Synergistic Flame Retardant Effect of Ammonium Polyphosphate and Aluminum Hydroxide on Polyurethane

The flame-retardant properties of polyurethane(PU)containing ammonium polyphosphate(APP)and aluminum hydroxide(ATH)were investigated.Moreover,the flame retardant performance was investigated through thermogravimetric analysis,limiting oxygen index(LOI),vertical combustion(UL 94),and cone calorimeter.When 15 wt%APP and 5 wt%ATH were added together,the PU/15%APP/5%ATH sample shows better thermal stability and flame-retardant properties.When 15 wt%APP and 5 wt%ATH were added together,the LOI value of the PU/15%APP/5%ATH sample was 30.5%,and UL 94 V-0 rating was attained.Compared with PU,the peak heat release rate(PHRR),total heat release(THR),and average effective heat combustion(av-EHC)of the PU/15%APP/5%ATH sample decreased by 43.1%,21.0%,and 29.4%,respectively.In addition,the flame-retardant mechanism was investigated through cone calorimeter.The APP/ATH addition simultaneously exerted condensed phase and gas phase flame retardant effects.APP and ATH have synergistic flame retardant properties.

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.

Recent advances in constructing new type of epoxy resin flame retardant system using ammonium polyphosphate

In recent years,research has focused heavily on the investigation of functionalized ammonium polyphosphate(APP)flame retardants to improve the fire safety of epoxy resins(EP).The reason for this is the dual nature of APP's performance in fire protection of EP.This article provides a comprehensive overview of the advances in the use of functionalized APP flame retardants to improve the fire resistance of EP materials.It then presents the improvement of the modification of the functionalized APP flame retardants in terms of the hydrophobicity,compatibility and catalytic ability of the flame retardants,as well as the effects on the fire resistance,heat resistance,smoke reduction and mechanical properties of the EP composites.After the summary and comparison of the relevant studies,it is clear that the functionalized APP flame retardants can effectively improve the fire safety of EP composites and offset the adverse effects of APP in EP flame retardant applications.In addition,APP flame retardants can obtain various excellent functions through the use of materials with different properties,and the interaction between APP and materials can also lead to more efficient fire protection.However,the current problem is to find ways to streamline the process and minimise the costs associated with functionalized APP flame retardants,as well as to use them effectively in industrial production.We hope that this review can provide valuable hints and insights for the practical application of functionalized APP in EP and perspectives for future research.

Effect of surface modification of ammonium polyphosphate-diatomite composite filler on the flame retardancy and smoke suppression of cellulose paper

Ammonium polyphosphate-diatomite composite filler(APP-diatomite composite filler)was modified with silane coupling agent KH550 to improve the flame retardancy of filled paper.Cone calorimeter was used to analyze the heat and smoke releasing rates,as well as smoke toxicity of the filled paper.The distribution of the composite filler particles in paper and the morphology of the charred residues after combustion were investigated by scanning electron microscope(SEM),and the chemical structure of the charred residues was studied with fourier transform infrared spectroscopy(FTIR).Results show that the peak heat releasing rate(PHRR),total heat release(THR)and peak mass loss rate(PMLR)of the filled paper with the modified APP-diatomite decreased markedly,compared with those for the control paper,while the charred residue after combustion increased.In addition,the filled paper had an increased peak rate of smoke release(RSR)and increased total smoke release(TSR)and peak CO production rates,but a decreased peak CO_(2) production rate.It was also found that part of the carbon element in the charred residue of the paper loaded with the modified APP-diatomite was in the forms of C=C=C,C≡C and C≡N,and the charred residue had a relatively more intact structure without apparent fiber breakage and longitudinal cracks.

A novel high-efficient P/N/Si-containing APP-based flame retardant with a silane coupling agent in its molecular structure for epoxy resin

