Phosphazene–triazine cyclomatrix network polymers: some aspects of synthesis,thermal‐ and flame‐retardant characteristics

Hydroxy phenyl‐substituted cyclotriphosphazenes were synthesized by reacting hexachlorocyclotriphosphazene with sodium phenolate and monosodium bisphenolate. The derivatives, consisting of a mixture of multi‐substituted and partly chain‐extended cyclophosphazenes, with overall functionality close to the targeted values, were transformed into the cyanatophenyl derivative. Thermal curing of the latter gave phosphazene–triazine cyclomatrix network polymers with varying ratios of phosphazene and triazine rings in the matrix. Although they manifested diminished T_g, the cured polymers were more thermally stable and provided higher char residue in comparison to the polycyanurate derived from bisphenol‐A dicyanate. The activation energies for thermal decomposition of the cyclomatrix networks increased with both phosphazene content and crosslink density, and showed a direct relationship with their thermal stability. The presence of phosphazene was conducive for enhancing the flame retardancy of the network. The flame retardancy improved with increase in crosslink density and char‐yielding property of the polymer, which implied that the flame‐retardant action was operative in the condensed phase. © 2000 Society of Chemical Industry     

Preparation of a chitosan‐based flame‐retardant synergist and its application in flame‐retardant polypropylene

A novel flame‐retardant synergist, chitosan/urea compound based phosphonic acid melamine salt (HUMCS), was synthesized and characterized by Fourier transform infrared spectroscopy and ³¹P‐NMR. Subsequently, HUMCS was added to a fire‐retardant polypropylene (PP) compound containing an intumescent flame‐retardant (IFR) system to improve its flame‐retardant properties. The PP/IFR/HUMCS composites were characterized by limiting oxygen index (LOI) tests, vertical burning tests (UL‐94 tests), microscale combustion calorimetry tests, and thermogravimetric analysis to study the combustion behavior and thermal stability. The addition of 3 wt % HUMCS increased the LOI from 31.4 to 33.0. The addition of HUMCS at a low additive amount reduced the peak heat‐release rate, total heat release, and heat‐release capacity obviously. Furthermore, scanning electron micrographs of char residues revealed that HUMCS could prevent the IFR–PP composites from forming a dense and compact multicell char, which could effectively protect the substrate material from combusting. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40845.     

Synthesis and characterization of water‐dispersed flame‐retardant polyurethane resin using phosphorus‐containing chain extender

In this research, a flame‐retardant water‐dispersed polyurethane resin was synthesized through incorporating phosphonate groups into the polyurethane structure in the chain‐extension step. A phosphorus‐containing reactive flame‐retardant compound was synthesized for this purpose. First, bis(4‐nitrophenyl)phenyl phosphine oxide was synthesized and then converted to bis(4‐amino phenyl)phenyl phosphine oxide (BAPPO) by reducing its nitro groups into amines. The obtained products were characterized by IR, ¹H‐NMR, and ³¹P‐NMR, and the thermal properties of the polymers were determined by DSC analysis. The BAPPO‐containing polyurethane showed physical properties that were almost similar to those of phosphorus‐free polyurethane and exhibited good flame resistance with a limiting oxygen index value of 27. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1314–1321, 2004     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

The flame‐retardant properties and mechanisms of poly(ethylene terephthalate)/hexakis (para‐allyloxyphenoxy) cyclotriphosphazene systems

Para‐allyl ether phenol derivative of cyclophosphazene (PACP) was prepared and used as a filler to modify the flame‐retardant properties of poly(ethylene terephthalate) (PET) by melting‐blending. The mechanism of flame‐retardant was discussed and the influences of flame‐retardant contents to the mechanical properties were studied. The results revealed that the incorporation of only 5 phpp PACP (0.37 wt % phosphorus containing) into PET matrix can distinctly increase the flame retardancy of PET/PACP composition, and it has a little effect on the mechanical properties of PET. The high flame‐retardant performance of PET/PACP composite was attributed to the combination of condensed‐phase flame retardant and gas‐phase flame retardant. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42711.     

