Preparation of phosphorus‐containing phenolic resin and its application in epoxy resin as a curing agent and flame retardant

For the sake of improving the flame retardancy of epoxy resin (EP), a novel phosphorus‐containing phenolic resin (PPR) synthesized in our group instead of conventional phenolic resin (PR) was used to cure EP in the present research. The curing processes and the corresponding crosslinking structure and mechanical performance were investigated by differential scanning calorimeter and dynamic mechanical thermal analysis. Because of the introduction of flame‐retarding elements including P and Si, PPR exhibited higher charring capacity in the condensed phase, which is helpful to construct a char layer of higher quality. Correspondingly, PPR‐cured EP displayed remarkably improved flame retardance as compared to conventional PR‐cured EP through the related evaluations including limiting oxygen index, vertical burning test, and microscale combustion colorimeter. As a multifunction agent, it is believable that PPR possesses potential commercial value to prepare flame‐retardant EP with high performance.     

Effect of a triazine ring‐containing charring agent on fire retardancy and thermal degradation of intumescent flame retardant epoxy resins

A triazine ring‐containing charring agent (PEPATA) was synthesized via the reaction between 2,6,7‐trioxa‐l‐phosphabicyclo‐[2.2.2]octane‐4‐methanol (PEPA) and cyanuric chloride. It was applied into intumescent flame retardant epoxy resins (IFR‐EP) as a charring agent. The effect of PEPATA on fire retardancy and thermal degradation behavior of IFR‐EP system was investigated by limited oxygen index (LOI), UL‐94 test, microscale combustion calorimetry (MCC), thermogravimetric analysis (TGA) and thermogravimetric analysis/infrared spectrometry (TG‐IR). The glass transition temperatures (T_g) of IFR‐EP systems were studied by dynamic mechanical analysis (DMA). The LOI values increased from 21.5 for neat epoxy resins (EPs) to 34.0 for IFR‐EP, demonstrating improved flame retardancy. The TGA curves showed that the amount of residue of IFR‐EP system was largely increased compared to that of neat EP at 700 °C. The new IFR‐EP system could apparently reduce the amount of decomposing products at higher temperatures and promotes the formation of carbonaceous charred layers that slowed down the degradation. Copyright © 2010 John Wiley & Sons, Ltd.     

Flame‐retardant performance and mechanism of epoxy thermosets modified with a novel reactive flame retardant containing phosphorus,nitrogen, and sulfur

A novel phosphorus‐containing, nitrogen‐containing, and sulfur‐containing reactive flame retardant (BPD) was successfully synthesized by 1‐pot reaction. The intrinsic flame‐retardant epoxy resins were prepared by blending different content of BPD with diglycidyl ether of bisphenol‐A (DGEBA). Thermal stability, flame‐retardant properties, and combustion behaviors of EP/BPD thermosets were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The flame‐retardant mechanism of BPD was studied by TGA/infrared spectrometry (TGA‐FTIR), pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), morphology, and chemical component analysis of the char residues. The results demonstrated that EP/BPD thermosets not only exhibited outstanding flame retardancy but also kept high glass transition temperature. EP/BPD‐1.0 thermoset achieved LOI value of 39.1% and UL94 V‐0 rating. In comparison to pure epoxy thermoset, the average of heat release rate (av‐HRR), total heat release (THR), and total smoke release (TSR) of EP/BPD‐1.0 thermoset were decreased by 35.8%, 36.5% and 16.5%, respectively. Although the phosphorus content of EP/BPD‐0.75 thermoset was lower than that of EP/DOPO thermoset, EP/BPD‐0.75 thermoset exhibited better flame retardancy than EP/DOPO thermoset. The significant improvement of flame retardancy of EP/BPD thermosets was ascribed to the blocking effect of phosphorus‐rich intumescent char in condensed phase, and the quenching and diluting effects of abundant phosphorus‐containing free radicals and nitrogen/sulfur‐containing inert gases in gaseous phase. There was flame‐retardant synergism between phosphorus, nitrogen, and sulfur of BPD.     

Improving Thermal and Flame Retardant Properties of Epoxy Resin with Organic NiFe‐Layered Double Hydroxide‐Carbon Nanotubes Hybrids

To improve the dispersion of carbon nanotubes (CNTs) and flame retardancy of layered double hydroxide (LDH) in epoxy resin (EP), organic nickel‐iron layered double hydroxide (ONiFe‐LDH‐CNTs) hybrids were assembled through co‐precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe‐LDH‐CNTs nanocomposites containing 4 wt% of ONiFe‐LDH‐CNTs with different ratios of ONiFe‐LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy (TEM). The results revealed a coexistence of exfoliated and intercalated ONiFe‐LDH‐ CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe‐LDH‐CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe‐LDH and synergistic effect between ONiFe‐LDH and CNTs.     