A flame retardant containing multiple antiflaming elements usually exhibits high-efficient flame retardancy. Here, a novel P/N/Si-containing ammonium polyphosphate derivative(APTES-APP) is synthesized from ammonium polyphosphate(APP) and silane coupling agent(3-aminopropyl)triethoxysilane(APTES)via cation exchange, which is quite different in the chemical structure from APTES-modified APP for retaining silicon hydroxyls. APTES-APP is highly efficient for the epoxy resin. 8%(mass) APTES-APP imparts excellent flame retardancy to the epoxy resin, with a V-0 rating at the UL-94 test(1.6 mm)and an LOI value of 26%(vol). The peak heat release rate and total smoke production of the flameretardant epoxy resin are decreased by 68.1% and 31.3%, respectively. The synergy of P/N/Si contributes to the well-expanded char residue with a strong and dense surface layer, which is a very good barrier against heat and mass transfer. Besides, there is no significant deterioration in the mechanical properties of flame-retardant epoxy resin thanks to silicon hydroxyls forming hydrogen bonds with epoxy molecules. Meanwhile, other molecules can be grafted onto APTES-APP via these silicon hydroxyls, if needed.Briefly, this work has developed a new strategy for amino silane as flame retardants. In conjunction with a low-cost and simple preparation method, APTES-APP has a promising prospect in the high-performance flame-retardant epoxy.

Preparation and Properties of Bio-Based Flame Retardant Polyvinyl Alcohol

Polyvinyl alcohol (PVA) has been widely used in the fields of medical, food and packaging due to its excellentbiocompatibility, good fiber-forming and film-forming properties. However, the high flammability of PVA hasgreatly limited its wider applications. The flame-retardant PVA was prepared by melt blending of a bio-basedflame retardant (prepared from lignin, phosphoric acid and carbamide) with thermoplastic PVA (TPVA). Thechemical structure, morphology, thermal properties, mechanical properties, fire property and fluidity of thisflame retardant PVA were investigated by Fourier transform infrared spectrometer(FTIR), field emission scanning electron microscope(SEM), thermogravimetric analyzer(TGA), impact tester, universal testing machine,horizontal-vertical burning tester, limiting oxygen indexer(LOI) and melt flow rate meter(MFR). The resultsshowed that the prepared flame retardant had good compatibility with the PVA substrate;The impact strength,melt flow rate, fire property and char residue of this PVA material increased with the content of bio-based flameretardant. When the content of flame retardant was of 20%, the five indices including impact strength, meltflow rate, UL-94 level, LOI and char residual were 11.3 KJ/m^(2), 21.2 g/10 min, V-0 UL-94 level, 33.1%, and19.2%, respectively. This research can promote the high-value utilization of lignin and the application ofPVA in the fields of fire protection.

Preparation and Properties of Bio-Based Flame Retardant L-APP/Poly(L-lactic acid)Composites

Poly(L-lactic acid)(PLLA)is a thermoplastic material with complete degradability,high biocompatibility and excellent mechanical properties.It can replace petroleum-based polymers are currently being used in the fields of packaging,agriculture,textiles,medical and so on.However,PLLA’s extremely flammability greatly limits its wider application.An bio-based flame retardant L-APP/PLLA composites was prepared by melt blending of the L-APP and PLLA.The morphology,impact properties,thermal properties and flame retardant properties of composites were investigated by field emission scanning electron microscope(SEM),impact tester,differential scanning calorimeter(DSC),thermogravimetric analyzer(TGA),limiting oxygen indexer(LOI)and horizontalvertical burning tester.The results showed that the degree of crystallization(X_(c))and LOI of L-APP/PLLA composites increased as increasing of L-APP content.What’s more,the impact strength first increased and then decreased,the glass transition temperature(T_(g))and melting temperature(T_(m))do not changed significantly.The impact strength of composites was 9.1 kJ/m^(2) at a 5 wt%loading for L-APP,which was the highest level.When the content of L-APP was 20%,the LOI was 30.8%,the Xc was 42.3%and the UL-94 level was V-0.This research can promote the value-added utilization of lignin and the application of PLLA in the fields of flame retardant materials.

聚苯乙烯基乙二醇/聚磷酸铵阻燃复合材料的制备及性能研究

阐述了复合材料的制备工艺,包括实验材料的准备、确定材料混合比例和操作条件,以及添加剂的选择和添加量控制。分析了复合材料的燃烧性能,包括燃烧特性和热解产物的生成情况,同时进行了力学性能的分析,包括强度性能、刚度性能、韧性性能,以及疲劳性能的分析。探讨了复合材料的优缺点,并提出可能的改进方向,为该复合材料在实际应用中的推广提供了科学的依据。

