Preparation, thermal properties and flame retardancy of phosphorus- and silicon-containing epoxy resins

Phosphorus- and silicon-containing epoxy resins were prepared from (2,5-dihydroxyphenyl)diphenyl phosphine oxide (Gly-HPO), diglycidyloxy methylphenyl silane (DGMPS) and 1,4-bis(glycidyloxydimethyl silyl)-benzene (BGDMSB) as epoxy monomers and diaminodiphenylmethane (DDM), bis(3-aminophenyl)methyl phosphine oxide (BAMPO) and bis(4-aminophenoxy)dimethyl silane (APDS) as curing agents. Epoxy resins with different phosphorus and silicon content were obtained. Their thermal, dynamic mechanical and flame retardant properties were evaluated. The high LOI values confirmed that epoxy resins containing hetero-atoms are effective flame retardants, but a synergistic efficiency of phosphorus and silicon on flame retardation was not observed.     

Kinetics study of thermal decomposition of epoxy resins containing flame retardant components

Hyperbranched polyphosphate ester (HPPE) and phenolic melamine (PM) were blended in different ratios with a commercial epoxy resin to obtain a series of flame retardant resins. The thermal decomposition mechanism of their cured products in air was studied by thermogravimetric analysis and in situ Fourier-transform infrared spectroscopy. The degradation behaviours of epoxy resins containing various flame retardant components were found to be greatly changed. The incorporation of phosphorus and nitrogen compounds improved the thermal stability at elevated temperature. The kinetics of thermal decomposition was evaluated by Kissinger method, Flynn-Wall-Ozawa method and Horowitz-Metzger method. The results showed that the activation energy at lower degree of the degradation decreased by the incorporation of flame retardant components, while increased at higher degree of the degradation.     

Metal compound-enhanced flame retardancy of intumescent epoxy resins containing ammonium polyphosphate

A series of intumescent flame-retardant epoxy resins (IFR-EPs) were prepared only by adding a 5 wt% total loading of ammonium polyphosphate (APP) and metal compounds. All the samples could achieve V-0 rating and did not generate dripping during UL-94 testing. The limiting oxygen index (LOI) values of the samples with 4.83 wt% APP and 0.17 wt% CoSA increase from 27.1 to 29.4, compared with epoxy resin containing 5 wt% APP. The samples also showed excellent water resistance of flame retardancy in 30 °C and 70 °C water for 168 h. The LOI results show that the composition of metal compounds (metal ions and ligands/anions) and the mass ratios of APP to metal compounds affect the flame retardancy of the samples. TG results indicate that the catalytic effect of CoSA on the decomposition of both APP and the epoxy resins containing APP is better than that of CuSAO. The fire behavior of epoxy resin and epoxy resins containing APP with/without CoSA were investigated by cone calorimeter. Cone calorimeter parameters of the samples such as HRR, THR, TSP and COP indicate that the addition of APP and CoSA improves the fire safety of epoxy resin significantly, and CoSA shows an obvious catalytic effect.     

Silicon-containing flame retardant epoxy resins: Synthesis, characterization and properties

Epoxy resins with different silicon contents were prepared from silicon-containing epoxides or silicon-containing prepolymers by curing with 4,4′-diaminodiphenylmethane. The reactivity of the silicon-based compounds toward amine curing agents was higher than that of the conventional epoxy resins. The T_g of the resulting thermosets was moderate and decreased when the silicon content increased. The onset decomposition temperatures decreased and the char yields increased when the silicon content increased. Epoxy resins had a high LOI value, according to the efficiency of silicon in improving flame retardance.     

Synthesis and thermal decomposition of a novel hyperbranched polyphosphate ester used for flame retardant systems

A novel hyperbranched polyphosphate ester (HPPE) was synthesized via the polycondensation of bisphenol-A as an A₂ monomer and phosphoryl trichloride as a B₃ monomer at 100 °C, without gelation. The initial molar ratio of A₂ to B₃ was set to be 1.5:1. The final product was precipitated from methanol. ³¹P NMR spectroscopy was used to monitor the reaction. The formed HPPE was characterized by FTIR and ¹H NMR to confirm its end groups. Differential scanning calorimetry data revealed that the cured bisphenol-A epoxy resin with HPPE as a curing agent possessed improved glass transition temperature. Dynamic mechanical thermal analysis also showed the increase in the glass transition temperature. The thermal degradation properties and flame retardancy were investigated by thermogravimetric analysis and limiting oxygen index (LOI). The results showed that the incorporation of HPPE into bisphenol-A epoxy resin increased its thermal stability and char yield during the decomposition by raising the second stage decomposition temperature. The LOI value increased from 23 to 31 when HPPE, instead of bisphenol-A, was used as a curing agent.     

