反应型磷氮阻燃剂/可膨胀石墨复配阻燃聚氨酯泡沫

将反应型阻燃剂六(4-磷酸二乙酯羟甲基苯氧基)环三磷腈(HPHPCP)和可膨胀石墨(EG)复配,制备了阻燃聚氨酯泡沫,详细研究了复配阻燃剂对聚氨酯泡沫的物理力学性能、热稳定性以及阻燃性能的影响。结果表明,阻燃聚氨酯泡沫的密度和热导率随着复配阻燃剂中EG含量的增加而升高;压缩强度随着EG含量的增加呈现先增加后降低的趋势。热失重表明复配阻燃剂大大提高了聚氨酯泡沫的热稳定性。聚氨酯泡沫的初始分解温度(T_10%)从212.9℃,分别提高到222.0、231.2和243.2℃;700℃残炭量从7.6%分别提高到26.3%、31.6%和37.9%。聚氨酯泡沫的阻燃性能随着复配阻燃剂中EG含量的增加而提高。阻燃聚氨酯泡沫的极限氧指数从19%提高到29%,均能通过UL-94水平燃烧HF-1等级和垂直燃烧V-0等级。     

反应型磷氮阻燃剂/可膨胀石墨复配阻燃聚氨酯泡沫

将反应型阻燃剂六(4-磷酸二乙酯羟甲基苯氧基)环三磷腈(HPHPCP)和可膨胀石墨(EG)复配,制备了阻燃聚氨酯泡沫,详细研究了复配阻燃剂对聚氨酯泡沫的物理力学性能、热稳定性以及阻燃性能的影响。结果表明,阻燃聚氨酯泡沫的密度和热导率随着复配阻燃剂中EG含量的增加而升高;压缩强度随着EG含量的增加呈现先增加后降低的趋势。热失重表明复配阻燃剂大大提高了聚氨酯泡沫的热稳定性。聚氨酯泡沫的初始分解温度(T10%)从212.9℃,分别提高到222.0、231.2和243.2℃;700℃残炭量从7.6%分别提高到26.3%、31.6%和37.9%。聚氨酯泡沫的阻燃性能随着复配阻燃剂中EG含量的增加而提高。阻燃聚氨酯泡沫的极限氧指数从19%提高到29%,均能通过UL-94水平燃烧HF-1等级和垂直燃烧V-0等级。     

锂电池电解液阻燃剂氟代磷腈的合成工艺研究

研究了锂电池电解液阻燃剂乙氧基五氟环三磷腈的合成工艺。以六氯环三磷腈(P3N3Cl6)为原料、氟化钠为氟化剂、DMI(1,3-二甲基-2-咪唑啉酮)为溶剂进行氟化反应,蒸馏得到六氟环三磷腈(>98%);以六氟环三磷腈(P3N3F6)为原料、正己烷为溶剂、乙醇钠为醚化试剂进行反应,粗品经精馏得到纯度>99.8%的乙氧基五氟环三磷腈。     

热塑性聚氨酯阻燃剂的合成及其在TPU中的应用

以六氯环三磷腈(HCCP)为主要原料,合成了针对热塑性聚氨酯(TPU)阻燃的含有磷腈环的高分子阻燃剂——磷腈化聚氨酯(P-EIPU),通过红外光谱及核磁共振P谱对其结构进行表征,证实了目标产物为P-EIPU,同时,热重分析表明P-EIPU具有良好的热性能。通过P-EIPU对TPU进行阻燃改性,结果表明:P-EIPU与TPU中均含氨基甲酸酯基团,相容性较好;当P-EIPU添加量15%时,TPU阻燃等级达V-0,LOI值为27.3%。     

环三磷腈阻燃剂研究进展

简述了环三磷腈阻燃剂的阻燃机理,重点介绍了六苯氧基环三磷腈、氨基环三磷腈、六对醛基环三磷腈、DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)羟甲基苯氧基环三磷腈及其他环三磷腈阻燃剂的研究进展,展望了环三磷腈阻燃剂的发展前景。     

β-萘酚取代环三磷腈的合成及其紫外-可见光谱性能研究

通过六氯环三磷腈与β-萘酚反应合成了一种新型六(β-萘氧基)环三磷腈化合物,其结构经核磁共振谱、红外光谱和质谱表征。紫外-可见吸收光谱法测定了β-萘酚和六(β-萘氧基)环三磷腈在乙醇、环己烷和乙腈中的最大吸收波长(λmax),并探讨了分子结构和溶剂对吸收光谱的影响。研究发现,溶剂效应对六(β-萘氧基)环三磷腈的吸收光谱无明显影响;六(β-萘氧基)环三磷腈相比β-萘酚最大吸收波长发生蓝移,说明六(β-萘氧基)环三磷腈相比β-萘酚的分子共轭程度降低。     

基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料,成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP）,用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性,氮气气氛下的初始分解温度为191.9℃,700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%,最大热释放速率和总热释放量分别从230 kW/m²和20.1 MJ/m²降低至213 kW/m²和16.6 MJ/m²,总产烟量从10.5 m²下降到5.3 m²。     

六(2,4,6-三溴苯氧基)环三磷腈(BPCPZ)的合成、热性能及应用

以六氯环三磷腈与2,4,6-三溴苯酚反应,制得有机磷腈化合物六(2,4,6-溴苯氧基)环三磷腈(BPCPZ).用红外、核磁、质谱及元素分析对产物结构进行了表征.研究了溶剂、原料配比、反应温度和反应时间对产物收率的影响.结果表明,合成的最佳条件是:四氢呋喃为溶剂,反应物料配比为n(三溴苯酚) ∶n(六氯环三磷腈)=6.5...     

