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1.
Synergistic effect was observed between expandable graphite (EG) and ammonium polyphosphate (APP) on flame retarded polylactide (PLA) in this paper using limiting oxygen index (LOI), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) and X-ray spectroscopy (XPS) and cone calorimeter tests etc. In the experiments, PLA composites with 15 wt% of APP/EG(1:3) combinations showed a LOI value of 36.5 and V-0 rating in UL-94 tests, greatly improved flame retardant properties from composites with APP or EG alone. Results from TGA and cone calorimeter demonstrated that APP/EG combination could retard the degradation of polymeric materials above the temperature of 520 °C by promoting the formation of a compact char layer. This char layer protects the matrix effectively from heat penetrating inside and prevents its further degradation, resulting in lower weight loss rate and better flame retarded performance.  相似文献   

2.
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 (Pf) in the cured films at the presence of a photofragmenting initiator were investigated. The results showed that the Pf 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 Tg 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.  相似文献   

3.
A novel flame retardant system of poly(vinyl alcohol) (PVA) is prepared via using ammonium polyphosphate (APP) and layered double hydroxide (LDH). The flammability of PVA composites containing APP-based LDH at a 15 wt.% global percentage showed that the flame retardancy of all PVA/APP/LDH samples increase with the increase of LDH concentration in the range of 0.1-1.0 wt.%, and reach a LOI value of up to 33 and UL-94 V-0 rating for most composites. Thermo-gravimetric analysis reveals that PVA/APP/LDH samples show higher initial decomposition temperature in comparison with PVA/APP composite. The morphology and structures of residues generated during LOI test were investigated by scanning electronic microscopy (SEM). Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to analyze the composition of the residue formed after thermo-oxidation to support a fundamental analysis for the mechanism of char formation. The test of mechanical properties demonstrated that LDH can enhance tensile strength, Young's modulus and elongation at break of PVA/APP composites.  相似文献   

4.
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.  相似文献   

5.
The combination of synergistic agent with intumescent flame retardant (IFR) systems provides a promising way to prepare high performance IFR composites. In this study, the effects of the synthetic zeolite 4 A in combination with the IFR system consisting of ammonium polyphosphate (APP) and tris (2-hydroxyethyl) isocynurate (THEIC) on thermal degradation, mechanical properties, flame retardancy and char formation of high-density polyethylene composites were investigated by limiting oxygen index (LOI) measurement, cone calorimetry, scanning electron microscopy and laser Raman spectroscopy. The LOI value of HD/FR/Z-0.5 composite with an optimum content of 0.5 wt. % zeolite 4 A and 25 wt. % of total flame retardant reaches 26.3 %. A low loading of zeolite 4 A can improve the bench-scale combustion performance as determined by cone calorimetry, and promote the formation of more compact char residue with a highly graphitic structure. However, a low loading of zeolite in combination with the IFR system consisting of APP and THEIC produces no significant changes in mechanical performance.  相似文献   

6.
A hyperbranched polyamine was prepared using an A2 + B3 approach. It acted as a hyperbranched charring and foaming agent (HCFA) in combination with ammonium polyphosphate (APP) to form a new intumescent flame retardant (IFR) system for polyamide 6 (PA6). Effect of HCFA on flame retardant and thermal degradation properties of IFR‐PA6 was investigated by limiting oxygen index (LOI), UL‐94 vertical burning, cone calorimeter, and thermogravimetric analysis (TGA) tests. The IFR system presented the most effective flame retardancy in PA6 when the weight ratio of APP to HCFA was 2:1. The LOI value of IFR‐PA6 could reach 36.5 with V‐0 rating when the IFR loading was 30 wt%. Even if the loading decreased to 25 wt%, IFR‐PA6 could still maintain V‐0 rating with an LOI value of 31. TGA curves indicated that APP would interact with both PA6 and HCFA in PA6/APP/HCFA composite under heating. The interaction between APP and HCFA improved the char formation ability of IFR system and then much more char was formed for PA6/APP/HCFA composite than for PA6/APP. Therefore, better flame retardancy was achieved. Moreover, the structure and morphology of char residue were studied by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The results indicated that compact and foaming char layer containing P‐O‐C structure was formed for PA6/APP/HCFA system during combustion. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