Synergistic flame‐retardant effect of phosphaphenanthrene derivative and aluminum diethylphosphinate in glass fiber reinforced polyamide 66

The synergistic flame‐retardant (FR) effect of 1,1′‐bis(4‐hydroxyphenyl)‐metheylene‐bis(9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide‐2‐hydroxypropan‐1‐yl) (DPOH) and aluminum diethylphosphinate (AlPi) composites on glass fiber reinforced polyamide 66 (PA) was investigated by limiting oxygen index (LOI) tests, vertical burning (UL94) tests, and cone calorimeter tests. DPOH/AlPi system with 1:1 mass ratio increased UL94 ratings, suppressed heat release rate and increased residue yields of PA composites, and DPOH/AlPi system also imposed high LOI values and lower total heat release values to PA composites. All these results verified excellent synergistic FR effect between DPOH and AlPi. The reason of DPOH/AlPi system with higher flame‐retardant efficiency was caused by the quenching effect as good as that of DPOH and also by the higher charring effect than that of AlPi. DPOH/AlPi system possesses good flame retardancy in gas phase and also the strengthened FR effect in condensed phase compared with DPOH and AlPi alone, which led to excellent synergistic FR effect between the two components DPOH and AlPi. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45126.     

Effect of expandable graphite on the properties of intumescent flame‐retardant polyurethane foam

Water‐blown rigid polyurethane foam (PUF) with two different particle sizes (180 and 300 μm) of expandable graphite (EG) as a flame‐retardant additive were prepared, and the effects on the mechanical, morphological, water absorption, thermal conductivity, thermal, and flame‐retardant properties were studied. In this investigation, EG content was varied from 5 to 50 php by weight. The mechanical properties of PUF decreased with increasing EG loading in both cases. The water absorption of the PUF increased with an increase in the EG loading mainly because of the collapse of foam cells, as evidenced from the scanning electron microscopy pictures. The thermal conductivity of the EG‐filled PUF showed that the insulation properties decreased with EG loading. The flame‐retardant properties (limiting oxygen index and char yield measurement) of the PUF improved with increasing EG loading. PUF filled with the higher particle size EG showed better mechanical properties and fire‐retardant properties than the PUF filled with the lower particle size EG. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semiaromatic polyamide poly(hexamethylene terephthalamide)‐co‐polycaprolactam: Thermal and flame‐retardant properties

The poly(hexamethylene terephthalamide)‐co‐polycaprolactam (PA6T/6; 50:50) copolymer was synthesized with a reactive extrusion method and subsequently mixed with a certain content of glass fibers (GFs) and different ratios of flame‐retardant aluminum diethyl phosphinate (AlPi) to fabricate a series of composites. These resulting composites were found to have excellent mechanical (tensile strength = 119–154 MPa) and thermal properties (heat‐deflection temperature = 263–293 °C). It is particularly worth mentioning that the value of the limiting oxygen index reached 29.5% and a UL‐94 V‐0 rating (1.6 mm) was achieved with the addition of 20 portions of AlPi. Also, the values of the peak heat‐release rate and total heat release in cone calorimetry were found to decrease with the addition of the flame‐retardant AlPi, which acted mainly as a flame inhibitor in the gas phase. Through visual observation, scanning electron microscopy after cone calorimetry testing, and thermogravimetric analysis, the condensed‐phase flame‐retardant mechanism of the PA6T/6–GF–AlPi system was confirmed to have a synergetic role. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46451.     

Effect of trisilanolphenyl‐POSS on rheological,mechanical, and flame‐retardant properties of poly(ethylene terephthalate)/cyclotriphosphazene systems

Poly(ethylene terephthalate) (PET) chips were coated by trisilanolphenyl–polyhedral oligomeric silsesquioxane (T‐POSS) and hexakis (para‐allyloxyphenoxy) cyclotriphosphazene (PACP) using the predispersed solution method, and PET/PACP/T‐POSS hybrids were further prepared by the melt‐blending method. The influence of T‐POSS on the rheological, thermal, and mechanical properties and flame retardancy of PET/PACP composites were discussed. The results suggest that T‐POSS was homogeneously dispersed in the PET matrix, which reduced the negative effects on polymer rheology and mechanical properties. For the PET/4%PACP/1%T‐POSS sample, the tensile strength at break and T_g increased from 29.67 MPa and 81.7 °C (PET/5%PACP) to 34.8 MPa and 85.8 °C, respectively, but the sample also self‐extinguished within 2 s, and the heat release capacity was reduced by 27.9% in comparison with that of neat PET.© 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45912.     

