MAPP阻燃EVA泡沫复合材料的制备及其性能

利用乙二胺(EDA)对聚磷酸铵(APP)进行改性,得到聚磷酸铵衍生物(MAPP)。采用MAPP、石墨(EG)和木粉(MF)复配的方式得到膨胀性阻燃剂,并与EVA复合得到泡沫复合材料。采用FT-IR、XRD、1H NMR表征接枝效果,利用LOI和UL-94测试仪、锥形量热仪(CONE)、TG及SEM等分析材料的阻燃性能、残炭的形态及力学性能。结果表明:EDA已成功接枝在APP上,所形成的MAPP能够有效提高复合发泡材料的阻燃性能、减少热释放量;MAPP/EVA复合发泡材料的残炭层更加致密和完整,能够有效起到隔热、隔氧的作用;并且MAPP能够提高材料的耐水性及与EVA基体的相容性。当MAPP添加量为20%时,体系的LOI可达27.6%,且UL-94为V-0级别,拉伸强度、断裂伸长率分别可达1.282 MPa、236.40%,阻燃材料的综合性能达到最优。     

三嗪膨胀阻燃聚乳酸的制备及其性能

将实验室自制的三嗪大分子成炭发泡剂(CFA)、聚磷酸铵(APP)及硅树脂复配成膨胀阻燃剂(IFR)添加到聚乳酸(PLA)材料中制备阻燃PLA(IFR-PLA)材料,通过极限氧指数(LOI)和垂直燃烧(UL-94)测试研究了材料的阻燃性能。通过热重分析(TGA)测试研究了材料的热降解行为和成炭性能,通过锥形量热(CONE)测试研究了材料的燃烧行为,并对其燃烧后残炭的形貌进行研究。结果表明:当APP与CFA的质量比为5∶1,IFR的添加量为15%时,IFR-PLA材料通过UL-94 V-0级,LOI值达33.5%。IFR的加入促进了PLA材料的降解和成炭,从而提高了材料的阻燃性能。     

APP/ADP体系阻燃木塑复合材料研究

选用聚磷酸铵(APP)与二乙基次膦酸铝(ADP)复配用于木塑复合材料(WPC)的阻燃并研究了材料的阻燃性能。结果表明,纯WPC的氧指数(LOI)值为23.5%,当单独添加19%(wt)的APP时,材料通过了垂直燃烧测试UL-94 V-0级,LOI值为28.9%。当APP与ADP以质量比为6∶1复配,阻燃剂总添加量仅为15%(wt)时,材料通过了UL-94 V-0级,LOI值达到了28.7%,表明ADP/APP体系对WPC具有很好的协同阻燃效应。力学性能测试表明,APP/ADP体系的加入对材料的力学性能影响较小。热重分析测试表明,APP/ADP体系促进了材料的初期热降解,但提高了材料的成炭性能。锥形量热测试及扫描电镜对残炭的测试表明,APP/ADP体系的加入使得材料在燃烧过程中形成了膨胀、连续的炭层,很好地抑制了材料的燃烧,使得材料的热释放速率、总热释放量显著降低。     

微胶囊聚磷酸铵的制备及阻燃环氧树脂的性能研究

采用三聚氰胺甲醛树脂预聚物通过原位聚合法制备了微胶囊聚磷酸铵阻燃剂(MAPP),利用扫描电镜观察到MAPP颗粒表面包覆了一层树脂。采用热重分析法、垂直燃烧法和氧指数法研究了聚磷酸铵(APP)和MAPP阻燃环氧树脂材料的热性能及阻燃性能。结果表明:与APP相比,MAPP阻燃环氧树脂的最大失质量温度、残炭量以及阻燃性能均显著提高。添加10%APP或MAPP的环氧树脂材料的氧指数均大于27.0%,阻燃性能均达到UL 94 V-0级,且MAPP样条燃烧后可形成膨胀炭层。相比于APP,MAPP阻燃材料的力学强度均有所改善,当阻燃剂填充10%时材料的拉伸强度从32.6 MPa提高到35.7 MPa,冲击强度从10.8 kJ/m2提高到11.6 kJ/m2,均高于纯环氧树脂材料的力学强度。     

