of polyaniline coupled graphitized carbon nitride nanosheets doped with different organic phosphoric acids (CP@PA, with phytic acid; CP@NP, with amino trimethyl phosphonic acid) are developed by in-situ polymerization. According to the analysis of the section morphology and element distribution of epoxy resin (EP) composites, although CP@PA and CP@NP show completely different morphology, they can significantly enhance the dispersion of graphitized carbon nitride nanosheets in EP. Moreover, the different oxidation states of phosphorus contained in the CP@PA and CP@NP lead to varying effects on the fire safety of EP. The flame retardancy Index (FRI) is a dimensionless index to evaluate the performance of flame retardants. When used as a flame retardant, CP@NP (FRI = 3.22) is better than CP@PA (FRI = 1.29) in flame retardant, especially in suppressing thermal hazards. As a synergist of intumescent flame retardants (IFR), CP@PA (FRI = 26.12) is most effective in improving the comprehensive fire safety property of EP and achieves an "Excellent" rating. Therefore, two different flame-retardant mechanisms of CP@PA and CP@NP are summarized by analyzing the combustion behavior and changes of condensed phase. In summary, this research may be helpful to the design of nano synergies for IFR systems.


Asunto(s)
Retardadores de Llama , Resinas Epoxi , Aminoácidos , Compuestos de Anilina , Ácidos Fosfóricos , Fósforo
17.
Int J Mol Sci ; 24(5)2023 Feb 21.
Artículo en Inglés | MEDLINE | ID: mdl-36901747

RESUMEN

Bisphenol A type benzoxazine (Ba) monomers and 10-(2, 5-dihydroxyphenyl)-10- hydrogen-9- oxygen-10- phosphine-10- oxide (DOPO-HQ) were employed to prepare flame retardant and heat insulated polybenzoxazine (PBa) composite aerogels. The successful preparation of PBa composite aerogels was confirmed by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The thermal degradation behavior and flame-retardant properties of the pristine PBa and PBa composite aerogels were investigated with thermogravimetric analysis (TGA) and cone calorimeter. The initial decomposition temperature of PBa decreased slightly after incorporating DOPO-HQ, increasing the char residue amount. The incorporation of 5% DOPO-HQ into PBa led to a decrease of 33.1% at the peak of the heat-release rate and a decrease of 58.7% in the TSP. The flame-retardant mechanism of PBa composite aerogels was investigated by SEM, Raman spectroscopy, and TGA coupled with infrared spectrometry (TG-FTIR). The aerogel has advantages such as a simple synthesis procedure, easy amplification, lightweight, low thermal conductivity, and good flame retardancy.


Asunto(s)
Benzoxazinas , Retardadores de Llama , Animales , Estro , Calor , Fósforo
18.
Int J Biol Macromol ; 239: 124252, 2023 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-36996951

RESUMEN

Rising concerns about the toxic effects and environmental issues associated with various fireproof treatments on textiles have led to a demand for "green" materials. Chitosan (CS) is an amino polysaccharide green, recyclable, and non-toxic highly biocompatible biopolymer that consists of multiple hydroxyl groups and has a wide range of applications, including as a flame retardant additive. In this study, an eco-friendly bio-based formaldehyde-free flame retardant containing a higher level of phosphorus and nitrogen in phytic acid ammonia (PAA) was synthesized to amplify the most plentiful green chitosan (CS)-modified polyamide 66 (PA66) fabric surface through a simple pad-dry-cure technique for the improvement of durable flame retardancy with hydrophilicity. The findings revealed that each UV-grafted CS fabric could entirely stop the melt-dripping tendency during the vertical burning (UL-94) test and reached a V-1 rating. Meanwhile, limiting oxygen index (LOI) testing showed a rapid increase from 18.5 % to 24 % for the PA66 control and the PAA-treated (i.e., PA66-g-5CS-PAA) fabric samples, respectively. Moreover, compared to the PA66 control sample, a dramatic decrease in the peak heat release rate (PHRR), fire growth rate (FGR), and total heat release (THR) by approximately over 52 %, 0.63 %, and 19.7 %, respectively, was observed for the PA66-g-5CS-PAA fabric sample. Additionally, this arrangement of PAA catalyzed the charring of grafted CS and acted as a condensed phase flame retardant, resulting in a significant improvement in char yield% in both air and N2 atmospheres for the PA66-g-5CS-PAA fabric sample in TGA. In addition, only the lower grafting ratio of CS with PAA-treated fabric sample (i.e., PA66-g-2CS-PAA) could encourage it to gain its lowest water contact angle of 00, as well as impersonating a positive effect in improving the flame retardant coating durability in washing and sustaining even after 10 home laundering cycles. This phenomenon suggests that an actual hydrophilic and durable flame retardant finishing procedure for polyamide 66 fabrics might be applied with the novel, plentiful, sustainable, and environmentally friendly bio-based green PAA ingredient.