Intrinsically flame retardant epoxy resin - Fire performance and background - Part I

The flame retardant effect of newly synthesized phosphorus-containing reactive amine, which can be used both as crosslinking agent in epoxy resins and as a flame retardant, was investigated. The effect of montmorillonite and sepiolite additives on the fire induced degradation was compared to pristine epoxy resin. The effect of combining the organophosphorous amine with clay minerals was also studied. It could be concluded that the synthesized phosphorus-containing amine, TEDAP can substitute the traditional epoxy resin curing agents providing additionally excellent flame retardancy: the epoxy resins flame retarded this way reach 960 °C GWFI value, 33 LOI value and V-0 UL-94 rating - compared to the 550 °C GWFI value, 21 LOI value and “no rate” UL-94 classification of the reference epoxy resin. The peak of heat release was reduced to 1/10 compared to non-flame retarded resin, furthermore a shift in time was observed, which increases the time to escape in case of fire. The flame retardant performance can be further improved by incorporating clay additives: the LOI and the HRR results showed that the optimum of flame retardant effect of clay additives is around 1 mass% filler level in AH-16-TEDAP system. Applying a complex method for mechanical and structural characterization of the intumescent char it was determined that the flame retarded system forms significantly more and stronger char of better uniformity with smaller average bubble size. Incorporation of clay additives (owing to their bubble nucleating activity) results in further decrease in average bubble diameter.     

Vegetable oil-based flame retardant epoxy/clay nanocomposites

Flammability of epoxy appears to be one of the greatest threats and hence limits its advanced applications. The present investigation, therefore, reports on vegetable oil-based self-extinguishing epoxy/clay nanocomposites for the first time. These nanocomposites were prepared by the ex-situ technique using mechanical shearing and ultrasonication at different loadings (1, 2.5 and 5 wt%) of nano-clay. Monoglyceride of Mesua ferrea L. seed oil, bisphenol-A and tetrabromobisphenol-A based epoxy resin was used as the matrix. XRD, TEM, SEM, FTIR and rheological studies confirmed partially exfoliated nanocomposites formation. The study demonstrates two fold improvements of tensile strength and scratch hardness, three-fold increase in adhesive strength and 20 units increase in gloss value without any change in impact resistance through nanocomposite formation. TG studied confirmed the enhancement of thermal stability of the nanocomposite by 25 °C. The limiting oxygen index values and UL 94 test indicated the self-extinguishing characteristic of the nanocomposites.     

Novel high Tg flame retardancy approach for epoxy resins

A novel halogen-free phosphorus- and nitrogen-containing heterocyclic flame retardant - 5,10-dihydro-phenophosphazine-10-oxide (DPPA) - was synthesised and characterised by NMR, MS, and XRD analyses. DPPA and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were successfully incorporated in the backbone of diglycidyl ether of bisphenol A (DGEBA). The resultant prepolymers were cured with 4,4′-diaminodiphenylmethane (DDM) and diethyldiamino toluene (DETDA 80). The burning behaviours of the thermosets obtained were studied by UL 94 and LOI and compared to each other. Also their glass transition temperatures (Tgs) were determined by differential scanning calorimetry (DSC). Due to the bridging incorporation of DPPA in DGEBA by fusion process, high T_gs for these samples were achieved.     

Thermal degradation behavior of hyperbranched polyphosphate acrylate/tri(acryloyloxyethyl) phosphate as an intumescent flame retardant system

The hyperbranched polyphosphate acrylate (HPPA) was blended in different ratios with tri(acryloyloxyethyl) phosphate (TAEP) to obtain a series of UV curable intumescent flame retardant resins. The thermal degradation mechanism of their cured films in air was studied by thermogravimetric analysis and in situ Fourier-transform infrared spectroscopy. The results showed that the addition of HPPA reduced the initial decomposition temperature (T_di) but increased the char residue. Moreover, the decomposition was considered to be divided into three stages: firstly the degradation of phosphate group, secondly ester group and finally alkyl chain. The morphological structure of the formed char was observed by scanning electron microscopy, demonstrating the formation mechanism of the intumescent charred crust.     

