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1.
A novel flame retardant (PSiN), containing silicon and nitrogen, was synthesized using N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (KH-602) and diphenylsilanediol through solution polycondesation and it was used together with potassium-4-(phenylsulfonyl)benzenesulfonate (KSS) to prepare a flame-retardant system for polycarbonate (PC). The structure and thermal property of PSiN were characterized by Fourier transform infrared spectroscopy (FTIR), 1HNMR and thermogravimetric analysis (TG) tests. Flammability and thermal behaviors of PC/KSS/PSiN systems were estimated by limited oxygen index (LOI), cone calorimeter, vertical burning test (UL-94), and TG tests. The results showed that the flame retardancy and char residues of PC/KSS system were improved with the addition of PSiN. When 1 mass% PSiN and 0.5 mass% KSS were incorporated, the LOI value of PC was found to be 46, and class V-0 of the UL-94 test. Moreover, both the heat release rate and the total heat release of PC/KSS/1 mass% PSiN decreased compared with those of PC and PC/KSS systems. The microstructures observed by scanning electron microscopy and FTIR indicated that the surface of the char for PC/KSS/PSiN system hold a more cohesive and denser char structure when compared with the pure PC and PC/KSS system.  相似文献   

2.
A novel flame retardant (PSiN), containing silicon and nitrogen, was synthesized using N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and diphenylsilanediol through solution polycondensation and it was added to polycarbonate (PC). The structure and thermal properties of PSiN were characterized by fourier transform infrared spectroscopy and thermogravimetric analysis (TG) tests. The effect of PSiN on the flame retardancy and thermal behaviors of PC was investigated by limited oxygen index (LOI), vertical burning test (UL-94), and TG tests. The results showed that the flame retardancy and the thermal stability of PC are improved with the addition of PSiN. When 1 mass% PSiN and 0.5 mass% diphenylsulfone sulfonate (KSS) are incorporated, the LOI value of PC is found to be 46, and class V-0 of UL-94 test is passed. The char structure observed by scanning electron microscopy indicated that the surface of the char for PC/KSS/PSiN system holds a firmer and denser char structure when compared with neat PC and PC/KSS system.  相似文献   

3.
The flame retardancy of bisphenol A polycarbonate (PC) containing potassium diphenylsulfone sulfonate (KSS), poly(aminopropyl/phenylsilsesquioxane) (PAPSQ) and poly(vinylidenefluoride) (PVDF) was measured by limited oxygen index (LOI) and examined according to UL94. A high LOI and UL94 V-0 rating for 1.6 mm thickness samples were obtained by a combined use of equivalent KSS, PAPSQ and PVDF at 0.1-0.3 wt% loading, respectively. The improvement in flame retardancy of PC compositions arose from the synergistic interaction of three additives. Thermogravimetric analysis (TGA) indicated that the combination decreased the activation energy (E) of PC degradation and elevated the thermal degradation rate of PC to ensure the formation of an insulating carbon layer. FTIR analysis showed that the LOI char of PC containing the three additives took on a highly cross-linking aromatic ester and ether structure.  相似文献   

4.
An intumescent flame retardant spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM) has been synthesized and its structure was characterized by Fourier transformed infrared spectrometry (FTIR), 1H and 31P nuclear magnetic resonances (NMR). A series of polylactide (PLA)-based flame retardant composites containing SPDPM were prepared by melt blending method. The combustion properties of PLA/SPDPM composites were evaluated through UL-94, limiting oxygen index (LOI) tests and microscale combustion calorimetry (MCC) experiments. It is found that SPDPM integrating acid, char and gas sources significantly improved the flame retardancy and anti-dripping performance of PLA. When 25 wt% flame retardant was added, the composites achieved UL-94 V0, and the LOI value was increased to 38. Thermogravimetric analysis (TGA) showed that the weight loss rate of PLA was decreased by introduction of SPDPM. In addition, the thermal degradation process and possible flame retardant mechanism of PLA composites with SPDPM were analyzed by in situ FTIR.  相似文献   