Microencapsulation of intumescent flame‐retardant agent: Application to flame‐retardant natural rubber composite

The first part of this investigation focused on the synthesis and characterization of a microencapsulated intumescent flame retardant (MIFR) agent. Two steps were used in the synthesis process. The structure was characterized by scanning electron microscopy, thermogravimetric anaylysis, and Fourier transform infrared spectroscopy. The addition of this MIFR agent into natural rubber (NR) led to an improvement in its physicomechanical and flame‐retardant (FR) properties. The second part focused on the evaluation of such characteristics as cure characteristics, FR property, tensile properties, abrasion resistance, and dynamic mechanical analysis of MIFR filled NR composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1828–1838, 2007     

Highly flame‐retardant bio‐based polyurethanes using novel reactive polyols

Poor flame retardancy of polyurethanes (PU) is a global issue as it limits their applications particularly in construction, automobile, and household appliances industries. The global challenge of high flammability of PU can be addressed by incorporating flame‐retardant materials. However, additive flame‐retardants are non‐compatible and depreciate the properties of PU. Hence, reactive flame‐retardants (RFR) based on aliphatic (Ali‐1 and Ali‐2) and aromatic (Ar‐1 and Ar‐2) structured bromine compounds were synthesized and used to prepare bio‐based PU using limonene dimercaptan. The aromatic bromine containing foams showed higher close cell content (average 97 and 100%) and compressive strength (230 and 325 kPa) to that of aliphatic bromine containing foams. Similar behavior was observed for a horizontal burning test where with a low concentration of bromine (5 wt %) in the foams for Ar‐1 and Ar‐2 displayed a burning time of 12.5 and 11.8 s while, Ali‐1 and Ali‐2 displayed burning time of 25.7 and 37 s, respectively. Neat foam showed a burning time of 74 s. The percentage weight loss for neat PU foam was 26.5%, while foams containing 5 wt % bromine in Ali‐1, Ali‐2, Ar‐1, and Ar‐2 foams displayed weight loss of 11.3, 14, 7.9, and 14%, respectively. Our results suggest that flame retardant PU foams could be prepared effectively by using RFR materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46027.     

Effects of inorganic fillers on the flame‐retardant and mechanical properties of rigid polyurethane foams

Rigid polyurethane foam (RPUF) composites filled with expandable graphite (EG), hollow glass microspheres (HGM), and glass fibers (GF) have been synthesized and characterized by limiting oxygen index, radiation ignition, compressing and torsion testing, and scanning electron microscopy. The results indicate HGM and GF benefit to the mechanical properties, while EG is good for flame retardancy. Proper ingredient of additive can lead to good flame retardancy and mechanical properties of the RPUF. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40253.     

Flame‐retardant properties and mechanisms of epoxy thermosets modified with two phosphorus‐containing phenolic amines

Two phosphorus‐containing phenolic amines, a 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO)‐based derivative (DAP) by covalently bonding DOPO and imine (SB) obtained from the condensation of p‐phenylenediamine with salicylaldehyde, and its analog (AP) via the addition reaction between diethyl phosphite and SB, were used to prepare flame‐retardant epoxy resins. The burning behaviors and dynamic mechanical properties of epoxy thermosets were studied by limited oxygen index (LOI) measurement, UL‐94 test, and dynamic mechanical analysis. The flame‐retardant mechanisms of modified thermosets were investigated by thermogravimetric analysis, Py‐GC/MS, Fourier transform infrared, SEM, elemental analysis, and laser Raman spectroscopy. The results revealed that epoxy thermoset modified with DAP displayed the blowing‐out effect during UL‐94 test. With the incorporation of 10 wt % DAP, the modified thermoset showed an LOI value of 36.1% and V‐0 rating in UL‐94 test. The flame‐retardant mechanism was ascribed to the quenching and diluting effect in the gas phase and the formation of phosphorus‐rich char layers in the condensed phase. However, the thermoset modified with 10 wt % AP only showed an LOI value of 25.7% and no rating in UL‐94 test, which was possibly ascribed to the mismatching of charring process with gas emission process during combustion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43953.     