含磷硅高分子阻燃剂与聚磷酸铵对EVA的协效阻燃作用

研究了聚酯型磷-硅无卤阻燃剂(EMPZR)与聚磷酸铵(APP)对乙烯-醋酸乙烯酯共聚物(EVA)阻燃及力学性能的影响。结果表明,添加为40 %（质量分数,下同）的由EMPZR和APP所组成的复合阻燃剂得到的阻燃EVA材料,其极限氧指数达到28.6 %,垂直燃烧测试达到V-0级,拉伸强度为6.4 MPa,断裂伸长率达592 %。热失重分析测试表明,阻燃EVA材料的热失重速率较纯EVA有明显下降;成炭率显著提高,阻燃EVA在800 ℃时残炭量为15 % ,纯EVA仅为0.2 %。通过扫描电子显微镜对残炭形貌进行表征,以及对氧指数测试前后的阻燃EVA材料的红外图谱分析,表明EMPZR与APP在EVA中具有协效阻燃作用。     

卡拉胶包覆APP/MnO2增强水性环氧树脂阻燃抑烟性能

用反相乳液法，以卡拉胶（KC）为壳材，聚磷酸铵（APP）和二氧化锰（MnO2）为芯材，制备了KC包覆APP/MnO2阻燃剂（KC-FR）。通过FTIR、 XRD、 SEM和 EDS对KC-FR进行了表征。结果表明：卡拉胶已成功包覆APP和MnO2，合成的样品具有微胶囊结构。将KC-FR应用于水性环氧树脂（EP）中，考察KC、APP、MnO2 三者质量比对EP阻燃、抑烟性能的影响。用极限氧指数（LOI）、垂直燃烧（UL-94）和锥形量热（CCT）测试了涂层的阻燃、抑烟性能。结果发现，当KC/APP/MnO2的质量比为2∶1∶1，并且在EP中添加量为20%时，制备的阻燃涂层EP2的LOI达到29.1%，UL-94达到V-0级，表现出较好的阻燃性能。EP2相比于其它涂层热释放峰值（pHRR）、热释放总量（THR）和烟释放总量（TSP）最低，相比于EP0分别下降了42%、37%和46%，表现出较好的抑烟性能。另外，热重分析（TGA）测试结果显示EP2在800℃残炭量（W800）为33%，表明KC-FR具有促进EP成炭的功能。通过SEM对残炭表面分析发现，EP2表面炭层更加致密，这表明KC-FR对促进形成稳定并且致密的炭层起到至关重要的作用。     

新型成炭剂对EVA/APP体系的阻燃性能影响研究

以新型成炭剂聚对苯二甲酰乙二胺(PETA)和聚磷酸铵(APP)复配制备了无卤阻燃乙烯-醋酸乙烯共聚物(EVA)/APP/PETA复合材料,通过极限氧指数法和垂直燃烧法表征了复合材料的阻燃性能,通过热失重分析仪(TGA)和扫描电镜(SEM)分析了复合材料的热稳定性能和残炭表面形貌。结果表明:APP与PETA复配(IFR)后可以极大地提高EVA的阻燃性能,EVA/APP/PETA(质量比70/25/5)体系极限氧指数(LOI)达到39%,较纯EVA提高了88.4%,UL 94测试为V-0级别;EVA/APP/PETA复合材料在600℃下的残炭率达到了42%,较纯EVA残炭率高37%。SEM表明:30%IFR(APP与PETA质量比5:1)的加入提高了样品残炭表面致密性。     

微胶囊化聚磷酸铵及其在聚丙烯中的阻燃性能

采用聚氨酯(PU)为囊材,聚磷酸铵(APP)为芯材制备了微胶囊阻燃剂(MAPP)。通过溶解度测试、傅里叶红外光谱(FTIR)和扫描电镜(SEM)对微胶囊的核壳结构进行了表征。采用氧指数法、垂直燃烧法和SEM考察了APP和MAPP对PP的阻燃效果。结果表明:与APP相比,MAPP溶解度明显下降,FITR和SEM测试表明APP被PU包覆了;通过SEM观察MAPP/PP体系在燃烧后能生成更加连续和致密的炭层,有效地保护了炭层下的材料。在聚丙烯复合材料中,当APP和MAPP添加量相同时(30%),LOI值从22.0%提高到32.0%,且UL-94达到V-0级。     

