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1.
Molecules ; 26(12)2021 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-34208392

RESUMO

Lyocell fabrics are widely applied in textiles, however, its high flammability increases the risk of fire. Therefore, to resolve the issue, a novel biomass-based flame retardant with phosphorus and nitrogen elements was designed and synthesized by the reaction of arginine with phosphoric acid and urea. It was then grafted onto the lyocell fabric by a dip-dry-cure technique to prepare durable flame-retardant lyocell fabric (FR-lyocell). X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) analysis demonstrated that the flame retardant was successfully introduced into the lyocell sample. Thermogravimetric (TG) and Raman analyses confirmed that the modified lyocell fabric featured excellent thermal stability and significantly increased char residue. Vertical combustion results indicated that FR-lyocell before and after washing formed a complete and dense char layer. Thermogravimetric Fourier-transform infrared (TG-FTIR) analysis suggested that incombustible substances (such as H2O and CO2) were produced and played a significant fire retarding role in the gas phase. The cone calorimeter test corroborated that the peak of heat release rate (PHRR) and total heat release (THR) declined by 89.4% and 56.4%, respectively. These results indicated that the flame retardancy of the lyocell fabric was observably ameliorated.


Assuntos
Arginina/química , Retardadores de Chama/síntese química , Ácidos Fosfóricos/química , Têxteis/análise , Ureia/química , Animais , Calorimetria/métodos , Temperatura Alta , Espectroscopia Fotoeletrônica/métodos , Fenômenos Físicos , Espectroscopia de Infravermelho com Transformada de Fourier/métodos
2.
Chem Biodivers ; 17(11): e2000481, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32924325

RESUMO

As an important branch of halogenated bisphenol compounds, the halogenated bisphenol monosubstituted-ether compounds have received a lot of attention in environmental health science because of their toxicity and variability. In this study, a synthetic method for bisphenol monosubstituted-ether byproduct libraries was developed. By using the versatile and efficient method, tetrachlorobisphenol A, tetrabromobisphenol A, and tetrabromobisphenol S monosubstituted alkyl-ether compounds were accessed in 39-82 % yield. Subsequently, the cytotoxicity of 27 compounds were screened using three different cell lines (HepG2, mouse primary astrocytes and Chang liver cells). Compound 2,6-dibromo-4-[3,5-dibromo-4-(2-hydroxyethoxy)benzene-1-sulfonyl]phenol was more toxic than other compounds in various cells, and the sensitivity of this compound to the normal hepatocytes and cancer cells was inconsistent. The compounds 2,6-dichloro-4-(2-{3,5-dichloro-4-[(prop-2-en-1-yl)oxy]phenyl}propan-2-yl)phenol and 2,6-dibromo-4-(2-{3,5-dibromo-4-[(prop-2-en-1-yl)oxy]phenyl}propan-2-yl)phenol were the most toxic to HepG2 cells, and most of the other compounds inhibited cell proliferation. Moreover, typical compounds were also reproductive and developmental toxic to zebrafish embryos at different concentrations. The synthetic byproduct libraries could be used as pure standard compounds and applied in research on environmental behavior and the transformation of halogenated flame retardants.


Assuntos
Compostos Benzidrílicos/química , Éteres/química , Retardadores de Chama/síntese química , Éteres Difenil Halogenados/química , Fenóis/química , Animais , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Embrião não Mamífero/efeitos dos fármacos , Embrião não Mamífero/fisiologia , Desenvolvimento Embrionário/efeitos dos fármacos , Retardadores de Chama/farmacologia , Éteres Difenil Halogenados/síntese química , Éteres Difenil Halogenados/farmacologia , Halogenação , Humanos , Camundongos , Bifenil Polibromatos/síntese química , Bifenil Polibromatos/química , Bifenil Polibromatos/farmacologia , Peixe-Zebra/crescimento & desenvolvimento
3.
Int J Mol Sci ; 21(12)2020 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-32560033