7.
The synergistic effect between a char forming agent (CFA) and microencapsulated ammonium polyphosphate (MAPP) on the thermal and flame retardancy of polypropylene (PP) are investigated by limiting oxygen index (LOI), UL‐94 test, cone calorimetry, thermogravimetric analysis (TGA), scanning electron micrograph (SEM), and water resistance test. The results of cone calorimetry show that heat release rate peak (PHRR), total heat release (THR), and the mass loss of PP with 30 wt% intumescent flame retardant (IFR, CFA/MAPP = 1:2) decreases remarkably compared with that of pure PP. The HRR, THR, and mass loss decrease, respectively from 1140 to 100 kW/m2, from 96 to 16.8 MJ/m2, and from 100 to 40%. The PP composite with CFA/MAPP = 1:2 has the best water resistance, and it can still obtain a UL‐94 V‐0 rating after 168 hr soaking in water. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

8.
The triazine-based charring agent (CFA) with perfect charring ability was synthesized and characterized. The synergistic effects between CFA and aluminum phosphinate (AlPi) on flame retardancy, thermal degradation, and flammability properties of thermoplastic polyester-ether elastomer (TPEE) were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimeter test (CCT), thermogravimetric analysis (TGA), laser Raman spectroscopy (LSR) and scanning electron microscopy (SEM). The results from UL-94 test showed that, by compounding 14 wt% AlPi and 4 wt% CFA with TPEE, the LOI value reached 28.5% and the UL-94 rating reached V-0 (1.6 mm). TGA results indicated that there is good synergistic charring ability between CFA and AlPi, especially the increased residues at high temperature (T > 700 °C). The CCT test results showed that CFA could change the combustion behavior of TPEE and effectively accelerate the formation of expanded carbon layers. The residues after combustion were measured by LRS and SEM, demonstrating that CFA can promote the formation of dense and stable carbon layers during the combustion, which could inhibit the melt dropping and improve the fire retardancy of TPEE composites. Thus, CFA was a promising synergistic agent in halogen-free flame retardant TPEE.  相似文献   

9.
A series of flame-retardant unsaturated polyester resin (UPR) were prepared by the addition of dimethyl methylphosphonate (DMMP) with various amounts of aluminum hydroxide (ATH) or ammonium polyphosphate (APP) as the flame retardants. The combustion resistance effects of ATH/DMMP and APP/DMMP systems were evaluated by limiting oxygen index test and vertical burning test (UL-94). The thermal properties of UPR were investigated by thermogravimetric analysis. The structure of char was observed by scanning electron microscopy. DMMP incorporated with ATH or APP improved the flame retardancy and thermal properties of UPR. However, the fire-retardant mechanism of these two systems were different: The ATH/DMMP system provided synergistic effect in charring property of the UPR, produced great amount of residual char, and thus revealed the excellent flame retardancy. The APP/DMMP system further improved the flame retardancy of the UPR due to the change in the residual char structure rather than the increase in the production of char.  相似文献   

10.
A monomer, acryloxyethyl phenoxy phosphorodiethyl amidate (AEPPA), was synthesized and characterized using Fourier transform infrared (FTIR), 1H nuclear magnetic resonance spectroscopy (1H NMR) and 31P NMR. The copolymer with various amounts of styrene (St) was obtained by the free radical bulk polymerization between AEPPA and St, and characterized using 1H NMR. The thermal properties of the copolymers were investigated with thermogravimetric analysis (TGA) in air and nitrogen atmosphere, and differential scanning calorimetry (DSC). The TGA results in air indicated the copolymers with AEPPA show higher thermal stability than those without AEPPA. However, the TGA results in nitrogen showed that the decomposition temperature decreased and the char residue increased with the increase of AEPPA. The glass transition temperature (Tg) of the copolymers from DSC indicated that a inverse proportion was observed between Tg and the amount of AEPPA incorporated. The flammability of the copolymers was evaluated by microscale combustion calorimeter (MCC). The MCC results showed that AEPPA can decrease the peak heat release rate (PHRR) and the heat release capacity (HRC), and the sample CP10 shows the lowest PHRR and HRC.  相似文献   