三嗪成炭剂对EVA阻燃性能的影响

三嗪成炭剂(CNCH-DA)与多聚磷酸铵(APP)复配成膨胀型阻燃剂(IFR)应用于EVA的阻燃改性,采用氧指数测定仪(LOI)、垂直燃烧测定仪(UL-94)分析了EVA/IFR复合材料的阻燃性能,采用微型量热仪(MCC)分析了其燃烧行为,并采用热重分析仪(TGA)和扫描电子显微镜(SEM)研究了其阻燃机理。结果表明,当APP与CNCH-DA的质量比为2∶1时,EVA/IFR复合材料的LOI值达到27. 7%,并且通过了UL-94 V-0级测试; MCC分析结果表明,添加了IFR后,EVA的燃烧性能下降; TGA分析结果表明,当添加IFR后,EVA/IFR复合材料的热降解推迟,残炭量增加;SEM分析表明,EVA/IFR在燃烧后能形成致密且蓬松的炭层,起到良好的阻燃效果,而EVA/CNCH-DA燃烧后,形成众多不致密的微球。     

TPS/EVA泡沫复合材料的制备及其阻燃与力学性能

以热塑性淀粉(TPS)为成炭剂与聚磷酸铵(APP)、可膨胀石墨(EG)复配组成膨胀型阻燃剂,通过熔融密炼、开炼塑化、硫化发泡制备了热塑性淀粉/乙烯-醋酸乙烯酯共聚物(TPS/EVA)泡沫复合材料,探讨了TPS用量对泡沫复合材料阻燃性能、力学性能的影响。结果表明,TPS的加入显著提高了TPS/EVA泡沫复合材料阻燃性能,可起到良好的成炭作用;TPS/EVA泡沫复合材料的拉伸强度、断裂伸长率以及撕裂强度随着TPS用量的增加呈现先增大后减小的趋势,相对密度则是小幅度上升。当TPS用量为6%时,TPS/EVA泡沫复合材料综合性能最好,其LOI可达26.5%且UL-94为V-0级,拉伸强度、断裂伸长率、撕裂强度以及相对密度可达2.395 MPa、177.48%、10.59 N·mm^-1、0.21452。     

Flame retardancy of unsaturated polyester composites with modified ammonium polyphosphate,montmorillonite, and zinc borate

Ammonium polyphosphate (APP) was modified using a new method, where the resulting modified APP (MAPP) was obtained by mixing APP with unsaturated polyester resin (UPR). MAPP was more effective in improving the flame retardancy of UPR than APP which was due to the improved dispersion of MAPP in UPR composite. Then, the UPR composites were prepared based on dimethyl methylphosphonate, MAPP, montmorillonite, and zinc borate. Finally, the flame-retardant and mechanical properties of the UPR composites were analyzed using the limited oxygen index (LOI), thermogravimetric analysis, UL-94 vertical burning test, scanning electron microscopy, cone calorimetry, mechanical tests, and viscosity measurements. The LOI and UL-94 tests showed that the flame-retardant properties clearly improved with the addition of fillers in the UPR composites compared to pristine UPR. The synergistic effect of Si- and P-containing flame retardants in this composite resulted in the LOI value increasing from 18.9 to 31.3% and achieved the UL-94 V-0 rating. Moreover, the heat release rate was lower than the pristine UPR. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47180.     

Vinyl polysiloxane microencapsulated ammonium polyphosphate and its application in flame retardant polypropylene

Vinyl polysiloxane microencapsulated ammonium polyphosphate (MAPP) was prepared by a sol-gel method using vinyltrimethoxysilane as a precursor to improve its thermal stability and hydrophobicity. The MAPP was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and thermogravimetric analyzer (TGA). The results showed that ammonium polyphosphate (APP) was successfully coated with vinyl polysiloxane. MAPP and pentaerythritol (PER) were used together to improve the flame retardancy of polypropylene (PP). The flame retardant properties of PP composites were investigated by limiting oxygen index (LOI), UL-94 test, TGA and SEM. When the MAPP was added as a flame retardant, with PER as a char forming agent, the LOI of PP/MAPP/PER composites was 33.1%, and it reached the UL-94 V-0 level. The results also demonstrated that the flame retardant properties of PP/MAPP/PER composites were better than those of PP/APP/PER composites at the same loading. Moreover, the addition of flame retardant and carbon forming agent could promote the crystallization behavior of PP.     