RESUMO

Two series of new hexasubstituted cyclotriphosphazene derivatives were successfully synthesized and characterized. These derivatives are differentiated by two types of linking units in the molecules such as amide-azo (6a-j) and azo-azo (8a-j). The homologues of the same series contain different terminal substituents such as heptyl, nonyl, decyl, dodecyl, tetradecyl, hydroxyl, carboxyl, chloro, nitro, and amino groups. All the intermediates and final compounds were characterized using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), and Carbon, Hydrogen, and Nitrogen (CHN) elemental analysis. Liquid crystal properties for all compounds were determined using polarized optical microscope (POM). It was found that only intermediates 2a-e with nitro and alkoxyl terminal chains showed a smectic A phase. All the final compounds with alkoxyl substituents are mesogenic with either smectic A or C phases. However, other intermediates and compounds were found to be non-mesogenic. The study on the fire retardancy of final compounds was determined using limiting oxygen index (LOI) method. The LOI value of pure polyester resin (22.53%) was increased up to 24.71% after treating with 1 wt% of hexachlorocyclotriphosphazene (HCCP). Moreover, all the compounds gave positive results on the LOI values and compound 6i with the nitro terminal substituent showed the highest LOI value of 27.54%.


Assuntos
Compostos Azo/síntese química , Retardadores de Chama/síntese química , Compostos de Fósforo/síntese química , Amidas/química , Compostos Azo/química , Compostos Azo/farmacologia , Retardadores de Chama/farmacologia , Cristais Líquidos/química , Microscopia de Polarização , Estrutura Molecular , Nitrilas/química , Oxigênio/química , Compostos de Fósforo/química , Espectroscopia de Infravermelho com Transformada de Fourier
4.
Molecules ; 25(24)2020 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-33348597

RESUMO

Epoxy resins (EP) have been used as a thermos-setting material in the field of coating, casting, bonding agent, and laminating. However, a major drawback associated with its use is the lack of good flaming properties, and it is responsible for heavy smoke along with hazardous gases considerably limiting its uses in various fields. In this study, N-ethanolamine triazine-piperizine, a melamine polymer (ETPMP), was established as a new charring-foaming agent and was successfully synthesized with ethanolamine, piperizine, cyanuric chloride, and melamine as precursor molecules via the nucleophilic substitution reaction method. Elemental analysis and Fourier transform infrared (FTIR) spectroscopy analysis were applied to approve the synthesis of ETPMP and confirmation of its structure and characterization. The epoxy coating of intumescent flame retardant (IFR) was equipped by introducing ETPMP, ammonium polyphosphate (APP), and copper oxide (CuO) in multiple composition ratios. CuO was loaded at various amounts into the IFR-coating system as a synergistic agent. The synergistic action of CuO on IFR coatings was scientifically examined by using different analytical tests such as vertical burning test (UL-94V), limited oxygen index (LOI), thermal gravimetric analysis (TGA), cone calorimeter, and scanning electron microscope (SEM). The results showed that small changes in the amount of CuO expressively amplified the LOI results and enhanced the V-0 ratings in the UL-94V test. The TGA data clearly demonstrate that the inclusion of CuO can transform the thermal deprivation behavior of coatings with a growing char slag proportion with elevated temperatures. Information from cone calorimeter data affirmed that CuO can decrease the burning factors by total heat release (THR) together with peak heat release rate (PHRR). The SEM images indicated that CuO can enrich the power and compression of the intumescent char that restricts the movement of heat and oxygen. Our results demonstrate a positive influence of CuO on the epoxy-headed intumescent flame retardant coatings.