Synthesis and polymerization of the bromoacrylated plant oil triglycerides to rigid,flame‐retardant polymers

Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N‐bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, ¹H‐NMR, ¹³C‐NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oil–styrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glass‐transition temperatures were also determined and soybean oil–based polymer and sunflower oil–based polymer showed a glass transition at 55–65 and 20–30°C, respectively. The storage moduli of the soybean‐based and sunflower‐based polymers at room temperature were approximately 1.0 × 10¹⁰ and 1.1 × 10⁸ Pa, respectively. Photopolymerization was also carried out by using 2,2‐dimethoxy‐2‐phenyl‐acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713‐78 and was found to be 5 B at 2.00 mm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91:2700–2710, 2004     

Synergistic flame‐retardant effect of halloysite nanotubes on intumescent flame retardant in LDPE

Synergistic flame‐retardant effect of halloysite nanotubes (HNTs) on an intumescent flame retardant (IFR) in low‐density polyethylene (LDPE) was investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), cone calorimeter (CC) test, and scanning electronic microscopy (SEM). The results of LOI and UL‐94 tests indicated that the addition of HNTs could dramatically increase the LOI value of LDPE/IFR in the case that the mass ratio of HNTs to IFR was 2/28 at 30 wt % of total flame retardant. Moreover, in this case the prepared samples could pass the V‐0 rating in UL‐94 tests. CC tests results showed that, for LDPE/IFR, both the heat release rate and the total heat release significantly decreased because of the incorporation of 2 wt % of HNTs. SEM observations directly approved that HNTs could promote the formation of more continuous and compact intumescent char layer in LDPE/IFR. TGA results demonstrated that the residue of LDPE/IFR containing 2 wt % of HNTs was obviously more than that of LDPE/IFR at the same total flame retardant of 30 wt % at 700°C under an air atmosphere, and its maximum decomposing rate was also lower than that of LDPE/IFR, suggesting that HNTs facilitated the charring of LDPE/IFR and its thermal stability at high temperature in this case. Both TGA and SEM results interpreted the mechanism on the synergistic effect of HNTs on IFR in LDPE, which is that the migration of HNTs to the surface during the combustion process led to the formation of a more compact barrier, resulting in the promotion of flame retardancy of LDPE/IFR. In addition, the mechanical properties of LDPE/IFR/HNTs systems were studied, the results showed that the addition of 0.5–2 wt % of HNTs could increase the tensile strength and the elongation at break of LDPE/IFR simultaneously. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40065.     

Effect of nano‐titanium nitride on thermal insulating and flame‐retardant performances of phenolic foam

In this work, titanium nitride (TiN) nanoparticles were employed to achieve enhanced thermal insulation and flame retardance of phenolic foam (PF)/TiN nanocomposites (PFTNs) via in situ polymerization. The morphologies of PFTNs were observed by scanning electron microscope and the images showed that the PFTNs have more uniform cell morphologies compared with pure PF. Thermal insulating properties of PFTNs were evaluated by thermal conductivity tests. The introduction of TiN obviously decreased the thermal conductivities of PF over a wide temperature range (?20 to 60 °C). Significantly, the thermal conductivity of PFTNs gradually decreased as the temperature increased from 30 to 60 °C, showing a contrary tendency with that of pure PF. Moreover, the thermal stability and flame‐retardant properties of PFTNs were estimated by thermogravimetric analysis (TGA), UL‐94 vertical burning and limited oxygen index (LOI) tests, respectively. The TGA and LOI results indicated that PFTNs possess enhanced thermal stabilities and fire‐retardant performances with respect to the virgin PF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43765.     