5.
A novel efficient halogen-free flame retardant system for polycarbonate   总被引:2,自引:0,他引:2  
A novel silicon- and phosphorus-containing flame retardant, poly (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide siloxane), P(DOPO-VTES) was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and vinyltriethoxy silane(VTES). Its chemical structure was confirmed by FTIR. The thermal gravimetrical analysis (TGA) showed that P(DOPO-VTES) had good thermal stability and a high of char yield (86.31%) at 700 °C in nitrogen atmosphere. Its XRD patterns showed that this compound had a certain ordered structure. P(DOPO-VTES) was blended with polycarbonate (PC) together with montmorillonite(MMT) to prepare a series of organic-inorganic hybrids of flame retardant (PC)/P(DOPO-VTES)/MMT via melt blending. The thermal degradation behavior and flame retardancy of those hybrids were investigated with TGA, limiting oxygen index (LOI), vertical burning test (UL-94), and cone calorimeter. The LOI value of the flame-retardant PC systems could reach a maximal value of 32.8 when the content of P(DOPO-VTES) was 5 wt%. When 2 wt% MMT was added into the PC/5%P(DOPO-VTES) system, the UL-94 rating reached V-0. The possible flame retardant mode of MMT was studied via the dynamic rheological properties of the systems and the morphology of the chars remaining after the LOI test and the cone calorimeter test.  相似文献   

6.
The molecular design for inherently flame-retardant poly(lactic acid) (IFR-PLA) was outlined and achieved by chemically incorporating an effective organophophorus-type flame retardant (FR) into the PLA backbone via the chain extension of the dihydroxyl-terminated prepolymer with 1, 6-hexamethylene diisocyanate (HDI). The structure of IFR-PLA was characterized by 1H- and 31P-nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. IFR-PLA was further blended with the commercial PLA to prepare flame retardant PLA blends (PLA-FR blend). The relevant properties of IFR-PLA and PLA-FR blends were evaluated by differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), limiting oxygen index (LOI) measurements and UL-94 tests. The thermal analysis revealed that the char yield of IFR-PLA and PLA-FR blend above 400 °C was greatly enhanced compared to that of pure PLA. The LOI value was significantly improved from 19 for pure PLA to 29 when 1 wt% of phosphorus content was introduced and all IFR-PLA samples achieved V-0 rating in the UL-94 tests. PLA-FR blends had an LOI value of 25-26 and UL-94 V-2 rating at 20 wt% of IFR-PLA content. The tensile strength of all the FR PLA systems was ca. 60 MPa. The method used in this study provided a novel route to permanently flame retard PLA.  相似文献   

7.
In order to prepare halogen-free flame-retardant glass-fiber-reinforced poly(ethylene terephthalate) (FR-GF-PET), a novel flame retardant containing three flame-retardant elements, P, N and S, was synthesized by melt condensation reaction. Its chemical structure was characterized by FT-IR and 1H NMR spectra. FR-GF-PET was prepared by melt-mixing the flame retardant with GF-PET. The effects of the flame retardant on the flammability and thermally decomposing behaviors of GF-PET were studied via LOI, UL-94 and TGA tests. The results showed that despite a negative effect on the thermal stability of GF-PET, the incorporation of the flame retardant improved the flame retardancy of GF-PET largely. The LOI values of GF-PET increase linearly with the increase of flame retardant content. The GF-PET passed the V-0 rating in UL-94 tests when 15 wt% of the flame retardant was added to GF-PET. An interesting phenomenon was found, that is, with the increase of flame retardant content, the flame retardancy of the system increased but the char yield decreased, which was explained according to the evidences of XPS tests and the kinetics of thermally decomposing reaction.  相似文献   