聚磷酸铵阻燃剂改性及应用研究进展

高分子量Ⅰ型聚磷酸铵是一种磷氮含量非常高的膨胀性阻燃剂,比卤系和有机磷系阻燃剂更加低碳环保。本文对聚磷酸铵改性阻燃剂的国内外研究现状、市场现状、国内的行业政策及规范进行了详细地分析,并对聚磷酸铵阻燃剂行业未来的发展趋势进行了预测。本文为我国聚磷酸铵阻燃剂行业企业的发展策略制定及技术升级改造提供了借鉴,同时也为我国阻燃剂行业的健康发展指明了方向。

聚乙烯醇/聚磷酸铵改性锂电隔膜的制备与性能

以高聚合度的聚磷酸铵(APP)为阻燃剂,聚乙烯醇(PVA)为成膜骨架材料,通过相转化法制备了PVA/APP改性隔膜,并测定了改性隔膜的机械强度、湿润性、热稳定性、微观形貌以及电化学性能。探究APP添加量对改性隔膜性能的影响,将改性隔膜在充满氩气的手套箱中组装成锂电池,并评价其循环倍率性能。结果表明,当PVA水溶液质量分数为10%、APP添加量为8%(以PVA质量为基准)时,改性隔膜具有优异的电解液湿润性以及热稳定性,吸液率达到215.0%,在200℃下几乎不收缩;改性隔膜的拉伸强度达到47.4 MPa。在0.1 C倍率充放电条件下循环50次,放电比容量为143.2 mA·h/g,库仑效率均>97%,容量保持率达到95.1%,而商用锂电池隔膜所组装电池的容量保持率只有82.8%。

桐油涂覆对多聚磷酸铵改性杉木阻燃性能与抗流失性的影响

为提高杉木的阻燃性,探讨多聚磷酸铵处理木材对其燃烧性能和抗流失性的影响,获得阻燃处理对杉木性能的影响规律。选取杉木为研究对象,以多聚磷酸铵为阻燃剂,通过满细胞法对杉木进行阻燃处理,再在杉木样品表面涂覆桐油,分别对未处理材和阻燃处理材的形貌、热解行为、阻燃性能及阻燃剂的抗流失性进行测试。结果表明,杉木试件的极限氧指数为20.2%,经质量分数为5%的多聚磷酸铵处理后的杉木极限氧指数为34.5%,燃烧性能分级达到B1级要求。涂覆桐油对木材的阻燃性能具有一定的负面影响,其极限氧指数下降到29.3%,燃烧性能分级为B2级。锥形量热仪(CONE)结果表明,较之素材,阻燃样品整个测试过程处于阴燃状态,HRR曲线为一直线,且PHRR下降了85.36%,THR和SPR与HRR具有相似的变化规律,TSP也显著降低。TG-DSC结果表明,涂覆桐油的阻燃处理样品在800℃的失重率仅为素材的74.18%,残炭量由15.75%上升到37.95%。涂覆桐油可提高APP的抗流失性,但对木材的力学性能未产生明显改良。研究结果表明,阻燃处理木材对延缓其在火灾中燃烧行为具有重要意义,并为实现理论指导综合性功能改良、木材生产应用提供重要的理论依据和参考。

DOPO衍生物-APP协同的阻燃水性聚氨酯的制备及性能研究

基于聚磷酸铵(APP)阻燃剂与阴离子聚氨酯相容性差,所得聚氨酯燃烧仍然产生大量熔滴,采用磷系阻燃剂对皮革用阴离子水性聚氨酯进行阻燃改性,探究APP和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的衍生物(DOPO-PHB)两种阻燃剂协同作用的阻燃改性体系。通过极限氧指数(LOI)、垂直燃烧试验和热重分析考察了其阻燃性能和热降解性能,用拉伸机测定了薄膜的力学性能。结果表明,当添加1%APP-4%DOPO-PHB阻燃剂时,聚氨酯LOI值为27.8%,垂直燃烧达到V-0级别,无熔滴,聚氨酯的力学性能提升,相容性提高。