Assuntos
Cobre/química , Resinas Epóxi/química , Retardadores de Chama/síntese química , Piperazinas/síntese química , Polímeros/química , Compostos Benzidrílicos/química , Calorimetria , Análise Diferencial Térmica , Fenóis/química , Piperazinas/química , Espectroscopia de Infravermelho com Transformada de Fourier , Triazinas/química
5.
Molecules ; 25(21)2020 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-33158075

RESUMO

Due to their chemical structure, conventional flame retardants are often toxic, barely biodegradable and consequently neither healthy nor environmentally friendly. Their use is therefore increasingly limited by regulations. For this reason, research on innovative flame retardants based on sustainable materials is the main focus of this work. Wheat starch, wheat protein, xylan and tannin were modified with phosphate salts in molten urea. The functionalization leads to the incorporation of phosphates (up to 48 wt.%) and nitrogen (up to 22 wt.%). The derivatives were applied on wood fibers and tested as flame retardants. The results indicate that these modified biopolymers can provide the same flame-retardant performances as commercial compounds currently used in the wood fiber industry. Besides, the flame retardancy smoldering effects may also be reduced compared to unmodified wood fibers depending on the used biopolymer. These results show that different biopolymers modified in phosphate/urea systems are a serious alternative to conventional flame retardants.


Assuntos
Retardadores de Chama/síntese química , Organofosfatos/química , Proteínas de Plantas/química , Amido/química , Taninos/química , Triticum/química , Ureia/química , Madeira/química , Xilanos/química
6.
Molecules ; 25(7)2020 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-32252261

RESUMO

Cellulose from cotton fibers was functionalized through a dissolution-regeneration process with phosphonate-based ionic liquids (ILs): 1,3-dimethylimidazolium methylphosphonate [DIMIM][(MeO)(H)PO2] and 1-ethyl-3-methylimidazolium methylphoshonate [EMIM][(MeO)(H)PO2]. The chemical modification of cellulose occurred through a transesterification reaction between the methyl phosphonate function of ILs and the primary alcohol functions of cellulose. The resulting cellulose structure and the amount of grafted phosphorus were then investigated by X-ray diffraction, ICP-AES, and ¹³C and ³¹P NMR spectroscopy. Depending on the IL type and initial cotton / IL ratio in the solution, regenerated cellulose contained up to 4.5% of phosphorus. The rheological behavior of cotton cellulose/ILs solutions and the microscale fire performances of modified cellulose were studied in order to ultimately prepare flame retardant cellulosic materials. Significant improvement in the flame retardancy of regenerated cellulose was obtained with a reduction of THR values down to about 5-6 kJ/g and an increase of char up to about 35 wt%.


Assuntos
Celulose/síntese química , Retardadores de Chama/síntese química , Líquidos Iônicos/química , Organofosfonatos/síntese química , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Celulose/química , Fibra de Algodão , Esterificação , Estrutura Molecular , Organofosfonatos/química , Reologia , Difração de Raios X
7.
Int J Mol Sci ; 20(12)2019 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-31212857

RESUMO

Organophosphate flame retardants (OPFRs) have been detected in various environmental matrices and have been identified as emerging contaminants (EC). Given the adverse influence of OPFRs, many researchers have focused on the absorption, bioaccumulation, metabolism, and internal exposure processes of OPFRs in animals and humans. This paper first reviews the evolution of various types of flame retardants (FRs) and the environmental pollution of OPFRs, the different absorption pathways of OPFRs by animals and humans (such as inhalation, ingestion, skin absorption and absorption), and then summarizes the environmental impacts of OPFRs, including their biological toxicity, bioaccumulation, persistence, migration, endocrine disruption and carcinogenicity. Based on limited available data and results, this study also summarizes the bioaccumulation and biomagnification potential of OPFRs in different types of biological and food nets. In addition, a new governance idea for the replacement of existing OPFRs from the source is proposed, seeking environmentally friendly alternatives to OPFRs in order to provide new ideas and theoretical guidance for the removal of OPFRs.