8.
邓聪  王玉忠 《高分子科学》2015,33(2):203-214
To improve the flame-retardant efficiency and water resistance of ammonium polyphosphate(APP), the UV-curable pentaerythritol triacrylate(PETA) was used to microencapsulate APP via the UV curing polymerization method. The prepared PETA-microencapsulated APP(PETA-APP) was characterized by Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM), and thermogravimetric(TG) analysis. PETA-APP was used as intumescent flame retardant(IFR) alone to flame retard polypropylene(PP). The water resistance of PP/PETA-APP composites was investigated, and the effect of PETA on the combustion behaviors of PP/APP composites was studied through limiting oxygen index(LOI), vertical burning test(UL-94) and cone calorimeter(CC) test, respectively. With 40 wt% of PETA-APP, the PP/PETA-APP system could achieve a LOI value of 30.0% and UL-94 V-0 rating after treatment in hot water for 168 h, while the LOI value of the system containing 40 wt% uncoated APP was only 19.2%, and it failed to pass the UL-94 rating. CC test results showed that the heat release rate(HRR), mass loss rate(MLR) and smoke production rate(SPR) of PP/PETAAPP system decreased significantly compared with PP/APP system, especially the peak of HRR was decreased by 51.4%. The mechanism for the improvement of flame reatardancy for PP/PETA-APP composites was discussed based on FTIR and X-ray photoelectron spectroscopy(XPS) tests. All these results illustrated that simultaneous improvement of flame retardancy and water resistance for PP/APP was achieved through coating UV-curable PETA onto APP.  相似文献   

9.
The two kinds of transition metal ion-incorporated nickel phosphates (TMIVSB-1) were synthesized by the hydrothermal method. The flame retardancy and thermal behavior of intumescent flame retardants (IFR), with and without TMIVSB-1 for PP, were investigated by LOI, UL-94 test, thermogravimetric analyses (TGA) and cone calorimetry. TMIVSB-1 can obviously improve the flame retardant behavior of IFR systems according to the results of LOI values and UL-94 test. The results of LOI show that 2 wt% TMIVSB-1 can increase the LOI value by 3–5 unit compared with that of PP/IFR composite. The UL-94 test shows that PP with 20% IFR burns and has no rating, but the addition of a small content 2 wt% of TMIVSB-1 with 18 wt% of IFR can reach a UL-94 V-0 rating. TGA results show that the thermal stability of PP/IFR/TMIVSB-1 increases obviously more than that of PP/IFR when the temperature is above 265°C. From cone calorimetry results, it can be observed that the HRR peaks are not obviously decreased, but the burning time of PP/IFR/FeVSB-1 (351s) and PP/IFR/ZnVSB-1 (380s) is obviously prolonged compared with that of PP/IFR (303s). The real time FTIR spectra (RTFTIR) demonstrates that the addition of TMIVSB-1 further staves the decomposition of the PP composites. The scanning electron microscopy (SEM) indicates the quality of char forming of PP/IFR/ TMIVSB-1 is superior to that of PP/IFR.  相似文献   

10.
An efficient flame retardant polymeric synergist poly[N4-bis(ethylenediamino)-phenyl phosphonic-N2, N6-bis(ethylenediamino)-1,3,5-triazine-N-phenyl phosphonate] (PTPA) was designed and synthesized from cyanuric chloride, ethylenediamine and phenylphosphonic dichloride. It was characterized by Fourier Transform Infrared (FTIR), 1H NMR and 31P NMR, Elemental Analysis (EA) and Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). Combined with ammonium polyphosphate (APP), a new intumescent flame retardant (IFR) was obtained. The flammability behaviors of polypropylene (PP)/IFR system were investigated by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimetry. With 25 wt% of IFR (APP:PTPA = 2:1), the PP/IFR system could achieve a LOI value of 34.0% and UL-94 V-0 rating, and the heat release rate (HRR), peak heat release rate (PHRR), total heat release (THR) and smoke production rate (SPR) were considerably reduced, especially HRR and SPR were decreased by 85% and 79%, respectively. The results indicate that there is an excellent synergism between APP and PTPA, which endows PP with both good flame retardancy and good smoke suppression. Furthermore, the thermal degradation mechanism of IFR and the flame-retardant mechanism of PP/IFR system were investigated by thermogravimetric analysis (TGA), FT-IR, TG-FTIR and scanning electron microscope (SEM). The study on the flame-retardant mechanism of IFR indicated that a structure containing –CN was formed due to the reaction between APP and PTPA.  相似文献   