Synthesis of bio‐based poly (cyclotriphosphazene‐resveratrol) microspheres acting as both flame retardant and reinforcing agent to epoxy resin

A highly cross‐linked poly (cyclotriphosphazene‐resveratrol) microsphere (PRV) was synthesized by using hexachlorocyclotriphosphazene (HCCP) and bio‐based resveratrol (REV) as raw materials, and the obtained PRV microspheres were applied to improve the flame retardancy and mechanical property of epoxy resin (EP). The TGA results showed that the PRV microsphere is an excellent charring agent and the char yield is as high as 62% at 800°C. The incorporation of PRV makes the initial degradation earlier yet significantly increases the char residue of EP composites. Moreover, the introduction of PRV microspheres into EP greatly promoted the flame retardancy performance. Under 3% of addition of PRV microspheres, the peak heat release rate (PHRR) and total heat release (THR) were decreased by 58.3% and 29.6%, respectively, the limited oxygen index (LOI) value was increased to 29.7% from 25.3% of pure EP. In addition, because of the uniform distribution in EP matrix and the enhancing effect of PRV microspheres, the mechanical properties including tensile modulus of EP composites were strengthened. PRV microspheres in this paper provide a possibility to synthesize a dual functional filler, which acts as both flame retardant and strengthening agent.     

Synergistic flame‐retardant effect and mechanisms of boron/phosphorus compounds on epoxy resins

To explore the component synergistic effect of boron/phosphorus compounds in epoxy resin (EP), 3 typical boron compounds, zinc borate (ZB), boron phosphate (BPO₄), and boron oxide (B₂O₃), blended with phosphaphenanthrene compound TAD were incorporated into EP, respectively. All 3 boron/phosphorus compound systems inhibited heat release and increased residue yields and exerted smoke suppression effect. Among 3 boron/phosphorus compound systems, B₂O₃/TAD system brought best flame‐retardant effect to epoxy thermosets in improving the UL94 classification of EP composites and also reducing heat release most efficiently during combustion. B₂O₃ can interact with epoxy matrix and enhance the charring quantity and quality, resulting in obvious condensed‐phase flame‐retardant effect. The combination of condensed‐phase flame‐retardant effect from B₂O₃ and the gaseous‐phase flame‐retardant effect from TAD effectively optimized the action distribution between gaseous and condensed phases. Therefore, B₂O₃/TAD system generated component synergistic flame‐retardant effect in epoxy thermosets.     

Synthesis of a novel phosphorus‐containing curing agent and its effects on the flame retardancy,thermal degradation and moisture resistance of epoxy resins

A novel phosphorus‐containing compound diphenyl‐(1, 2‐dicarboxylethyl)‐phosphine oxide defined as DPDCEPO was synthesized and used as a flame retardant curing agent for epoxy resins (EP). The chemical structure of the prepared DPDCEPO was well characterized by Fourier transform infrared spectroscopy, and ¹H, ¹³C and ³¹P nuclear magnetic resonance. The DPDCEPO was mixed with curing agent of phthalic anhydride (PA) with various weight ratios into epoxy resins to prepare flame retardant EP thermosets. The flame retardant properties, combustion behavior and thermal analysis of the EP thermosets were respectively investigated by limiting oxygen index (LOI), vertical burning tests (UL‐94), cone calorimeter measurement, dynamic mechanical thermal analysis and thermogravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of the char residues for EP thermosets were respectively investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS). The water resistant properties of the cured EP were evaluated by putting the samples into distilled water at 70°C for 168 hr. The results revealed that the EP/20 wt% DPDCEPO/80 wt% PA thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value was as high as 33.2%. The cone test results revealed that the incorporation of DPDCEPO effectively reduced the combustion parameters of the epoxy resin thermosets, such as heat release rate and total heat release. The dynamic mechanical thermal analysis test demonstrated that the glass transition temperature (Tg) decreased with the increase of DPDCEPO content. The TGA results indicated that the incorporation of DPDCEPO promoted the decomposition of epoxy resin matrix ahead of time and led to a higher char yield and thermal stability at high temperatures. The surface morphological structures and analysis of the XPS of the char residues of EP thermosets revealed that the introduction of DPDCEPO benefited the formation of a sufficient, compact and homogeneous char layer with rich flame retardant elements on the epoxy resin material surface during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After water resistance tests, the EP/20 wt% DPDCEPO/80 wt% PA thermosets retained excellent flame retardancy, and the moisture adsorption of the EP thermosets decreased with the increase of DPDCEPO content in EP thermosets because of the existence of the P–C bonds and the rigid aromatic hydrophobic structure in DPDCEPO. Copyright © 2015 John Wiley & Sons, Ltd.     