11.
Abstract

A triazine-based macromolecular hybrid charring agent containing zinc borate (MCA-K-ZB) was synthesized and combined with ammonium polyphosphate (APP) to improve the flame retardancy of polypropylene (PP). The flame retardancy and thermal properties of PP composites were investigated using limited oxygen index, vertical burning test, and thermogravimetric analysis. The results showed APP/MCA-K-ZB can improve the flame retardancy of PP compared with APP/MCA-K/ZB. The morphology of the char residues was investigated by scanning electron microscopy (SEM). The SEM result shows that MCA-K-ZB can improve the compactness and continuity of char residue compared with MCA-K/ZB, therefore improving the flame retardancy of PP composites.  相似文献   

12.
A crosslinked silicone‐containing macromolecular charring agent (CSi‐MCA) was synthesized via “one‐pot” process, and it was combined with ammonium polyphosphate (APP) to synergistically improve the flame retardancy of poly(l ‐lactic acid) (PLA). The chemical structure of synthesized CSi‐MCA was characterized by Fourier transform infrared spectroscopy and solid‐state 13C nuclear magnetic resonance. The thermal gravimetric analyzer indicated that the CSi‐MCA displayed good thermal stability and high residue via the catalytic crosslinking. Furthermore, the flame retardant effect of CSi‐MCA and APP as intumescent flame retardants in PLA system was investigated by limited oxygen index, UL94, and cone calorimeter test. When the content of CSi‐MCA was 5 wt% and APP was 10 wt% (CSi‐MCA/APP = 1/2), the limited oxygen index value of composites was 33.6 and UL94 classed a V‐0 rating. The peak heat release rate and total heat release of PLA composites containing both APP and CSi‐MCA decreased significantly in comparison with those with APP or CSi‐MCA alone. The flame retardancy mechanism was investigated via analyzing residual chars by scanning electron microscopy and X‐ray photoelectron spectroscopy as well as the possible chemical reaction between APP and CSi‐MCA by thermal gravimetric analyzer and Fourier transform infrared spectroscopy. The results showed that the enhanced flame retardancy was attributed mainly to synergistic effect of CSi‐MCA and APP, which could form a compact, continuous, and protective layer during combustion. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

13.
A new triazine polymer was synthesized by using cyanuric chloride, ethanolamine and ethylenediamine as raw materials. It is used both as a charring agent and as a foaming agent in intumescent flame retardants, designated as charring-foaming agent (CFA). Effect of CFA on flame retardancy, thermal degradation and mechanical properties of intumescent flame retardant polypropylene (PP) system (IFR-PP system) has been investigated. The results demonstrated that the intumescent flame retardant (IFR) consisting of CFA, APP and Zeolite 4A is very effective in flame retardancy of PP. It was found that when the weight ratio of CFA to APP is 1:2, that is, the components of the IFR are 64 wt% APP, 32 wt% CFA and 4 wt% Zeolite 4A, the IFR presents the most effective flame retardancy in PP systems. LOI value of IFR-PP reaches 37.0, when the IFR loading is 25 wt% in PP. It was also found that when the IFR loading is only 18 wt% in PP, the flame retardancy of IFR-PP can still pass V-0 rating, and its LOI value reaches 30.2. TGA data obtained in pure nitrogen demonstrated that CFA has a good ability of char formation itself, and CFA shows a high initial temperature of the thermal degradation. The char residue of CFA can reach 35.7 wt% at 700 °C. APP could effectively promote the char formation of the APP-CFA system. The char residue reaches 39.7 wt% at 700 °C, while it is 19.5% based on calculation. The IFR can change the thermal degradation behaviour of PP, enhance Tmax of the decomposition peak of PP, and promote PP to form char, based upon the results of the calculation and the experiment. This is attributed to the fact that endothermic reactions took place in IFR charring process and the char layer formed by IFR prevented heat from transferring into inside of IFR-PP system. TGA results further explained the effective flame retardancy of the IFR containing CFA.  相似文献   