改性赤泥协同膨胀型阻燃剂阻燃聚乙烯

以聚磷酸铵（APP）、季戊四醇（PER）和三聚氰胺（MEL）复配的膨胀型阻燃体系（IFR）为主要阻燃剂,表面改性后的赤泥（Ti-MRM）作为协效剂阻燃聚乙烯（PE）,采用熔融共混法制备PE基阻燃复合材料（PE/IFR-Ti-MRM）。通过热重分析仪（TGA）、垂直燃烧仪（UL-94）、极限氧指数测定仪（LOI）及扫描电镜（SEM）等对其热氧稳定性、燃烧等级、阻燃性能和残炭形貌进行了表征与分析。结果表明：加入改性赤泥的PE/IFR-Ti-MRM复合材料形成的炭层更加致密和连续,当最优配比时,复合材料的极限氧指数达到32.2,燃烧等级达到V-0级;而PE/IFR阻燃复合材料的极限氧指数只能达到27.5,燃烧等级为V-2级。     

Combustion Behavior and Thermal Oxidative Degradation of EVA Containing Intumescent Flame Retardant

Microencapsulated ammonium polyphosphate (VAPP) with poly(vinyl alcohol)- melamine-formaldehyde (VMF) shell was introduced in ethylene vinyl acetate copolymer (EVA) to improve its flame retardancy. Due to the presence of VMF shell, VAPP shows better compatibility, flame retardancy and water resistance compared with ammonium polyphosphate (APP) in EVA. The flammability of EVA and its flame-retarded composites was studied by LOI, UL-94 and cone calorimeter. The composite containing 40 wt% VAPP can pass V-0 in UL-94 test, and hot water treatment shows few effects on its LOI value and UL-94 rating. The cone results indicated that the use of VAPP in EVA can significantly decrease heat release rate and total heat release compared with APP. To understand the mechanism of action of VAPP, dynamic FTIR experiments were carried out on EVA and EVA/VAPP composites. Based on above studies, the flame retardant mechanism of VAPP in EVA composite is discussed.     

Flame retardant and antibacterial properties of PLA/PHMG-P/APP composites

Poly(lactic acid) (PLA) has evolved into a commodity polymer with numerous applications. However, its high flammability limits its viability as a perfect alternative to petrochemical engineering plastics. In this study, PLA was modified using polyhexamethyleneguanidine phosphate (PHMG-P) and ammonium polyphosphate (APP). The flame retardant performance of PLA/PHMG-P/APP was investigated based on the limiting oxygen index (LOI), vertical burning test (UL-94), thermogravimetric analysis (TGA), cone calorimetry (CC), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and Raman Spectrometry. Qualitative and quantitative methods were used to determine the antibacterial properties of PLA composites. The LOI of PLA-10% (P:A = 1:4) was 31.7% and was rated V-0 in the UL-94 V-0 test. The antibacterial properties of the composites reflected the antibacterial effects of PLA-10% (P: A = 1:4) against Escherichia coli and Staphylococcus aureus, with the antibacterial rates reaching 93.41% and 93.26%, respectively. PHMG-P and APP had a synergistic flame-retardant effect and improved the flame retardancy of PLA while exhibiting excellent antibacterial properties.     

苯基聚硅氧烷微胶囊化聚磷酸铵的制备及其在PP中阻燃性能研究

采用苯基三甲氧基硅烷为前驱体,通过溶胶凝胶法制备出苯基聚硅氧烷微胶囊化聚磷酸铵（MAPP）。将MAPP作为阻燃剂,季戊四醇（PER）作为成炭剂,制备阻燃聚丙烯（PP）。用傅里叶红外光谱、扫描电子显微镜、能谱仪及热重分析仪对MAPP进行表征。结果表明,聚磷酸铵（APP）被苯基聚硅氧烷成功包覆;较之APP,MAPP的热稳定性和疏水性显著提高;MAPP的阻燃性能优于APP,PP/MAPP/PER复合材料达到V-0级别;阻燃剂及成炭剂的加入对PP的结晶行为有促进作用。     

Microencapsulated ammonium polyphosphate by polyurethane with segment of dipentaerythritol and its application in flame retardant polypropylene