六氯环三磷腈合成新工艺

提出了五氯化磷气化法合成六氯环三磷腈新工艺。以氮气做载气,五氯化磷气态进料,与氯化铵在惰性有机溶剂中催化反应合成了六氯环三磷腈。在N2流量60mL/min,五氯化磷升华温度170℃,溶剂用量110mL,反应温度131±1℃,ZnCl20.1g,PCl523.1g,NH4Cl5.4g,反应时间185min条件下得粗磷腈12.0g,收率92.31%。经精制,得到六氯环三磷腈7.9g,总产率达40%(以五氯化磷计)。产品六氯环三磷腈熔点112.4～114℃。元素分析结果N11.98%,P26.50%,Cl60.64%;用IR谱、质谱进行了表征。     

六(4-醛基苯氧基)环三磷腈的合成、表征及其热性能研究

通过六氯环三磷腈和4-羟基苯甲醛的亲核取代反应,成功合成出目标化合物六(4-醛基苯氧基)环三磷腈(HAPCP).并考察了溶剂和缚酸剂类型、缚酸剂粒度、原料配比及反应时间对产物收率的影响.利用红外光谱和核磁共振对目标化合物的结构进行了表征,同时用热失重分析研究了目标化合物的热稳定性.结果表明:目标化合物在400℃左右有明...     

聚苯基甲氧基硅氧烷改性环氧树脂的阻燃性能研究

采用氧指数(LOI),UL-94,热失重(TGA)等手段考察了聚苯基甲氧基硅氧烷(PPMS)改性对环氧树脂(E-20)固化体系阻燃性能的影响.相比未改性环氧体系,当m(E-20)∶m(PPMS)=73∶时,改性环氧体系的LOI由纯E-20环氧树脂的17.5%上升到21.5%;水平火蔓延速率由36.23 mm/min降低到26.60 mm/min;质量损失为5%时的热分解温度由134.7℃上升到163.0℃,750℃时残炭量由0.21%增加到25.79%.此外,还通过红外光谱对燃烧后的残炭结构进行了分析,探讨了相关阻燃机理.     

Grafting modification bamboo kraft lignin and its performance in rigid polyurethane foams

In order to improve the efficiency of intumescent flame retardant (IFR), bamboo kraft lignin (BKL) was chemically functionalized by grafting melamine (MEL) and diethyl phosphite (DEP) and used for rigid polyurethane (RPU) foam. The BKL, MEL, and DEP in IFR system were used as char forming agent, gas, and acid source, respectively. The FTIR and XPS results indicated that the nitrogen (N) and phosphorus (P) containing BKL was successfully synthesized. The limiting oxygen index (LOI) value of N-BKL and N/P-BKL RPU foams were higher than BKL RPU foam, suggesting that N-BKL and N/P-BKL improved flame retardancy of the foams. The total heat release (THR), heat release rate (HRR), effective heat of combustion (EHC), and fire growth rate (FIGRA) values of N-BKL and N/P-BKL RPU foams were much lower than that of BKL RPU foam. The flame retardancy index value of N/P-BKL RPU foams was higher comparing to N-BKL RPU foam. These results indicated that the synergistic interaction between N containing compound of MEL and P containing compound of DEP led to the improvement flame retardant properties. Comparing to BKL RPU foam, the N/P-BKL RPU foam increased 74°C of maximum weight loss temperature and decreased 18.1 wt% of mass loss, indicating enhanced thermal stability. The morphology of char after cone calorimeter testing showed the N/P-BKL RPU foam presented more continuous and compact char residues, which could reduce heat and mass transfer, protecting underlying materials from further combustion in a fire, thus resulting in good flame retardancy and thermal stability properties. This work suggests a promising route to enhancing the flame-retardant performance of RPU foam using nontoxic and more environmentally friendly grafted bamboo lignin.     