Assuntos
Poluentes Ambientais , Retardadores de Chama , Organofosfatos , Animais , Poluentes Ambientais/química , Poluição Ambiental , Ésteres , Retardadores de Chama/síntese química , Humanos , Estrutura Molecular , Organofosfatos/química , Compostos Organofosforados/química
8.
Molecules ; 24(17)2019 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-31455031

RESUMO

Poly- and cyclophosphazenes are excellent flame retardants but currently, are not used as textile finishing agents because water-soluble and permanent washing systems are missing. Here, we demonstrate for the first time, the successful usage of a water-soluble cyclotriphosphazene derivative for textile finishing for cotton, different cotton/polyester, and cotton/polyamide blend fabrics. A durable finish was achieved using a photoinduced grafting reaction. The flame retardant properties of the various fabrics were improved with a higher limiting oxygen index, a reduced heat release rate, and an exhibition of intumescent. Furthermore, the finished textiles passed several standardized flammability tests.


Assuntos
Retardadores de Chama/síntese química , Química Verde/métodos , Compostos Organofosforados/síntese química , Microscopia Eletrônica de Varredura , Compostos Organofosforados/química , Solubilidade , Têxteis , Termogravimetria
9.
Molecules ; 24(14)2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31340573

RESUMO

In this article, we report the synthesis of 2,4,6-substituted s-triazine-based organophosphorus compounds via a two-step process, which enables their production in high yields, and with a high purity as solids. In the first step, a Michaelis-Arbuzov rearrangement of cyanuric chloride with triethyl phosphite afforded 2,4,6-trisdiethoxyphosphinyl-1,3,5-triazine (HEPT). Subsequently, the nucleophilic substitution reaction on the triazine carbon was achieved, owing to the electron-withdrawing ability of the phosphonate groups. This characteristic of HEPT facilitated its derivatization with bi-functional amines, producing novel P-C containing bridged triazine organophosphorus compounds. The molecular structures of all of the compounds were confirmed by NMR spectroscopy, CHN elemental analysis, and single crystal X-ray analysis. In the thermogravimetric analysis in an N2 environment, >33% char formation was observed for the bridged compounds. The chemical composition analysis of the char obtained under the oxidative thermal decomposition of the bridged compounds confirmed the presence of phosphorus- and nitrogen-enriched species, which indicate their function in the condensed phase. Comparatively, the detection of HPO and H-C≡P in the gas phase during the pyrolysis of the bridged compounds can act as a source for PO•, which is known for its gas phase flame inhibition reactions. The synergy of significant char formation and the generation of intermediates leading to PO• during pyrolysis makes these molecules promising flame-retardant additives.


Assuntos
Retardadores de Chama/síntese química , Compostos Organofosforados/síntese química , Triazinas/síntese química , Humanos , Estrutura Molecular , Fosfitos/química , Pirólise , Triazinas/química
10.
Molecules ; 24(23)2019 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-31779081

RESUMO

The aim of this work was an investigation of the ability of gallic (GA) and ellagic (EA) acids, which are phenolic compounds encountered in various plants, to act as flame retardants (FRs) for epoxy resins. In order to improve their fireproofing properties, GA and EA were treated with boric acid (to obtain gallic acid derivatives (GAD) and ellagic acid derivatives (EAD)) to introduce borate ester moieties. Thermogravimetric analysis (TGA) highlighted the good charring ability of GA and EA, which was enhanced by boration. The grafting of borate groups was also shown to increase the thermal stability of GA and EA that goes up respectively from 269 to 528 °C and from 496 to 628 °C. The phenolic-based components were then incorporated into an epoxy resin formulated from diglycidyl ether of bisphenol A (DGEBA) and isophorone diamine (IPDA) (72, 18, and 10 wt.% of DGEBA, IPDA, and GA or EA, respectively). According to differential scanning calorimetry (DSC), the glass transition temperature (Tg) of the thermosets was decreased. Its values ranged from 137 up to 108 °C after adding the phenolic-based components. A cone calorimeter was used to evaluate the burning behavior of the formulated thermosets. A significant reduction of the peak of heat release rate (pHRR) for combustion was detected. Indeed, with 10 wt.% of GA and EA, pHRR was reduced by 12 and 44%, respectively, compared to that for neat epoxy resin. GAD and EAD also induced the decrease of pHRR values by 65 and 33%, respectively. In addition, a barrier effect was observed for the resin containing GAD. These results show the important influence of the biobased phenolic compounds and their boron derivatives on the fire behavior of a partially biobased epoxy resin.