Novel flame retardancy effects of DOPO-POSS on epoxy resins

A series of flame retarded epoxy resins (EP) was prepared with a novel polyhedral oligomeric silsesquioxane containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-POSS). The flame retardancy of these EPs was tested by the LOI, UL-94, which indicates that DOPO-POSS has meaningful effects on the flame retardancy of EP composites. 2.5 wt.% DOPO-POSS incorporation into epoxy resin (EP-2.5), results in a LOI value 30.2 and UL-94 V-1 (t₁ = 8 s and t₂ = 3 s) rating. Moreover, self-extinguishing effect through the pyrolytic gases spurt is observed in UL-94 test for the EP-2.5. The pyrolytic gases and thermal stability of epoxy resins with and without DOPO-POSS were detected by TGA-FTIR under air atmosphere. Releases of gaseous species are found to be similar for the pure EP and EP-2.5. The details of fire behaviour, such as TTI, HRR, p-HRR, TSR, SEA, COPR, CO₂PR, and TML, were tested by cone calorimeter. It is notable that 2.5 wt.% DOPO-POSS could make COPR and CO₂PR reach a maximum, which could explain the blowing-out extinguishing effect.     

Boron-containing novolac resins as flame retardant materials

Boron-containing novolac resins were prepared from novolac resins and bis(benzo-1,3,2-dioxaborolanyl)oxide and bis(4,4,5,5-tetramethyl-1,3,2-dioxa-borolanyl)oxide. The reaction of the model compound 2,6-dimethylphenol with these organoborates was complete but when the novolac resin was reacted, the degree of modification was moderate, even when there was an excess of boron compounds. The thermal degradation was investigated by TGA and pyrolysis, collecting volatiles which were investigated by GC-MS analysis, and the various compounds detected at different degradation temperatures were shown. The thermal degradation under air showed that the presence of boron is significant in the residue at high temperature. LOI values were high. Correlations between the high char yields and LOI values mean that the flame retardancy of the novolac resins improves when they are modified with bis(benzo-1,3,2-dioxaborolanyl)oxide.     

Synthesis of three novel phosphorus-containing flame retardants and their application in epoxy resins

One symmetric diamine (4) and two symmetric phenols (5) and (6) were synthesized as phosphorus-containing flame retardants. The synthesis comprised a two-step procedure: the condensation of p-phenylenediamine with benzaldehyde, 4-hydroxybenzaldehyde and 2-hydroxybenzaldehyde respectively, followed by the addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the imine linkage. The structures of (4)-(6) were characterized by FTIR, NMR and mass spectra. (4)-(6) served as co-curing agents of diaminodiphenylmethane for epoxy resins, and epoxy thermosets exhibited excellent flame retardancy, moderate changes in glass transition temperature (T_g) and thermal stability. When the phosphorus content reached 1.0 wt.%, the epoxy resin system met the UL-94 V-0 classification and the limiting oxygen index (LOI) reached more than 35.6, probably because of the nitrogen-phosphorus synergistic effect.     

Synthesis and properties of a novel hyperbranched polyphosphate acrylate applied to UV curable flame retardant coatings

A series of hyperbranched polyphosphate acrylates (HPPAs) being used for UV curable flame retardant coatings were prepared by the reaction of tri(acryloyloxyethyl) phosphate (TAEP) with piperazine at given ratios, and characterized using FTIR, ¹H NMR and GPC measurements. HPPA was blended with TAEP in different ratios to obtain a series of UV curable resins. Their maximum photopolymerization rates and final unsaturation conversion (P^f) in the cured films at the presence of a photofragmenting initiator were investigated. The results showed that the P^f increased along with HPPA content and the pure HPPA has the maximum value of 82.1% in the photo-DSC analysis. The data from dynamic mechanical thermal analysis showed that HPPA has good miscibility with TAEP. The crosslinking density and T_g of the cured film decrease along with the content of HPPA in the blend. The mechanical properties of the cured films were also investigated. Less than 20% HPPA addition improved both the tensile strength and elongation at break without damaging the modulus. The HPPA₂₀TAEP₈₀ film with 20% HPPA addition has the highest tensile strength of 31.7 MPa and an elongation at break two times that of cured TAEP. The flame retardancy of the UV cured films was investigated by the limiting oxygen index (LOI). The cured TAEP/HPPA samples greatly expanded when burning, and the degree of expansion increased along with HPPA content. However, the LOI values decreased from 47.0 to 34.0 along with HPPA content, which can be ascribed to that the flame retardancy of TAEP is mainly acting in the gas phase, whereas HPPA mainly acting in condensed phase, and the gas phase mechanism holds the dominant effect while their blends are burning.     