Computer-aided cooling curve thermal analysis and microstructural evolution of Mg–5Zn–xY cast alloys

The organo-montmorillonite (MT), combined with a DOPO-based oligomer (PDAP), was used to improve the flame retardancy of epoxy thermoset. The thermal stabilities and flame-retardant properties of thermosets were investigated by thermogravimetric analysis, limiting oxygen index (LOI) and UL-94 tests. The synergistic effect of MT and PDAP was studied by Py–GC/MS, Fourier transform infrared spectroscopy, elemental analysis, laser Raman spectroscopy and scanning electron microscope. Results revealed that 0.5 mass% MT combined with 4 mass% PDAP showed obvious synergistic effect on enhancing the flame retardancy of thermoset. The corresponding thermoset achieved an LOI value of 35.5% and V-0 rating in UL-94 test, which was attributed to the intense blowing-out effect during combustion. The synergistic mechanism was probably ascribed to the formation of silicoaluminophosphate (SAPO) originating from the reaction between MT and PDAP. The SAPO serving as a solid acidic catalyst, coupled with the acid sites from the decomposition of organomodifier in MT, could promote the charring process. With the further increase in MT content, the charring process was strongly promoted and more phosphorus element was retained in the condensed phase, which inevitably resulted in the remarkable decrease of the amount of pyrolytic gases containing phosphorus-based radicals and nonflammable gases. These factors were responsible for the diminished blowing-out effect during combustion, which was adverse to the further improvement of flame retardancy.     

Synergistic effects of β‐cyclodextrin containing silicone oligomer on intumescent flame retardant polypropylene system

The effects of β‐cyclodextrin containing silicone oligomer(CDS), as a synergistic agent, on the flame retardancy and mechanical properties of intumescent flame retardant polypropylene composites were studied by adding different amounts of CDS in intumescent flame retardants. The limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) were utilized to evaluate the synergistic effects of CDS in the composites. It was found that after a little amount of CDS partially replaced a charring‐foaming agent (CFA) in IFR, LOI values of the composites were enhanced and they obtained a UL‐94 V‐0 rating. IFR system containing 6.25wt% CDS presented the best flame retardancy in PP. The experimental results obtained from LOI and UL‐94, TGA, SEM, and mechanical properties indicated that the combination of CDS and CFA presents synergistic effects in flame retardancy, char formation, and mechanical properties of the composites. This is probably due to different structures of polyhydroxyl macromolecules (CDS and CFA), the existence of dimethyl silicone group in CDS, and the toughness of epoxy silicon chain in CDS. SEM results proved that the interfacial compatibility between IFR and PP was improved by CDS. Copyright © 2009 John Wiley & Sons, Ltd.     

Flame‐retardant epoxy resins with high glass‐transition temperatures from a novel trifunctional curing agent: Dopotriol

A novel phosphorus‐containing trifunctional novolac (dopotriol) was synthesized through the addition reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide and rosolic acid. The structure of dopotriol was confirmed with NMR spectroscopy and elemental analyses. The dopotriol was blended with phenol novolac in the ratios of 10/0, 8/2, 6/4, 4/6, 2/8, and 0/10 to serve as a curing agent for diglycidyl ether of bisphenol A. Thermal properties, such as the glass‐transition temperature, thermal decomposition temperature, and flame retardancy, moisture absorption, and dielectric properties of the cured epoxy resins were evaluated. The activity and activation energy of curing were studied with the methods of Kissinger and Ozawa by dynamic differential scanning calorimetry scans. The glass‐transition temperatures of the cured epoxy resins were 138–159 °C, increasing with the phosphorus content. This is rarely seen in the literature after the addition of a flame‐retardant element. The flame retardancy increased with the phosphorus content, and a UL‐94 V‐0 grade was achieved with a phosphorus content of 1.87%. Similar dielectric properties and moisture absorption were observed for these phosphorus‐containing epoxy resins, and this implied that the addition of phosphorus to epoxy did not affect the dielectric properties and moisture absorption. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2862–2873, 2005     