Assuntos
Ácido Elágico/química , Resinas Epóxi/química , Retardadores de Chama/síntese química , Ácido Gálico/química , Compostos Benzidrílicos/química , Calorimetria/métodos , Cicloexilaminas/química , Fenóis/química , Temperatura de Transição
11.
Molecules ; 24(20)2019 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-31627395

RESUMO

Phosphorus-containing flame retardants synthesized from renewable resources have had a lot of impact in recent years. This article outlines the synthesis, characterization and evaluation of these compounds in polyesters and epoxy resins. The different approaches used in producing biobased flame retardant polyesters and epoxy resins are reported. While for the polyesters biomass derived compounds usually are phosphorylated and melt blended with the polymer, biobased flame retardants for epoxy resins are directly incorporated into the polymer structure by a using a phosphorylated biobased monomer or curing agent. Evaluating the efficiency of the flame retardant composites is done by discussing results obtained from UL94 vertical burning, limiting oxygen index (LOI) and cone calorimetry tests. The review ends with an outlook on future development trends of biobased flame retardant systems for polyesters and epoxy resins.


Assuntos
Resinas Epóxi/síntese química , Retardadores de Chama/síntese química , Lignina/química , Fósforo/química , Poliésteres/síntese química , Benzaldeídos/química , Biomassa , Resinas Epóxi/química , Fermentação , Humanos , Poliésteres/química , Propilenoglicol/química
12.
Molecules ; 24(20)2019 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-31627459

RESUMO

In order to improve the flame retardancy of polyacrylonitrile (PAN) fabrics, glycidyl methacrylate (GMA) was first grafted onto the surface of PAN fabric (PAN-g-GMA) by means of UV-induced photo grafting polymerization process. Then, PAN-g-GMA was chemically grafted with chitosan to obtain a bigrafted PAN fabric (PAN-g-GMA-g-CS). Finally, the flame-retardant PAN fabric (FR-PAN) was prepared by phosphorylation. The structure and elemental analysis of the samples were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The thermal degradation properties and combustion characteristics of the fabrics were accessed by thermogravimetric analysis (TG), differential scanning calorimetry (DSC), and cone calorimeter (CC). The results show that the onset thermal decomposition temperature of FR-PAN fabric is lower than that of the control sample due to the degradation of the grafting groups. The combustion test indicates that the FR-PAN fabric has an excellent flame-retardant property and the combustion rate is significantly reduced. In addition, the char residue of the burned FR-PAN fabric is over 97%, indicating excellent char-forming ability.


Assuntos
Resinas Acrílicas/efeitos da radiação , Quitosana/química , Retardadores de Chama/análise , Têxteis/análise , Compostos de Epóxi/química , Retardadores de Chama/síntese química , Retardadores de Chama/efeitos da radiação , Humanos , Teste de Materiais , Metacrilatos/química , Fosforilação , Polimerização/efeitos da radiação , Raios Ultravioleta
13.
Molecules ; 23(10)2018 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-30332755

RESUMO

Polylactide (PLA) is one of the most widely used organic bio-degradable polymers. However, it has poor flame retardancy characteristics. To address this disadvantage, we performed melt-blending of PLA with intumescent flame retardants (IFRs; melamine phosphate and pentaerythritol) in the presence of organically modified montmorillonite (OMMT), which resulted in nanobiocomposites with excellent intumescent char formation and improved flame retardant characteristics. Triphenyl benzyl phosphonium (OMMT-1)- and tributyl hexadecyl phosphonium (OMMT-2)-modified MMTs were used in this study. Thermogravimetric analysis in combination with Fourier transform infrared spectroscopy showed that these nanocomposites release a smaller amount of toxic gases during thermal degradation than unmodified PLA. Melt-rheological behaviors supported the conclusions drawn from the cone calorimeter data and char structure of the various nanobiocomposites. Moreover, the characteristic of the surfactant used for the modification of MMT played a crucial role in controlling the fire properties of the composites. For example, the nanocomposite containing 5 wt.% OMMT-1 showed significantly improved fire properties with a 47% and 68% decrease in peak heat and total heat release rates, respectively, as compared with those of unmodified PLA. In summary, melt-blending of PLA, IFR, and OMMT has potential in the development of high-performance PLA-based sustainable materials.