NPM阻燃聚丙烯的研究

通过氧指数(LOI)、水平燃烧(HB)、热重分析(TGA)、扫描电镜(SEM)和红外(IR)等表征方法,研究了单组分膨胀型阻燃剂新戊二醇磷酸脂三聚氰胺盐(NPM)阻燃PP体系的阻燃性能、燃烧炭层结构及阻燃机理,评价了NPM的添加量对体系物理性能的影响。结果表明:PP/NPM(100/30)体系的氧指数为26．8%,600℃时的成炭率为8．30%,NPM显著提高了体系的热稳定性。     

Preparation of a novel phosphorus‐ and nitrogen‐containing flame retardant and its synergistic effect in the intumescent flame‐retarding polypropylene system

A novel phosphorus‐ and nitrogen‐containing flame retardant (melamine phytate) was synthesized via the reaction between melamine and phytic acid. The chemical structure of melamine phytate (MPA) was confirmed by Fourier transform‐infrared spectra (FT‐IR) and elemental analysis. And the thermal behavior of MPA investigated by thermogravimetric analysis (TGA) demonstrates that MPA possesses a good char‐forming ability at high temperature. Besides, limiting oxygen index (LOI) and vertical burning tests (UL‐94) illustrate that polypropylene/melamine phytate/dipentaerythritol (PP/MPA/DPER) (70/22.5/7.5) can reach the LOI value of 28.5% and achieve V‐0 rating at the flame retardant loading of 30 wt%. Except that, the thermal weight loss of MPA and DPER in PP composites was investigated by TGA in detail. Moreover, the char residue of PP composite after combustion was systematically analyzed by FT‐IR, scanning electron microscope (SEM) and X‐ray photoelectron spectroscopy (XPS), which can further propose and confirm the flame retardant mechanism. POLYM. COMPOS., 36:1606–1619, 2015. © 2014 Society of Plastics Engineers     

Melamine amino trimethylene phosphate as a novel flame retardant for rigid polyurethane foams with improved flame retardant,mechanical and thermal properties

Melamine amino trimethylene phosphate (MATMP) as a novel nitrogen‐phosphorus flame retardant, was synthesized by the reaction of melamine with amino trimethylene phosphonic acid (ATMP) in aqueous solution. The structure of MATMP was characterized by Fourier transform infrared spectroscopy, solid state 31 P nuclear magnetic resonance, and thermogravimetric analysis. Rigid polyurethane (RPU) foams were prepared by one‐shot and free‐rise method, using MATMP as a flame retardant. The flame retardant, mechanical and thermal properties of MATMP in RPU foams were studied. It is found that the RPU foam containing 15 wt % MATMP (sample RPUMA‐15) can pass the UL‐94 V0 test with a limiting oxygen index of 25.5%. The cone calorimeter test results show that the peak heat release rate of RPUMA‐15 is reduced about 34% compared with that of untreated RPU foam. SEM results indicate that the RPU foams with MATMP can form the good and compact char during burning which provides better flame retardancy. The compressive strength of the RPU foams filled with MATMP first increases and then slightly decreases with an increase in the MATMP content comparing with that of untreated RPU foam. Moreover, thermal conductivities of the MATMP filled RPU foams are about 0.03 W/m K. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45234.     

阻燃聚丁二酸丁二醇酯复合材料的制备及其阻燃性能研究

采用熔融共混技术,将次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MC)引入聚丁二酸丁二醇酯(PBS),制备了一系列阻燃PBS复合材料,并采用极限氧指数、垂直燃烧、微型量热测试以及热失重分析研究了复合材料的阻燃性能以及热稳定性。结果表明,AHP可以有效提高PBS复合材料的阻燃性能;AHP与MC复配可以进一步提高复合材料的阻燃性能,两者质量比为2∶1,添加量为20 %（质量分数,下同）即可使复合材料达到UL 94 V 0级别,极限氧指数达到29 %;AHP以及复合阻燃体系可以有效提高复合材料初始分解温度及其高温稳定性。     

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.     

三嗪膨胀阻燃剂/硅酸镁协效阻燃TPU的制备及性能研究

以三嗪成炭发泡剂（CFA）及聚磷酸铵（APP）复配成膨胀阻燃剂(IFR),以硅酸镁(MgSiO3)为协效剂添加到热塑性聚氨酯弹性体(TPU)中制备阻燃TPU材料,研究了阻燃TPU材料的阻燃性能、力学性能、热降解行为和炭层的表面形貌。结果表明,纯TPU材料的极限氧指数仅为22.0 %,在空气中极易燃烧,当IFR添加量为28 %（质量分数,下同）,MgSiO3添加量5 %时,材料的极限氧指数提高到37.1 %,通过UL 94 V-0级,表现出很好的阻燃效果;但是IFR/MgSiO3的加入使材料的拉伸强度和断裂伸长率明显下降,也使得TPU材料的起始热分解温度提前,最大热降解速率峰值降低,同时材料的残炭量得到了很大程度的提高。     

纳米Al_2O_3对含磷环氧树脂体系的性能影响

研究了以纳米Al_2O_3作为协同阻燃剂,对EP/DOPO和EP/HPCTP树脂固化物阻燃性能的影响。通过热重分析测试(TGA)、动态热机械分析测试(DMA)、氧指数测定(LOI)及垂直燃烧测试(UL-94)重点探讨了树脂固化物的耐热及阻燃性能。测试结果表明,含磷阻燃剂有助于提高环氧树脂固化物的阻燃性能,但会降低其玻璃化转变温度(Tg)。随着纳米Al_2O_3的加入,残炭率(800℃)、极限氧指数(LOI)得到进一步的提高,并且能够在一定程度上提升树脂固化物的玻璃化转变温度(Tg)和初始热裂解温度(T5%)。