11.
Nano-Mg(OH)2 (nanometre magnesium hydroxide, nano-MH) was successfully introduced into the esterification and polycondensation system by in situ polymerization to obtain PET/magnesium salt composites (PETMS). The thermal properties and flame retardancy of PETMS were investigated by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), UL-94 vertical burning and limited oxygen index (LOI) test. The DSC and TGA results show that magnesium salts in the PET matrix have little effect on the thermal properties of PET, but a significant effect on the thermal stabilities of the composites. The results of LOI and UL-94 test show PETMS have higher LOI values (≥25%) and V-0 rating without melt dripping in the UL-94 test, indicating that PETMS have good flame retardancy and anti-dripping property. Moreover, the residues of magnesium salts and composites after TGA test were also studied by Fourier transform infrared spectroscopy (FTIR) to better understand the mechanism of flame retardancy, which reveals that magnesium salts accelerate the degradation of PET and catalyze the formation of char. The SEM results show the morphological structures of the char effectively protect the composites’ internal structures and inhibit the heat, smoke transmission and reduce the fuel gases when the fire contacts them.  相似文献   

12.
利用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和马来酸酐(MA)对淀粉进行改性得到磷化淀粉(DOPOMASt),通过红外光谱(FTIR)、核磁共振谱(1H-NMR)和X射线光电子能谱(XPS)确定其结构.利用DOPOMASt作为碳源,与聚磷酸铵(APP)复配后通过熔融共混制备了阻燃聚乳酸(PLA)...  相似文献   

13.
Tao  Zhenxiang  Yang  Rui  Li  Cong  Yao  Yina  Zhu  Pei  Zhang  Hui 《Journal of Thermal Analysis and Calorimetry》2018,132(3):1617-1628
A phosphorus-containing maleimide flame retardant (BDMP) was synthesized via the addition reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide and N,N′-bismaleimide-4,4′-diphenylmethane. The structure of BDMP was characterized by Fourier-transform infrared spectroscopy (FTIR), 1H and 31P nuclear magnetic resonance and elemental analysis. The thermal, flame-retardant and mechanical properties of the flame-retardant cyanate ester system were investigated by thermogravimetric analysis (TG), limiting oxygen index (LOI), vertical burning (UL-94), cone calorimeter test and dynamic mechanical analysis. The TG results indicated that the initial decomposition of modified CE resin shifted from 416 to 363 °C, and on the contrary, the char yield increased from 38.8 to 44.5%. The results of combustion tests indicated that the CE with highest phosphorus content acquired LOI value of 37% and achieved a UL-94 V-0 rating. The peak heat release rate, average heat release rate and average of effective heat combustion (av-EHC) of that group decreased by 39.5, 31.2 and 41.8%, respectively. In addition, the increase in phosphorus content led to a decrease in av-EHC and average CO2 yield, and an increase in average CO yield, indicating that BDMP led to an incomplete combustion of the modified CE system. The flame-retardant mechanism was investigated by TG–FTIR, scanning electron microscope and cone calorimeter. Last but not least, the dielectric constant of modified CE system showed a slight fluctuation from 2.96 to 3.02 at 1 GHz, which was lower than that of neat CE.  相似文献   