聚苯氧基磷酸联苯二酚酯/聚磷酸铵膨胀阻燃剂对环氧树脂阻燃性能影响研究

以聚苯氧基磷酸联苯二酚酯(PBPP)与聚磷酸铵(APP)组成复合阻燃剂,对环氧树脂(EP)进行阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法研究改性环氧树脂的阻燃性能和阻燃机理.结果表明,PBPP/APP体系对EP具有较好的阻燃性能,阻燃剂添加量为10%时能使环氧树脂的氧指数提高到29.6%,垂直燃烧等级达到UL94 V-0级,残炭量大大增加;平均热释放速率下降45.7%,热释放速率峰值下降51.0%,有效燃烧热平均值下降21.1%;TGA、CONE、SEM等综合分析显示了PBPP/APP改性后的环氧树脂比纯环氧树脂具有更高的热稳定性,燃烧后能够形成连续、致密、封闭、坚硬的焦化炭层,在聚合物表面产生有效覆盖、隔绝了氧气,改善了环氧树脂的燃烧性能.     

Facile preparation of novel epoxy curing agents and their high‐performance thermosets

Two flame‐retardant epoxy curing agents, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐yl‐tris(4‐hydroxyphenyl)methane (1) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐yl‐ (4‐aminophenyl)‐bis(4‐hydroxyphenyl)methane (2), were prepared by a facile, economic, one‐pot procedure. The structures of the curing agents were confirmed by IR, high‐resolution mass, 1‐D, and 2‐D NMR spectra. A reaction mechanism was proposed for the preparation, and the effect of electron withdrawing/donating effects on the stabilization of the carbocation was discussed. (1‐2) served as curing agents for diglycidyl ether of bisphenol A (DGEBA), dicyclopentadiene epoxy (HP‐7200), and cresol novolac epoxy (CNE). Properties such as glass transition temperature, coefficient of thermal expansion, thermal decomposition temperature, and flame retardancy of the resulting epoxy thermosets were evaluated. The resulting epoxy thermosets show high T_g, low thermal expansion, moderate thermostability, and excellent flame retardancy. The bulky biphenylene phosphinate pendant makes polymer chains difficult to rotate, explaining the high T_g and low thermal expansion characteristic. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7898–7912, 2008     

Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin

A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine),defined as PPAP,was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid,and the dehydration polymerization under heating in nitrogen atmosphere.Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy,13C and 31p solid-state nuclear magnetic resonance measurements.The synthesized PPAP and curing agent m-phenylenediamine were blended into epoxy resin (EP) to prepare flame retardant EP thermosets.The effects of PPAP on the fire retardancy and thermal degradation behavior of cured EP/PPAP composites were investigated by limiting oxygen index (LOI),vertical burning (UL-94),thermogravimetric analysis/infrared spectrometry (TG-IR) and cone calorimeter tests.The morphologies and chemical compositions of char residues for cured epoxy resin were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS),respectively.The results demonstrated that the flame retardant EP thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 30.8％ when incorporating 5wt％ PPAP into the EP thermosets.The TGA results indicated that the synthesized PPAP flame retardant additive possessed high thermal stability and excellent charring capability.Meanwhile,the incorporation of PPAP stimulated the epoxy resin matrix to decompose and charring ahead of time due to its catalytic decomposition effect,which led to a higher char yield at high temperature.The morphological structures and the analysis results of XPS for char residues of EP thermosets revealed that the introduction of PPAP benefited the formation of a sufficient,more compact and homogeneous char layer containing phosphorus-nitrogen flame retardant elements on the material surface during combustion.The formed char layer with high quality effectively prevented the heat transmission and diffusion,limited the production of combustible gases,and inhibited the emission of smoke,leading to the reduction of heat and smoke release.     