Asunto(s)
Quitosano , Retardadores de Llama , Nylons , Fósforo , Textiles , Amoníaco , Ácido Fítico
19.
Int J Biol Macromol ; 235: 123737, 2023 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-36805506

RESUMEN

With the growing environmental awareness, poly(lactic acid) (PLA) is regarded as one of the most promising varieties of bio-based polyesters owing to its environment-friendly and biodegradable advantages. However, poor thermal stability and flammability disadvantages limit the applications of PLA. Herein, a series of biodegradable intrinsic flame-retardant thermoset PLA resins (DMMP-M4sPLA) were designed. DMMP-M4sPLA resins exhibit excellent flame retardancy, achieving UL 94 V-0 rating and limiting oxygen index (LOI) of 28.1 %-31.7 %. Meanwhile, the cured DMMP-M4sPLA resins show a high glass transition temperature and tensile strength. In addition, the resins demonstrate full degradation with no harmful degradation products. This work provides an advanced design strategy to create bio-based and biodegraded resins with superior flame retardant and mechanical performance, holding great potentials in the fields of aviation interior, automotive, etc.


Asunto(s)
Retardadores de Llama , Fósforo , Poliésteres , Resinas de Plantas , Suelo
20.
Molecules ; 28(4)2023 Feb 10.
Artículo en Inglés | MEDLINE | ID: mdl-36838679

RESUMEN

Natural polysaccharides with high viscosity, good thermal stability, and biocompatibility can improve the mechanical properties of inorganic silica aerogels and enhance their application safety. However, the effects of the preparation methods of polysaccharide-silica aerogels on their microstructure and application properties have not been systematically studied. To better investigate the effect of the microstructure on the properties of aerogel materials, two aerogels with different structures were prepared using Konjac glucomannan (KGM) and tetraethoxysilane (TEOS) via physical blending (KTB) and co-precursor methods (KTC), respectively. The structural differences between the KTB and KTC aerogels were characterized, and the thermal insulation and fire-retardant properties were further investigated. The compressive strength of the KTC aerogels with a cross-linked interpenetrating network (IPN) structure was three times higher than that of the KTB aerogels, while their thermal conductivity was 1/3 of that of the KTB aerogels. The maximum limiting oxygen index (LOI) of the KTC aerogels was 1.4 times, the low peak heat release rate (PHRR) was reduced by 61.45%, and the lowest total heat release (THR) was reduced by 41.35% compared with the KTB aerogels. The results showed that the KTC aerogels with the IPN have better mechanical properties, thermal insulation, and fire-retardant properties than the simple physically blending KTB aerogels. This may be due to the stronger hydrogen-bonding interactions between KGM and silica molecules in the KTC aerogels under the unique forcing effect of the IPN, thus enhancing their structural stability and achieving complementary properties. This work will provide new ideas for the microstructure design of aerogels and the research of new thermal insulation and fire-retardant aerogels.


Asunto(s)
Retardadores de Llama , Mananos , Fuerza Compresiva , Dióxido de Silicio
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