14.
The synergistic effect of phosphorus oxynitride(PON) with a novolac-based char former modified by salification (NA-metal salt) on the flame retardance of polyamide 6(PA6) was investigated.For this purpose,various flame-retardant PA6 systems were melt-compounded with PON,PON/NA,PON/NA-V2O5 and PON/NA-Fe2O3,and their flame retardance was evaluated by measuring the limiting oxygen index(LOI) values and UL-94 vertical burning ratings.The results showed that,compared with the PA6/PON/NA system,the combination of two char formers(NA-V2O5,NA-Fe2O3) with PON could obviously improve the char formation and flame retardance of PA6.The flame retardance and cone calorimetric analyses showed the stronger synergism as well as the better flame retardant performance of PON/NA-Fe2O3 flame retardant system. The effects of different char formers on the flame retardance and thermal stability of this system were also discussed.  相似文献   

15.
A phosphorus-nitrogen reactive flame retardant curing agent poly-(isophorondiamine spirocyclic pentaerythritol bisphosphonate) (PIPSPB) was synthesized. The chemical structure of the obtained compound was identified by FTIR, 1HNMR, and mass spectroscopies. Different proportions of DDS and PIPSPB were compounded as the curing agents to prepare a series of flame retardant epoxy resins with different phosphorus contents. The curing behavior of E-44/PIPSPB?+?DDS system was studied by DSC. A series of tests were conducted to characterize E-44/PIPSPB?+?DDS thermosetting system’s performance. The result demonstrates that the residual carbon content of EP/PIPSPB?+?DDS system is obviously higher than that of EP/DDS system after 500?°C with the increase of phosphorus content in the system, and the heat release rate of the system during combustion is significantly reduced. The generated phosphorus-containing carbon layer is obviously foamed, which shows that the flame retardancy of the system is the result of the combined action of condensed phase and gas phase. When the phosphorus content is 1.77wt%, EP-3 successfully passed UL94 V-0 flammability rating, the LOI value was as high as 29%, the impact strength and tensile strength of it were 6.08KJ/m2 and 49.10MPa respectively, the adhesive strength could reach 13.89?MPa, the system presents a good overall performance.  相似文献   

16.
The effects of lanthanum oxide (La2O3) as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (IFR-PP) were studied, and the new IFR system mainly consisted of the charring-foaming agent (CFA) and ammonium polyphosphate (APP). The limiting oxygen index (LOI), UL-94 test, thermogravimetric analysis (TGA), cone calorimeter (CONE) and scanning electron microscopy (SEM) were used to evaluate the synergistic effects of La2O3. It was found that when IFR was fixed at 20 wt% in IFR-PP composites, only a little amount of La2O3 could enhance LOI value and pass the UL-94 V0 rating test (1.6 mm). The TGA data showed that La2O3 could enhance the thermal stability of the IFR-PP systems at high temperature and effectively increase the char residue formation. The CONE results revealed that La2O3 and IFR could clearly change the decomposition behavior of PP and form a char layer on the surface of the composites, consequently resulting in efficient reduction of the flammability parameters, such as heat release rate (HRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), ignition time (IT) and so on. The morphological structures observed by SEM demonstrated that La2O3 could promote to form the homogenous and compact intumescent char layer. Thus, a suitable amount of La2O3 plays a synergistic effect in the flame retardancy and smoke suppression of IFR composites.  相似文献   