Preparation and characterization of phosphorus‐containing Mannich‐type bases as curing agents for epoxy resin

Two novel phosphorus‐containing Mannich‐type bases, [(2‐{[(diethoxy‐phosphoryl)‐phenyl‐methyl]‐amino}‐ ethylamino)‐phenyl‐methyl]‐phosphonic acid diethyl ester (PEDA) and ({2‐[2‐(2‐{[(diethoxy‐phosphoryl)‐phenyl‐methyl]– amino}‐ethylamino)‐ethylamino]‐ethylamino}‐phenyl‐methyl)‐phosphonic acid diethyl ester (PTTA) were prepared and employed as curing agents in an attempt to prepare flame retardant epoxy systems. Through a curing reaction, phosphorus was incorporated in the backbone of the epoxy polymer. The processing characteristic of these systems was studied in terms of gel time at different temperatures. Thermal and flame retardancy properties of the cured epoxy thermosets were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and flammability test. The degradation activation energy was calculated by Kissinger's model. The results showed that the gel time of the phosphorus‐containing epoxy systems was prolonged; the glass transition temperature (T_g) was increased due to the introduction of phosphorus and the initial degradation activation energy of phosphorus‐containing epoxy systems was lower than phosphorus‐free epoxy systems. High char yield (23–27 wt%) and limiting oxygen index (LOI) values of 28–30 were observed for the phosphorus‐containing epoxy thermosets, indicating their improvement in flame retardancy. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis of a caged bicyclic phosphates derived anhydride and its performance as a flame‐retardant curing agent for epoxy resins

A novel curing and flame‐retardant agent (PEPA‐TMAC) was successfully synthesized. The chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Use of PEPA‐TMAC as part of the curing agent in combination with another anhydride for a commercial epoxy resin (EP) was studied. Results of differential scanning calorimetry (DSC) indicated that PEPA‐TMAC was an effective curing agent for EP. The dynamic mechanical analysis (DMA) results showed that the glass transition temperature (T_g) and cross‐linking density (V_e) of EP composites exhibited an increase trend with the addition of PEPA‐TMAC. The limiting oxygen index (LOI) value of EP composites reached 26.9%, and the cone calorimeter results indicated that peak heat release rate (PHRR), total heat release (THR), smoke produce rate (SPR), and total smoke produce (TSP) remarkably decreased with increasing PEPA‐TMAC content. TGA data showed that the addition of PEPA‐TMAC greatly increased the amount of residual char during combustion. The morphology of the residual char was studied by SEM and showed that the addition of PEPA‐TMAC greatly increased the stability of EP composites. The thermogravimetric analysis (TGA), energy‐dispersive X‐ray spectroscopy (EDS), and FTIR results revealed the flame‐retardant mechanism that PEPA‐TMAC can promote the formation of charred layers with the phospho‐carbonaceous complexes in the condensed phase during burning of EP composites.     

Low flammability and smoke epoxy resins with a novel DOPO‐based imidazolone derivative

In this work, a DOPO‐based imidazolone derivative named DHI was synthesized using DOPO, 5‐amino‐2‐benzimidazolinone and 4‐hydroxybenzaldehyde as raw materials. The chemical structure of DHI was characterized by ¹H‐NMR, ³¹P‐NMR and Fourier transform infrared spectra (FTIR). Then, a series of different flame‐retardant epoxy resin (EP) thermosets were prepared by mixing flame retardant DHI. The thermal properties of the cured EPs was investigated by thermogravimetry analysis (TGA) and differential scanning calorimeter (DSC), and the results showed the thermal stability and glass transition temperature (T_g) of the cured EP modified with DHI declined slightly compared with that of neat EP. The limited oxygen index (LOI) and UL94 test results exhibited DHI imparted good flame retardancy to EP. The EP‐4 (phosphorus content of 1.25%) possessed a LOI value of 36.5% and achieved a V‐0 rating. Furthermore, the peak of heat release rate (PHRR) and total heat release rate (THR) of EP‐4 decreased by 38.7% and 24.5%, respectively. Excitedly, the total smoke production (TSP) of EP‐4 sample declined by 62.5%, which meant DHI also made EP obtain excellent smoke suppression property. Moreover, the flame‐retardant mechanism was studied by scanning electron microscopy (SEM) and pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS). It was reasonable inferred that DHI could not only promote EP to form dense char layer in condensed phase, but also restrain combustion in gaseous phase through catching the free radicals sourced from the degradation of EP.     