Smoke and toxicity suppression by zinc salts in flame‐retardant polyurethane‐polyisocyanurate foams filled with phosphonate and chlorinated phosphate

Three types of zinc salts, ZnAl₂O₄, ZnFe₂O_4, and Zn₂SiO_4, were prepared by coprecipitation. Potential smoke and toxicity suppression by zinc salts in flame‐retardant polyurethane‐polyisocyanurate foams (FPUR‐PIR) with dimethylmethylphosphonate (DMMP) and tris (2‐chloropropyl) phosphate (TCPP) were investigated. The crystal structure and dispersity of zinc salts in FPUR‐PIR were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Smoke density, flame retardancy, and thermal degradation were studied using smoke density rating (SDR), limiting oxygen index (LOI), the cone calorimeter test, and thermogravimetry coupled with FTIR spectrophotometry (TGA‐FTIR). The results indicated that pure zinc salts were obtained and evenly dispersed on the cell wall of FPUR‐PIR. SDR and the specific extinction area (SEA) were significantly decreased, the time to second heat release rate peak (pk‐HRR) of FRUP‐PIR was delayed after incorporation of the zinc salts; zinc salts partially inhibited phosphorus oxide release into the gas phase, enhanced the condensed phase effect of phosphorus, reduced, and prolonged the release of isocyanate compound and hydrogen cyanide from FRUP‐PIR; due to an increase in the amount of char residues, which indicated the suppression of smoke and toxicity volatiles. ZnFe₂O₄ resulted in better char formation at the initial degradation stage of FPUR‐PIR, and ZnAl₂O₄ retained more phosphorus in the solid phase at higher temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41846.     

A facile one‐step synthesis of flame‐retardant coatings on cotton fabric via ultrasound irradiation

This article reports a facile one‐step methodology to increase fire resistance properties of cotton fabric. The flame‐retardant coating for cotton fabric was synthesized with methyltriethoxysilane and organophosphates (M102B) through an ultrasound irradiation process. The coating structure and surface morphology of uncoated and coated fabrics were investigated by Fourier transform infrared spectroscopy and scanning electron microscope, respectively. The flame‐retardant properties, bending modulus, air permeability and thermal stability were studied by vertical burning test, cantilever method, air permeability test and thermogravimetric analysis (TGA). As a result, the cotton fabric coated with 29.2% (mass increased) of flame‐retardant coating was able to balance the flame retardant property and wearing comfort of the fabrics. The TGA results showed that the residue char of cotton was greatly enhanced after treatment with the coating, which has a high char forming effect on cellulose during testing. Furthermore, flame‐retardant property of coated fabrics did not change significantly after 10 washing cycles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45114.     

Reactive,intumescent, halogen‐free flame retardant for polypropylene

A reactive, intumescent, halogen‐free flame retardant, 2‐({9‐[(4,6‐diamino‐1,3,5‐triazin‐2‐yl)amino]‐3,9‐dioxido‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5]undecan‐3‐yl}oxy)ethyl methacrylate (EADP), was synthesized through a simple three‐step reaction from phosphorus oxychloride, pentaerythritol, hydroxyethyl methacrylate, and melamine. EADP exhibited excellent thermal stability and char‐forming ability, as revealed by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The TGA results show that the temperature at 5% weight loss was 297.8°C and the char yield at 700°C was 51.75%. SEM observation revealed that the char showed a continuous and compact surface and a cellular inner structure with different sizes. Composite of polypropylene (PP) with a 25 wt % addition of EADP (PP/EADP25) passed the UL‐94 V‐0 rating and showed a limiting oxygen index value of 31.5. Compared with those of neat PP, the flexural strength and modulus values of PP/EADP25 were somewhat improved, the tensile strength was basically unchanged, and the notched Izod impact strength was slightly decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.     

Halogen‐free intumescent flame‐retardant ethylene‐vinyl acetate copolymer system based on organic montmorillonite and graphene nanosheets

Halogen‐containing flame retardants are not preferred for environmental reasons. Herein, a halogen‐free intumescent flame‐retardant ethylene‐vinyl acetate copolymer (EVA/IFR) system containing organic montmorillonite (OMMT) and graphene nanosheets (GNSs) is fabricated with well dispersion structure, enhanced thermal‐oxidative resistance at high temperature. Interestingly, the amount of residual chars from thermogravimetric analysis is increased to 12.7 wt % at 700 °C, the EVA/IFR composite containing both OMMT and GNSs exhibits the best flame retardancy with the lowest peak heat release rate value of 529.58 kW m^?2, and the highest limited oxygen index value of 24.8%. The excellent flame retardancy is attributed to the formation of complete and compact protective char layer. Furthermore, the decreases of the mechanical properties caused by the addition of IFR are relieved and a high volume resistivity is maintained when combining OMMT and GNSs in the EVA/IFR system together. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46361.