Synthesis, characterization, and cure properties of phosphorus-containing epoxy resins for flame retardance

An organophosphorus compound, 10-(2,5-dihydroxyl phenyl)-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DHPDOPO), was synthesized through the reaction of 9,10-dihydro-9-oxa-10-phosphaphnanthrene-10-oxide (DOPO) and p-benzoquinone, and characterized by elemental analysis, Fourier transform infrared spectrum (FTIR), and ¹H-NMR and ³¹P-NMR spectroscopes. Consequently, the phosphorus-containing epoxy resins with phosphorus content of 1 and 2 wt.% were prepared via the reaction of diglycidyl ether of bisphenol-A with DHPDOPO and bisphenol-A, and confirmed with FTIR and gel permeation chromatography (GPC). Phenolic melamine, novolak, and dicyanodiamide (DICY) were used as curing agents to prepare the thermosetted resins with the control and the phosphorus-containing epoxy resins. Thermal properties and thermal degradation behaviors of these the thermosetted resins were investigated by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Phenolic melamine-cured resins exhibited higher glass transition temperatures than the other cured resins due to the high rigidity of their molecular chain. TGA studies demonstrated that the decomposition temperatures of the novolak-cured resins were higher than those of the others. A synergistic effect from the combination of the phosphorus-containing epoxy resin and the nitrogen-containing curing agent can result in a great improvement of the flame retardance for their thermosetted resins.     

Facile synthesis of bio-based phosphorus-containing epoxy resins with excellent flame resistance

The development of high-performance biomass-derived epoxy thermosets with excellent flame resistance is vital to various applications (i.e., composites, coatings and adhesives). Herein, a difunctional epoxy monomer bis(2-methoxy-4-(oxiran-2-ylmethyl)phenyl) phenyl phosphate (BEU-EP) was synthesized from abundant and biobased eugenol. In addition, BEU-EP was cured by 4,4′-diaminodiphenyl methane (DDM) and the cured resin diglycidyl ether of bisphenol A (DGEBA)/DDM was used as a reference. Results indicated that BEU-EP/DDM not only showed a 58.1%, 28.8% and 35.1% increase in residual char (at 700 °C), flexural and storage modulus (at 30 °C) compared with DGEBA/DDM, but also exhibited excellent flame resistance and smoke suppression. BEU-EP/DDM passed V-0 rating (in UL-94 testing) with limiting oxygen index (LOI) of 38.4% and greatly decreased the peak heat release rate (pHRR) and total smoke production (TSP) by 84.9% and 80.5%, respectively. The mechanism analysis confirmed that the phosphorus-containing group and aromatic structure from BEU-EP contributed both the gas and condensed-phase flame retardation of BEU-EP/DDM network. This work provides an efficient and scalable route for synthesizing biobased epoxy thermosets with high integrated performance and superior flame resistance.     

Synthesis and properties of a phosphorus-containing flame retardant epoxy resin based on bis-phenoxy (3-hydroxy) phenyl phosphine oxide

A reactive phosphorus-containing compound, bis-phenoxy (3-hydroxy) phenyl phosphine oxide (BPHPPO) was first successfully synthesized to produce the phosphorus-containing flame retardant epoxy resin (BPHPPO-EP). The chemical structures were characterized from FTIR, MS, NMR spectra and elemental analyses. Thermal degradation behaviors and flame retardant properties of the cured epoxy resins were investigated from the thermogravimetric analysis (TGA) and the limiting oxygen index (LOI) test using 4,4′-diaminodiphenylsulfone (DDS) as curing agent. The high char yields and the high limiting oxygen index values were found to certify the great flame retardancy of this phosphorus-containing epoxy resin.     

A quantitative study of carbon monoxide and carbon dioxide evolution during thermal degradation of flame retarded epoxy resins

Thermogravimetric analysis (TGA) combined with infrared analysis of the evolved gases analysis (EGA) has been used to study the thermal degradation behaviour of epoxy resin both in air and nitrogen. The mass loss as a function of temperature has been correlated with the evolution of carbon monoxide (CO) and carbon dioxide (CO₂), and oxygen consumption as measured using an oxygen analyser. An analytical technique has been developed to quantitatively measure the carbon monoxide and dioxide gases evolved. The effect of a range of flame retardants containing phosphorus, nitrogen and halogen elements on CO and CO₂ evolution during thermal degradation of flame retarded epoxy resins has also been observed.     