14.
A novel polyhedral oligomeric silsesquioxane containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-POSS) has been incorporated into polycarbonate (PC) composites in order to study its effect on mechanical and thermal properties and flame retardancy. The mechanical and thermal properties of the DOPO-POSS/PC composites have been investigated by tensile and flexural testing, DSC, and DMA. Slight enhancements of yield stress, and flexural strength and modulus, and obvious decreases of fracture strength and strain of the DOPO-POSS/PC composites were observed with an increase in DOPO-POSS loading. The glass transition temperatures (Tg) of the composites were reduced with increasing DOPO-POSS loading. The morphology of the PC composites was evaluated by SEM, which indicated that the DOPO-POSS was dispersed with a particle size of 100-250 nm in the PC matrix. The thermal degradation behaviour and flame retardancies of PC composites with different DOPO-POSS loadings were investigated by TGA, LOI, UL-94 standard, and cone calorimetry. The composite had an LOI value of 30.5 and a UL-94 rating V-0 when the content of DOPO-POSS was 4%.  相似文献   

15.
The high flammability of vinyl ester resin (VE) significantly limits its widespread application in the fields of electronics and aerospace. A new phosphorus-based flame retardant 6,6’-(1-phenylethane-1,2 diyl) bis (dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (PBDOO), was synthesized using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and acetophenone. The synthesized PBDOO was further incorporated with VE to form the VE/PBDOO composites, which displayed an improved flame retardancy with higher thermal stability. The structure of PBDOO was investigated using Fourier transformed infrared spectrometry (FTIR) and nuclear magnetic resonances (NMR). The thermal stability and flame retardancy of VE/PBDOO composites were investigated by thermogravimetric analysis (TGA), vertical burn test (UL-94), limiting oxygen index (LOI), and cone calorimetry. The impacts of PBDOO weight percentage (wt%) on the flame-retardant properties of the formed VE/PBDOO composites were also examined. When applying 15 wt% PBDOO, the formed VE composites can meet the UL-94 V-0 rating with a high LOI value of 31.5%. The peak heat release rate (PHRR) and the total heat release (THR) of VE loaded 15 wt% of PBDOO decreased by 76.71% and 40.63%, respectively, compared with that of untreated VE. In addition, the flame-retardant mechanism of PBDOO was proposed by analyzing pyrolysis behavior and residual carbon of VE/PBDOO composites. This work is expected to provide an efficient method to enhance the fire safety of VE.  相似文献   

16.
以三氯氧磷和双酚A为原料制备了具有超支化结构的聚磷酸酯阻燃剂(HPPEA),通过红外(FTIR),核磁(1H-NMR,31P-NMR)及热重分析表征了产物的结构和热稳定性.将HPPEA与三聚氰胺聚磷酸盐(MPP)进行复配,通过熔融共混法制备阻燃尼龙6,通过氧指数法和垂直燃烧法测试了其阻燃性能,采用热重分析(TGA)研究...  相似文献   

17.
Compared with poly(butylene terephthalate) (PBT), glass-fibre-reinforced poly(butylene terephthalate) (GF-PBT) is difficult to flame retard with halogen-free flame retardants. In the present study, the aluminium salt of hypophosphorous acid (AP) was used as a flame retardant for GF-PBT. A series of flame-retardant GF-PBT composites was prepared via melt compounding. The flame retardance and combustion behaviour of the composites were studied by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimetric test. Thermal behaviours and thermal decomposition kinetics were investigated by thermogravimetric analysis (TGA) under N2 atmosphere. The addition of AP to the composites could result in an increased LOI value, a UL-94 V-0 (1.6 mm) classification and a better fire performance in cone calorimetric tests. The char morphology observation after flame-retardant tests, calculation of decomposition kinetics, X-ray photoelectron spectroscopy (XPS) and infra-red spectral analysis of the char residue confirmed the condensed-phase flame-retardant mechanism. Furthermore, the mechanical properties of the flame-retardant composites were not deteriorated, retaining an acceptable level.  相似文献   