Dipentaerythritol (DPER), 4, 40-diphenylmethanediisocyanate (MDI) and melamine (MEL) are used as raw materials to microencapsulate ammonium polyphosphate (MAPP) in situ polymerization. The MAPP is characterized by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA). The results show that the coating operation can effectively improve water resistance of ammonium polyphosphate (APP), and MAPP has higher residual rate than that of APP after combustion. The flame retardant action of MAPP and APP in polypropylene (PP) is investigated by the limited oxygen index (LOI), vertical burning test (UL-94), TGA, SEM, and cone calorimeter test (CCT). The LOI value of the PP/MAPP composite at the same loading is higher than that of PP/APP composite. UL 94 ratings of PP/MAPP composites are raised to V-0 at 20 wt% loading. The results of CCT also show that MAPP is more efficient than APP. The morphological structures observed by digital photos and SEM demonstrated that MAPP could be promoted to form the continuous and compact intumescent char layer. The flame retardant mechanism of PP/MAPP is also discussed.     

A novel bio-based charcoal-forming agent based on chitosan and phytate@Mg to improve the flame retardancy of poly(lactic acid)

A novel bio-based carbon forming agent (Mg@PA-CS) containing P and N elements was were synthesized using the complexation characteristics of chitosan (CS) and phytate (PA). The flame retardant behavior of poly(lactic acid) (PLA)/Mg@PA-CS/APP composites (addition of 20 wt% of different ratios of Mg@PA-CS and APP to polylactic acid composites) were investigated by the limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimetry test (CCT), and thermogravimetric analysis (TGA). Due to the biphasic flame retardant and synergistic effect, since the 20 wt% flame retardant system (Mg@PA-CS:APP = 1:2), PLA composites passed the UL-94 test V-0 rating, reached 34% LOI value. The peak heat release rate (PHRR) and total heat release rate (THR) were reduced to 1/2 of the pure PLA, char residue could be as high as 11.49% at 800°C. Moreover, the flame-retardant mechanism of PLA composites during thermal decomposition was analyzed using a scanning electron microscope (SEM) and the coupling techniques of TGA linked with FT-IR (TG-FTIR).     

Intumescent Flame Retardation of EVA Using Microencapsulated Ammonium Polyphosphate and Pentaerythritols

With a melamine-formaldehyde (MF) resin coating layer, microencapsulated ammonium polyphosphate (MCAPP) is prepared by in situ polymerization and is characterized by XPS and water leaching test. The microencapsulation of APP with the MF resin leads to a decrease in the particle's water leaching rate. The flame-retardant action of MCAPP and APP in EVA are studied using LOI and UL 94 test, and their thermal stability is evaluated by thermogravimetric analysis (TGA). The LOI value of the EVA/MCAPP composite at the same loading is higher than the value of the EVA/APP composite. In comparison with the EVA/MCAPP composites, it is found that the LOI values of the EVA/MCAPP/PER and EVA/MCAPP/DPER ternary composites at the same additive loading increase, and UL 94 ratings of most ternary composites are raised to V-0. The water-resistant properties of the EVA composites are studied, and the results of the composites containing with APP and MCAPP are compared. Moreover, the peroxide cross-linking of the EVA composites is investigated, and the mechanical properties and thermal stability of the composites increase after the cross-linking.     

Synergistic flame retardant effect of piperazine salt and ammonium polyphosphate as intumescent flame retardant system for polypropylene

Amino trimethylene phosphonic acid piperazine (ATPIP) salt, as a novel charring agent, is prepared via a simple ionic reaction in distilled water using amino trimethylene phosphate (ATMP) and piperazine as raw materials. The synergistic flame retardant effect of ATPIP and ammonium polyphosphate (APP) as an intumescent flame retardant (IFR) is investigated by various characterization and testing methods. The results show that the polypropylene (PP)/modified APP with piperazine (MAPP)/ATPIP ternary blend passes UL-94 V-0 rating and achieve a limiting oxygen index (LOI) of 30% at a loading level of 25 wt% IFR (MAPP:ATPIP = 3:1). Meanwhile, the total smoke production (TSP) value of IFR-PP samples is 3.3 m², which decreases by 93.2% compared with that of pure PP, exhibiting excellent smoke suppression performance. Besides, the analysis of gaseous pyrolysis products and char residue indicates that the IFR-PP samples show a synergistic flame-retardant mechanism including the gas phase and the condensed phase.