Synthesis and characterization of UV-curable polydimethylsiloxane epoxy acrylate

UV-curable polydimethylsiloxane epoxy acrylate (PSEA) was synthesized by hydrosilylation of allyl glycidyl ether with hydrogen-containing polydimethylsiloxane to give polydimethylsiloxane-type epoxy resin which modified with acrylic acid. The curing speed and the double bond conversion in the UV cured film were influenced by the purity of PSEA with Fourier transform infrared spectroscopy (FT-IR) measurements. The influences of the synthetic process, such as, the reaction temperature, the concentration of reactants and the catalyst which determined the purity and activity of resins were discussed in detail. The structures of this resin were characterized by ¹H-NMR and FT-IR spectra. The molecular weight was checked by gel permeation chromatography, and M_n is 45,000. The properties of the cured film were also investigated by thermogravimetric analyzer, dynamical thermal mechanical analysis, and etc. For example, tensile strength (6.9 Mpa), elongation (20%), hardness (A; 18), water absorption (24 h; 2%), weight loss (40 min, 300 °C; 5%) and etc.     

The non-halogen flame retardant epoxy resin based on a novel compound with phosphaphenanthrene and cyclotriphosphazene double functional groups

A novel flame retardant additive hexa-(phosphaphenanthrene -hydroxyl-methyl-phenoxyl)-cyclotriphosphazene (HAP-DOPO) with phosphazene and phosphaphenanthrene double functional groups has been synthesized from hexa-chloro-cyclotriphosphazene, 4-hydroxy-benzaldehyde and 9,10-dihydro-9-oxa-10- phosphaphenanthrene 10-oxide(DOPO). The structure of HAP-DOPO was characterized by Fourier transformed infrared (FT-IR) spectroscopy and ¹H nuclear magnetic resonance (¹H NMR) and ³¹P nuclear magnetic resonance (³¹P NMR). The additive HAP-DOPO was blended into diglycidyl ether of bisphenol-A (DGEBA) to prepare flame retardant epoxy resins. The flame retardant properties and thermal properties of the epoxy resins cured by 4, 4′-Diamino-diphenyl sulfone (DDS) were investigated from the differential scanning calorimeter (DSC), the thermogravimetric analysis (TGA), UL94 test, the limiting oxygen index (LOI) test and Cone calorimeter. Compared to traditional DOPO-DGEBA and ODOPB-DGEBA thermosets, the HAP-DOPO/DGEBA thermosets have higher T_gs at the same UL94 V-0 flammability rating for their higher crosslinking density and have higher char yield and lower pk-HRR at same 1.2 wt.% phosphorus content which confirm that HAP-DOPO has higher flame retardant efficiency on thermosets. The scanning electron microscopy (SEM) results shows that HAP-DOPO in DGEBA/DDS system obviously accelerate formation of the sealing, stronger and phosphorus-rich char layer to improve flame retardant properties of matrix during combustion.     

Novel tetrapotassium azo diphosphonate (INAZO) as flame retardant for polyurethane adhesives

An inorganic azo diphosphonate (INAZO), (KO)₂(O)P-NN-P(O)(OK)₂·4H₂O, was synthesized and tested as a novel type of flame retardant additive for castor oil and oligomeric methylene diphenyl diisocyanate (PMDI) based two component polyurethane adhesive with or without using dolomite ((CaMg(CO₃)₂) as filler. Flammability according to UL 94 test and performance under forced-flaming conditions (cone calorimeter) were investigated at the additive loadings of 5, 10 and 20 wt %. It was shown that INAZO improves flame retardancy by significantly reducing heat release rate (HRR), maximum average rate of heat emission (MARHE) and total smoke release (TSR) values in comparison to CaMg(CO₃)₂ filled polyurethane adhesives. The macroscopic structure of the sample residues after cone calorimeter measurement was also analysed. The action mechanism of the developed INAZO flame retardant is suggested to be mainly in the condensed phase. UL 94 V-0 rating was achieved in the vertical burning test when 10 wt % loading of INAZO was used, whereas the reference flame retardant ammonium polyphosphate (APP) required a loading of 20 wt % to reach the V-0 classification.