18.
The flame retardancy mechanisms of a novel polyhedral oligomeric silsesquioxane containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO‐POSS) in polycarbonate/acrylonitrile‐butadiene‐styrene (PC/ABS) blends are discussed. The thermal stability of PC/ABS composites with different DOPO‐POSS loadings are investigated by TGA and the enhancement of the thermal stability could be found at high temperature range. Their fire behavior is tested by the LOI, UL‐94, and cone calorimeter. Excellent flame retardancy of PC/ABS composites have been discovered with 10 wt% DOPO‐POSS loading. TGA‐FTIR, FTIR, XPS, and SEM, respectively, are used to characterize the gaseous products and the condensed residue in thermal decomposition, and the micro‐structure of the chars from cone calorimeter tests. The decomposition of PC/ABS with 10 wt% DOPO‐POSS shows significant changes compared with PC/ABS by TGA, FTIR, TGA‐FTIR, and XPS analysis. The enhancement of the thermal‐oxidative stability of PC/ABS with DOPO‐POSS is attributed to the interaction between DOPO‐POSS and PC/ABS at high temperature, which might be the key for improvement of the flame retardancy. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

19.
The flammability characteristics and flame retardant mechanism of phosphate-intercalated hydrotalcite (MgAl-PO4) in the halogen-free flame retardant ethylene vinyl acetate (EVA) blends have been studied by X-ray diffraction (XRD), Fourier transfer infrared (FTIR) spectroscopy, cone calorimeter test (CCT), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), limiting oxygen index (LOI) and UL-94 tests. The results show that the hydrotalcite MgAl-PO4 intercalated by phosphate possesses the enhanced thermal stability and flame retardant properties compared with ordinary carbonate-intercalated hydrotalcite MgAl-CO3 in the EVA blends. The CCT tests indicate that the heat release rate (HRR) and mass loss rate (MLR) values of the EVA/MgAl-PO4 samples are much lower than those of the EVA/MgAl-CO3 samples. The TGA data show that the thermal degradation rates of MgAl-PO4 and EVA/MgAl-PO4 samples are much slower and leave more charred residues than those of MgAl-CO3 and its corresponding EVA blends. The LOI values of EVA/MgAl-PO4 samples are 2% higher than those of the corresponding EVA/MgAl-CO3 samples at the range of 40–60 wt% loadings, while the EVA sample with 55 wt% MgAl-PO4 can reach the UL-94 V-1 rating. The dynamic FTIR spectra reveal that the flame retardant mechanism of MgAl-PO4 can be ascribed to its catalysis degradation of the EVA resin, which promotes the formation of charred layers with the P–O–P and P–O–C complexes in the condensed phase. The SEM observations give further evidence of this mechanism that the compact charred layers formed from the EVA/MgAl-PO4 sample effectively protect the underlying polymer from burning.  相似文献   

20.
邓聪  王玉忠 《高分子科学》2014,32(1):98-107
Aluminum hypophosphite (AP) was used to prepare flame-retarded thermoplastic polyurethane (FR-TPU) composites, and their flame retardancy, thermal degradation and mechanical properties were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), thermogravimetric analysis (TGA), cone calorimeter (CC) test, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and tensile test. TPU containing 30 wt% of AP could reach a V-0 rating in the UL-94 test, and its LOI value was 30.2. TGA tests revealed that AP enhanced the formation of residual chars at high temperatures, and slightly affected the thermal stability of TPU at high temperatures. The combustion tests indicated that AP affected the burning behavior of TPU. The peak of heat release rate (PHRR), total heat release (THR) and mass loss rate (MLR) greatly reduced due to the incorporation of AP. The tensile test results showed that both the tensile strength and the elongation at break slightly decreased with the addition of AP. The digital photos and SEM micrographs vitrified that AP facilitated the formation of more compact intumescent char layer. Based on these results mentioned above, the flame-retarding mechanism of AP was discussed. Both the self-charring during the decomposing process of AP and its facilitation to the charring of TPU led to the great improvement in the flame retardancy of TPU.  相似文献   

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