铜尾矿/聚磷酸铵阻燃聚氨酯的制备及研究

以聚磷酸铵(APP)/铜尾矿(CTS)为阻燃体系,采用一步全水发泡法制备硬质聚氨酯泡沫/聚磷酸铵/铜尾矿(RPUF/APP/CTS)复合材料。阻燃测试表明,RPUF-30APP的极限氧指数(LOI)达到24.0%,垂直燃烧测试达到V-0级别,其阻燃性明显提高。锥形量热测试表明,RPUF-30APP的热释放速率峰值(PHRR)由纯样的300.5 kW/m^(2)降低至139.4 kW/m^(2),下降幅度高达53.6%;总热释放(THR)由纯样的40.0 MJ/m^(2)下降至28.1 MJ/m^(2),降低幅度高达29.8%,表明APP/CTS体系明显降低复合材料燃烧过程中的热释放,其火灾安全性提高。炭渣分析表明,CTS/APP/RPUF复合材料燃烧过程中形成了致密的炭层,提高了复合材料的阻燃性能。该研究为CTS提供了一个新的应用领域,并为提高聚合物的防火安全性铺平了道路。

聚磷酸铵表面改性及对天然橡胶复合材料性能的影响

先使用碱性硅溶胶在聚磷酸铵(APP)表面形成一层无机自组装微胶囊化APP(SiO2@APP),再使用硅烷偶联剂3-巯丙基三乙氧基硅烷(KH 580)通过溶胶-凝胶法对SiO2@APP表面进行接枝改性制备了接枝改性APP(KH 580-SiO2@APP)阻燃剂,将其应用到天然橡胶(NR)中制备了NR复合材料,研究了APP表面改性对NR复合材料的疏水性、热稳定性、阻燃性能和物理机械性能的影响。结果表明,已成功对APP表面进行改性。相较于APP,经碱性硅溶胶改性后所得SiO2@APP的水接触角增加了205.7%,热稳定性提高了约25.7%;相较于APP/NR复合材料,SiO2@APP/NR复合材料的拉伸强度提高了43.7%,但是其极限氧指数(LOI)有所下降。SiO2@APP经硅烷偶联剂KH 580改性后,所得KH 580-SiO2@APP的水接触角增加了9.1%,热稳定性提高幅度将近11.6%。此外,KH 580-SiO2@APP/NR复合材料的拉伸强度得以提高,达到了16.2 MPa,扯断伸长率上升幅度达到了539%,而LOI略下降至24.3%。

多元复配阻燃剂对水性漆阻燃性能的影响研究

研究旨在提高木制品的阻燃性能,减少火灾威胁。通过选择聚磷酸铵(APP)、四水八硼酸二钠(DOT)和硼酸硼砂(BABX)作为多元复配阻燃剂,探究不同阻燃剂间复配后的协同阻燃机制。试验以桉木单板为基材,制备阻燃型水性漆并进行阻燃测试。单因素试验确定了阻燃剂的优化添加量区间,响应面设计试验分析了三种阻燃剂交互协同作用对阻燃和抑烟效果的影响。结果表明,APP、DOT、BABX的添加均能减小燃烧半径,且APP效果最好,BABX次之;APP与DOT、BABX的协同作用能增加初烟时间,DOT与BABX的协同作用能有效抑制烟雾产生。模型预测的最优配比为APP2.96%、DOT5.89%、BABX4.4%,验证测试结果与理论值接近,表明模型具有良好可靠性。此外,阻燃剂的添加对涂料的漆膜强度影响不大。该研究为制备高效、环保的阻燃涂料提供了理论依据和实践指导。

聚磷酸铵阻燃应用研究进展

聚磷酸铵(APP)凭借其无毒、无卤、抑烟、阻燃效果好、环境友好等特点,被广泛应用于聚丙烯、聚氨酯、环氧树脂等聚合物阻燃领域。然而,APP存在吸湿性强、添加量高、分散性差、与聚合物相容性差等缺点,限制了其进一步发展。针对上述问题,对聚磷酸铵的阻燃机理及应用进行了系统综述,并总结了相关的解决方法。首先简单介绍了APP的物化性质及阻燃机理;然后梳理了近年来国内外APP阻燃剂的研究进展,详细介绍了单独阻燃、复配阻燃、微胶囊化包覆、化学改性和纳米复配等不同阻燃方式的阻燃效果,并归纳总结了不同阻燃方式的优缺点;最后讨论了APP在聚合物阻燃研究中存在的主要问题,并展望了其未来的发展方向。