Effect of charring agents on solvent‐free fireproof coatings

The choice of charring agent is one of the major issues for solvent‐free fireproof coatings. The effects of processing method and charring agent on the thermal insulation and fire resistance of the coatings were investigated in simulated fire scenarios. Dipentaerythritol (DPER), triazine agent (CFA), and pentaerythritol phosphate (PEPA) were compared as charring agent, and the thermal, combustion, fire resistance, and charring behaviors in different fire scenario were characterized for the fireproof coatings. Compared with high‐speed dispersing equipment, kneading processing equipment is favorable for improving the thermal stability and fire resistance of the coatings, because the stronger shearing force has promoted mixing and dispersion of the ingredients in solvent‐free fireproof coatings. As for charring agents, it is found that the fireproof coatings containing CFA or PEPA show better thermal and flame‐retardant performances. More residue was observed under nitrogen atmosphere in thermogravimetric analysis, less heat and smoke were released in cone calorimetry test. However, during the high temperature fire resistance test, their char layers were prone to delaminate while DPER‐containing coatings produced intact and stronger char layer with better heat insulation. For practical applications, the coating formulations need to be optimized to achieve both fire resistance and flame retardancy.     

Flame‐retardant epoxy resins with high glass‐transition temperatures. II. Using a novel hexafunctional curing agent: 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐yl‐tris(4‐aminophenyl) methane

We synthesized a novel phosphorus‐containing triamine [9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐yl‐tris(4‐aminophenyl) methane (dopo‐ta)] from the nucleophilic addition of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide and pararosaniline chloride, using triethylamine as an acid receiver. We confirmed the structure of dopo‐ta by IR, mass, and NMR spectra and elemental analysis. dopo‐ta served as a curing agent for diglycidyl ether of bisphenol A (DGEBA) and dicyclopentadiene epoxy (hp7200). Properties such as the glass‐transition temperature (T_g), thermal decomposition temperature, flame retardancy, moisture absorption, and dielectric properties of the cured epoxy resins were evaluated. The T_g's of cured DGEBA/dopo‐ta and hp7200/dopo‐ta were 171 and 190 °C, respectively. This high T_g phenomenon is rarely seen in the literature after the introduction of a flame‐retardant element. The flame retardancy increased with the phosphorus content, and a UL‐94 V‐0 grade was achieved with a phosphorus content of 1.80 wt % for DGEBA/dopo‐ta/diamino diphenylmethane (DDM) systems and 1.46 wt % for hp7200/dopo‐ta/DDM systems. The dielectric constants for DGEBA/dopo‐ta and hp7200/dopo‐ta were 2.91 and 2.82, respectively, implying that the dopo‐ta curing systems exhibited low dielectric properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5971–5986, 2005     

Development of novel phosphorus‐containing epoxy resins from renewable resources

Novel biobased epoxy resins were prepared from two fatty acid derivatives; epoxidized 10‐undecenoyl triglyceride and epoxidized methyl 3,4,5‐tris(10‐undecenoyloxy)benzoate, with 4,4′‐diaminodiphenylmethane as a crosslinking agent. The flame retardancy of these epoxy resins was improved by the addition of 10‐[2′, 5′‐bis(9‐oxiranyl‐nonayloxy)phenyl]‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and by crosslinking with a phosphorus‐containing curing agent, bis(m‐aminophenyl)methylphosphine oxide. The thermal, thermomechanical, and flame‐retardant properties of the cured materials were measured with differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and the limiting oxygen index. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6717–6727, 2006     

Fabrication of ZIF‐8@Polyphosphazene core‐shell structure and its efficient synergism with ammonium polyphosphate in flame‐retarding epoxy resin

A novel zeolitic imidazolate framework (ZIF‐8) nanoparticles@polyphosphazene (PZN) core‐shell architecture was synthesized, and then, ZIF‐8@PZN and ammonium polyphosphate (APP) were applied for increasing the flame retardancy and mechanical property of epoxy resin (EP) through a cooperative effect. Herein, ZIF‐8 was used as the core; the shell of PZN was coated to ZIF‐8 nanoparticles via a polycondensation method. The well‐designed ZIF‐8@PZN displayed superior fire retardancy and smoke suppression effect. The synthesized ZIF‐8@PZN observably raised the flame retardancy of EP composites, which could be demonstrated by thermogravimetric analysis (TGA) and a cone calorimeter test (CCT). The chemical structure of ZIF‐8@PZN was characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with pure epoxy, with the incorporation of 3 wt% ZIF‐8@PZN and 18 wt% APP into the EP, along with 80.8%, 72.6%, and 64.7% decreased in the peak heat release rate (pHRR), the peak smoke production rate (pSPR), and the peak CO production rate (pCOPR), respectively. These suggested that ZIF‐8@PZN and APP generated an intumescent char layer, and ZIF‐8@PZN can strengthen the char layer, resulting in the enhancement in the flame resistance of EP.