Assuntos
Bentonita/química , Retardadores de Chama/síntese química , Poliésteres/síntese química , Estrutura Molecular , Nanocompostos/química , Poliésteres/química , Propilenoglicóis/química , Reologia , Espectroscopia de Infravermelho com Transformada de Fourier , Termogravimetria , Triazinas/química
14.
Chem Soc Rev ; 45(24): 6855-6887, 2016 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-27785498

RESUMO

Enzymes, being remarkable catalysts, are capable of accepting a wide range of complex molecules as substrates and catalyze a variety of reactions with a high degree of chemo-, stereo- and regioselectivity in most of the reactions. Biocatalysis can be used in both simple and complex chemical transformations without the need for tedious protection and deprotection chemistry that is very common in traditional organic synthesis. This current review highlights the applicability of one class of biocatalysts viz."lipases" in synthetic transformations, the resolution of pharmaceutically important small molecules including polyphenols, amides, nucleosides and their precursors, the development of macromolecular systems (and their applications as drug/gene carriers), flame retardants, polymeric antioxidants and nanocrystalline solar cells, etc.


Assuntos
Biocatálise , Lipase/química , Substâncias Macromoleculares/síntese química , Amidas/síntese química , Antioxidantes/síntese química , Portadores de Fármacos/síntese química , Retardadores de Chama/síntese química , Humanos , Nanoestruturas/química , Nucleosídeos/síntese química , Polifenóis/síntese química , Energia Solar
15.
Int J Mol Sci ; 18(11)2017 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-29117109

RESUMO

To reduce fire hazards and expand high-value applications of lignocellulosic materials, thin films comprising graphene nanoplatelets (GnPs) and multi-wall carbon nanotubes (CNTs) pre-adsorbed with alkali lignin were deposited by a Meyer rod process. Lightweight and highly flexible papers with increased gas impermeability were obtained by coating a protective layer of carbon nanomaterials in a randomly oriented and overlapped network structure. Assessment of the thermal and flammability properties of papers containing as low as 4 wt % carbon nanomaterials exhibited self-extinguishing behavior and yielded up to 83.5% and 87.7% reduction in weight loss and burning area, respectively, compared to the blank papers. The maximum burning temperature as measured by infrared pyrometry also decreased from 834 °C to 705 °C with the presence of flame retardants. Furthermore, papers coated with composites of GnPs and CNTs pre-adsorbed with lignin showed enhanced thermal stability and superior fire resistance than samples treated with either component alone. These outstanding flame-retardant properties can be attributed to the synergistic effects between GnPs, CNTs and lignin, enhancing physical barrier characteristics, formation of char and thermal management of the material. These results provide great opportunities for the development of efficient, cost-effective and environmentally sustainable flame retardants.


Assuntos
Retardadores de Chama/síntese química , Grafite/química , Lignina/química , Nanotubos de Carbono/química , Celulose/química , Retardadores de Chama/economia , Microscopia Eletrônica de Varredura , Estrutura Molecular , Permeabilidade , Polímeros/química , Termogravimetria
16.
J Nanosci Nanotechnol ; 16(3): 2811-21, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-27455714