聚硅氧烷包覆改性聚磷酸铵及其阻燃聚乙烯性能的研究

分别以二甲基二乙氧基硅烷(DMDES)、甲基三乙氧基硅烷(MTES)、苯基三甲氧基硅烷(PTMS)3种硅氧烷与正硅酸四乙酯(TEOS)共同作为前驱体,采用溶胶-凝胶工艺对聚磷酸铵(APP)进行微胶囊化包覆改性,分别制备得到改性聚磷酸铵APP/DMDES、APP/MTES和APP/PTMS,以改善其阻燃性、热稳定性和疏水性。通过傅里叶红外光谱、水接触角、扫描电子显微镜、能谱仪以及热失重分析等测试与表征手段,对3种不同聚硅氧烷包覆改性聚磷酸铵(MAPP)进行了对比研究,并研究了MAPP对低密度聚乙烯(PE-LD)阻燃性能、力学性能和热性能的影响。结果表明,在合适的工艺条件下,均可以制备得到聚硅氧烷包覆改性聚磷酸铵;较改性前的APP,改性聚磷酸铵的疏水性和热稳定性均显著提高;在PE-LD/APP/PTMS/季戊四醇(PER)/三聚氰胺(MEL)的质量比为65/18.7/11.7/4.6时,PELD复合材料的综合性能最好,极限氧指数为26.6%,高于包覆前APP的23.3%,达到UL 94 V-0级别,且拉伸性能最高,为12.84 MPa。

高岭土对APP/PER/PP复合材料性能的影响

以PP废玩具料(W-PP)为主材,高岭土(Kaol)、聚磷酸铵(APP)和季戊四醇(PER)为阻燃剂,通过熔融挤出制备一系列Kaol/APP/PER/W-PP复合材料,对复合材料的极限氧指数(LOI)、UL 94阻燃等级、力学性能和热变形温度(HDT)进行测试,并用锥形量热仪进行分析,结果表明,APP/PER添加后,复合材料的阻燃性能和HDT明显提高,力学强度逐渐降低;适量的Kaol和APP/PER具有较好的协同阻燃效果,而且,添加Kaol后,复合材料的力学性能和HDT明显提升,当在W-PP中同时加入3%的Kaol和25%的APP/PER时,复合材料的LOI为32.1%,阻燃达到UL 94(1.6 mm)V-0级,与单独添加相比,拉伸强度、弯曲模量、弯曲强度和缺口冲击强度均提高了28%APP/PER的性能分别提高了16.9%、15.0%、27.4%和31.3%。

竹基多孔碳协同聚磷酸铵阻燃环氧树脂的分子动力学与耗散粒子动力学模拟

添加剂与基材的相容性是影响复合材料综合性能的重要因素。采用分子模拟技术建立竹基多孔碳材料(PCM)协同聚磷酸铵(APP)复合于环氧树脂(EP)体系的分子模型,利用分子动力学和耗散粒子动力学进行模拟计算;通过实验对模拟结果进行验证。模拟结果表明,与PCM*2相比,表面含有更多含氧活性基团的PCM*1更有利于通过组分之间氢键的形成增强相互作用;与EP/APP/PCM*2(391.9 kJ/mol)相比,EP/APP/PCM*1的结合能显著增大,其值为470.2 kJ/mol,径向分布函数g(r)曲线更高。PCM的介观形貌证明了其表面活性基团有利于组分在EP中的分散,提高了其与基材的相容性。验证结果表明,PCM1的O/C更高,提高了APP在EP中的分散性,EP/APP/PCM1的氧指数达到了27.3%,与未阻燃EP相比,热释放速率峰值降低了45.4%,表征潜在火灾危险性与轰燃性的pk-HRR/TTI值降低至8.6 kW/(m^(2)·s)。分散性的改善使PCM与APP表现出了更好的协同阻燃作用,与分子模拟结果一致。

磷-硅涂层对芳纶1313/聚酰亚胺织物阻燃性能的影响

为进一步提高消防服外层织物的阻燃性能,采用芳纶1313和聚酰亚胺织造3/1斜纹机织物,并配制聚磷酸铵和纳米二氧化硅复合阻燃剂对其进行功能化修饰。测试结果表明,配制的阻燃剂涂料,能够有效提高试样的阻燃性能,LOI值提高到了35.1%,热释放量下降了70.69%,烟释放量降低了98.84%。所制备的涂层织物可应用于消防服外层,提高消防服的热防护性能。