17.
In order to explore the structure mode of intumescent flame retardants (IFRs) with higher efficiency, IFR particles with joint‐aggregation structure (@IFR) were obtained through the treatment of ammonium polyphosphate (APP) and a charring agent (PT‐Cluster) in their aqueous solution. Then, the joint‐aggregation IFR effect was researched using its application in polypropylene. In case of 20 wt% IFR loading, the limiting oxygen index (LOI) value of @IFR/PP was 1.1% higher than that of 15APP/5PT‐Cluster/PP mixture, and a 1.6 mm‐thick @IFR/PP composite passed the UL 94 V‐2 rating test, while 15APP/5PT‐Cluster/PP demonstrated no flame‐retardant rating in UL 94 vertical burning tests. In a cone calorimeter test, @IFR also had a better inhibition effect on heat release. The average heat release rate (av‐HRR) value during 0 to 120 seconds of @IFR/PP was only 41 kW m?2, which was 33.9% lower than that of the 15APP/5PT‐Cluster/PP. Furthermore, the peak heat release rate (pk‐HRR) of @IFR/PP was 20.5% lower than that of 15APP/5PT‐Cluster/PP, and the time to pk‐HRR of @IFR/PP was 710 seconds, while that of 15APP/5PT‐Cluster/PP was 580 seconds. The better inhibition effect on HRR and the delay of time to pk‐HRR were caused by the joint‐aggregated structure of @IFR, which can rapidly react to form stable and efficient char layers. This kind of join‐aggregation IFR effect has great significance in suppressing the spread of fire in reality. In addition, @IFR also increased the mechanical properties of PP composites slightly compared with the APP/PT‐Cluster mixture.  相似文献   

18.
Ammonium polyphosphate (APP)/polypropylene (PP) composites were prepared by melt blending and extrusion in a twin-screw extruder. APP was first modified by a silane coupling agent KH-550 then added to polypropylene. The surface modification of APP by the coupling agent decreased its water solubility and its interface compatibility with the PP matrix. Limiting oxygen index (LOI) and thermogravimetric analysis (TGA) were used to characterize the flame retardant property and the thermal stability of the composites. The addition of APP improved the flame retardancy of PP remarkably. The crystal structures of APP/PP composites were characterized by X-ray diffraction (XRD). The results indicated that β-crystal phase PP may be formed. The structures and morphologies of APP, KH-550/APP and APP/PP composites were characterized by field-emission scanning electron microscope (FESEM). The mechanical property tests showed good mechanical properties of composite materials. Compared with unmodified one, the impact strength, tensile strength and elongation of modified APP/PP were all improved.  相似文献   

19.
A novel type of hyperbranched (3-hydroxyphenyl) phosphate (HHPP) with high functionality as a curing agent of epoxy resins was synthesized and characterized by FTIR, 1H NMR and vapor phase osmometry (VPO). The cured epoxy resin with HHPP possessed improved glass transition temperature. The thermostability and flame retardancy of O-cresol novolac epoxy resin cured with different contents of HHPP were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI) and cone calorimetry. The obtained results show that the samples containing a higher percentage of HHPP exhibit relatively lower thermostability at lower temperature while higher thermostability at elevated temperature and more char was formed compared with those containing a lower percentage of HHPP. The LOI value increased from 22.0 to 30.0 when HHPP, instead of 1,3-dihydroxybenzene, was used as a curing agent. The 25 wt% addition of HHPP in the curing agent complex effectively decreased the heat release rate and improved the char yield to the content nearly similar as those of the epoxy resin cured with pure HHPP.  相似文献   

20.
A s-triazine containing hyperbranched polyamine (HBPA) has been synthesized from cyanuric chloride and aromatic diamine, 4,4′-(1,4-phenylenediisopropylidene) bis-aniline by nucleophilic displacement polymerization technique using an A2 + B3 approach with high yield (>80%). The synthesized polymer has been characterized by 1H NMR, 13C NMR, FT-IR spectroscopic studies, elemental analysis, solubility and measurement of solution viscosity. The thermogravimetric (TG) analysis and differential scanning calorimetric (DSC) studies indicate that the polymer is thermostable upto 290 °C without any decomposition and has glass transition temperature of 243 °C. The flame retardancy of the pure powder polymer and the blends with linear commercial polymers such as plasticized PVC and LDPE with this hyperbranched polymer were investigated by the measurement of limiting oxygen index (LOI) value. The results show that the polymer has self-extinguishing characteristic (LOI = 38) and acts as an effective flame retardant additive for the above linear base polymers. The synergistic effect of this hyperbranched flame retardant was observed with triphenyl phosphine oxide in the same base polymers. The flammability efficiency of the hyperbranched polyamine is also evaluated by help of thermogravimetric (TG) analysis. The heat aging and leaching in different chemical media did not influence the flame retardancy of the blends.  相似文献   

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