RESUMO

A novel phosphorus-containing compound diphenyl-(2,5-dihydroxyphenyl)-phosphine oxide defined as DPDHPPO was synthesized and used as flame retardant and curing agent for epoxy resins (EP). The chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, 1H, 13C and 31P nuclear magnetic resonance. The flame retardant properties, combusting performances and thermal degradation behaviors of the cured epoxy resins were investigated by limiting oxygen index (LOI), vertical burning tests (UL-94), cone calorimeter and thermogravimetric analysis (TGA) tests. The morphologies and chemical compositions of char residues for cured epoxy resins were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The water resistant properties were evaluated by putting the samples into distilled water at 70 degrees C for 168 h. The results revealed that the EP/40 wt% DPDHPPO/60 wt% PDA thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 31.9%. The cone tests results revealed that the incorporation of DPDHPPO efficiently reduced the combustion parameters of epoxy resins thermosets, such as heat release rate (HRR), total heat release (THR) and so on. The TGA results indicated that the introduction of DPDHPPO promoted epoxy resins matrix decomposed ahead of time compared with that of pure EP and led to a higher char yield and thermal stability at high temperature. The morphological structures and analysis of XPS of char residues revealed that DPDHPPO benefited to the formation of a sufficient, compact and homogeneous char layer with rich flame retardant elements on the epoxy resins materials surface during combustion. After water resistance tests, EP/40 wt% DPDHPPO/60 wt% PDA thermosets still remained excellent flame retardancy, the moisture absorption of epoxy resins thermosets decreased with the increase of DPDHPPO contents in the thermosets due to the existing of P-C bonds and the rigid aromatic hydrophobic structure.


Assuntos
Resinas Epóxi/química , Retardadores de Chama/síntese química , Fósforo/análise , Microscopia Eletrônica de Varredura , Espectroscopia Fotoeletrônica , Espectroscopia de Infravermelho com Transformada de Fourier , Termogravimetria
17.
Int J Biol Macromol ; 267(Pt 2): 131358, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38580028

RESUMO

Polylactic acid (PLA) nonwovens, recognized as eco-friendly substitutes for petroleum-based synthetic fibers, face a significant challenge due to their inherent flammability. This work addresses this concern by synthesizing a hyperbranched polyphosphoramide flame retardant (TPDT) through a one-step polycondensation process without using solvent and catalyst. TPDT is subsequently applied to PLA nonwovens using a dip-pad finishing technique. Notably, with a mere 7 wt% weight gain of TPDT, the PLA nonwovens exhibit a substantial increase in the limited oxygen index (LOI) value, reaching 32.3 %. Furthermore, the damaged area in the vertical burning test is reduced by approximately 69.2 %. In the cone calorimeter test, 17 wt% weight gain of TPDT results in a 51.4 % decrease in peak heat release rate and a 56.0 % reduction in total heat release compared to the control PLA. Additionally, char residue increases from 1.5 wt% to 31.1 wt% after combustion. The strong affinity between TPDT and PLA molecules persists even after repeated abrasion, ensuring sustained flame retardancy. Importantly, the introduction of TPDT also imparts increased softness to the PLA nonwovens. This work addresses this concern by synthesizing a hyperbranched polyphosphoramide flame retardant (TPDT) through a solvent-free, catalyst-free, and one-step polycondensation process.


Assuntos
Retardadores de Chama , Poliésteres , Poliésteres/química , Retardadores de Chama/síntese química , Solventes/química , Têxteis
18.
Int J Biol Macromol ; 277(Pt 4): 134644, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39128740

RESUMO

This research describes the synthesis of a silane derivative containing phosphorus and nitrogen atoms, leveraging their synergistic flame retardant effect through the incorporation of a PH bond to the isocyanate moiety. The synthesized silane featured alkoxysilyl groups, facilitating permanent bonds with the cotton fabric surface via hydrolysis. Cotton fabrics were modified using silane solutions of varying concentrations (2.5 %, 5 %, and 10 %) through a dip-coating process to determine the effect of the modifier amount on fabric properties. The modified fabrics were subjected to FT-IR, TGA, SEM, and EDS analyses, as well as microcalorimetric and LOI tests, to assess changes in flammability. FT-IR, SEM/EDS, and add-on analyses confirmed effective coverage of the cotton fabric with the flame retardant. Thermogravimetric tests indicated a significant reduction in the mass loss rate during thermal degradation. LOI analyses demonstrated a decrease in flammability (increase in LOI value), while microcalorimetric tests showed a substantial decrease in the heat release rate, correlating with increased modifier concentration on the fabric surface. Post-washing analyses revealed that, although some of the modifier was washed out, the samples still retained reduced flammability.


Assuntos
Fibra de Algodão , Retardadores de Chama , Retardadores de Chama/síntese química , Silanos/química , Têxteis , Espectroscopia de Infravermelho com Transformada de Fourier , Termogravimetria , Organofosfonatos/química
19.
Int J Biol Macromol ; 271(Pt 1): 132636, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38795567

RESUMO

The synthesis and characterization of [Ce2(PPPA)4(OH)2]·4H2O, wherein PPPA denotes 3-(hydroxy(phenyl)phosphoryl)propanoate, were conducted. Its potential as a flame-retardant additive for poly(L-lactic acid) (PLA) in conjunction with ammonium polyphosphate (APP) was investigated. Remarkably, with just incorporation of the 1 % Ce-complex and 4 % APP, the resulting PLA composite (PLA-8) meets the V-0 standard, exhibiting an impressive limiting oxygen index (LOI) of 29.4 %. Moreover, the introduction of the Ce-complex leads to a significant extension of ignition time (TTI), a significant 24.1 % decrease in total heat release (THR) compared to pure PLA, and a notable increase in residual carbon rate from 0.3 % to 3.51 %. Although PLA-8 exhibits a minor decline of 8.7 % in tensile strength and 3.4 % in elongation at break, respectively, compared to pure PLA, there is a substantial improvement of 32.2 % in Young's modulus and 29.9 % in impact resistance. These results emphasise the potential of cerium-based phosphorus-containing flame retardants, with cerium playing a key role in enhancing the flammability characteristics of PLA. This study contributes to the development of sustainable and fire-resistant materials in polymer chemistry.


Assuntos
Cério , Retardadores de Chama , Fósforo , Poliésteres , Retardadores de Chama/síntese química , Poliésteres/química , Poliésteres/síntese química , Cério/química , Fósforo/química , Resistência à Tração , Polifosfatos/química
20.
Int J Biol Macromol ; 273(Pt 2): 132775, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38823732

RESUMO

A novel flame retardant containing Si, N, and S elements, ((2-(triethoxysilyl)ethyl)thio)ethan-1-amine hydrochloride (TETEA), was synthesized via a click reaction and characterized using nuclear magnetic resonance spectroscopy (NMR) and fourier transform infrared spectroscopy (FTIR). Subsequently, the flame-retardant cotton fabric was fabricated by sol-gel method. The results indicated that TETEA was successfully loaded on cotton fabric and formed a uniform protective layer on the surface of cotton fabric, exhibiting excellent flame retardancy. The flame-retardant cotton fabric achieved limiting oxygen index (LOI) of 28.3 % and passed vertical combustion test without after-flame or afterglow time at TETEA concentration of 500 g/L. Thermogravimetric analysis revealed that the residual carbon content of the flame-retardant cotton fabric was much higher than that of the control under air and N2 conditions. Besides, the flame-retardant cotton fabric was not ignited in cone calorimeter test with an external heat flux of 35 kW/m2. The peak heat release rate and the total heat release decreased from 133.4 kW/m2 to 25.8 kW/m2 and from 26.46 MJ/m2 to 17.96 MJ/m2, respectively. This phosphorus-free flame retardant offers a simplified synthesis process without adverse environmental impacts, opening up a new avenue for the development environmentally friendly flame retardants compared to traditional alternatives.


Assuntos
Celulose , Fibra de Algodão , Retardadores de Chama , Retardadores de Chama/síntese química , Retardadores de Chama/análise , Fibra de Algodão/análise , Celulose/química , Celulose/análogos & derivados , Nitrogênio/química , Silício/química , Espectroscopia de Infravermelho com Transformada de Fourier , Termogravimetria , Substâncias Macromoleculares/química , Substâncias Macromoleculares/síntese química
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