基于环三磷腈/磷酸酯反应型磷-氮阻燃剂的合成、热降解及应用

以六氯环三磷腈(HCCP)、对羟基苯甲醛及亚磷酸二乙酯等为原料,成功合成了一种反应型磷-氮膨胀阻燃剂六(4-磷酸二乙酯羟甲基苯氧基)环三磷腈(HPHPCP),HPHPCP结构经傅里叶红外光谱(FTIR)、核磁共振(NMR)证实。热失重(TG/DTG)表明HPHPCP具有较高的热稳定性及良好的成炭性,氮气氛下的起始分解温度为162.7℃,800℃时残炭量大于40%(质量分数);利用HPHPCP的羟基结构,应用于硬质聚氨酯泡沫塑料中,可以显著提高聚氨酯硬泡的阻燃性能,添加30%的HPHPCP就可以使聚氨酯氧指数达到27%。     

PET纤维及其织物的阻燃技术进展

概述了聚对苯二甲酸乙二醇酯(PET)纤维及其织物的阻燃技术,包括共缩聚阻燃PET纺丝、PET与阻燃剂共混纺丝及PET织物阻燃后处理等。其中,阻燃剂主要有磷系及磷-氮系阻燃剂,如:9,10-二氢-9-氧杂-10-磷杂蒽-10-氧化物(DOPO)衍生物、次膦酸(酯)及其聚合物、氧化膦聚合物、膦酸酯及螺环磷酸酯等。今后应积极开发生态和环境兼容的阻燃PET纤维新技术。     

含磷共聚酯纤维的阻燃及热降解性能研究

采用含磷反应型阻燃剂、对苯二甲酸和乙二醇共聚,纺丝得到共聚酯纤维,研究了共聚酯纤维的阻燃性能和热降解行为。结果表明,共聚酯纤维含磷质量分数为0．36％,极限氧指数达31．5％,燃烧时无熔滴、烟雾产生。共聚酯起始热分解温度达391℃,热降解温度390～470℃,氮气气氛下的热分解表观活化能为170～200 kJ／mol(分解度为0．15～0．80),且随分解度的增加而增加,其热降解机理比较复杂。     

Post-polymerization functionalization to a novel phosphorus- and nitrogen-containing polyether coating for flame retardant treatment of PET fabric

Concerns about the rising trend of stringent fire safety regulations and demands for reduction in the fire hazard call for a careful evaluation of the environmental impact of flame retardant materials choices. With the worldwide bans and restrictions in the use of traditional halogen-based fire retardant systems, phosphorus/nitrogen synergistic flame retardants became evident. We report here a novel phosphorus- and nitrogen-containing polyether (PN-PEO) prepared by post-polymerization functionalization. The resultant polyethers (PN-PEO) were subsequently coated onto the surface of poly(ethylene terephthalate) (PET) fabrics by a simple solution-dipping method to exploit a highly efficient fire retardant. It was found that the loadings of 17.8% PN-PEO had a strong barrier effect in the char layer of the PN-POE-coated PET fabrics after exposed to the torch flame, and resulted in complete suppression of PET fabrics ignition on radiant heat exposure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47299.     

Synthesis of a novel intumescent flame retardant and its application in EVM

A novel phosphorous-nitrogen structure containing intumescent flame retardant, 4,4-diaminodiphenyl methane bi(2,2-dimethyl-1,3-propanediol) phosphoramidate (DBDPP) was synthesized and characterized. Thermal stability and flammability properties of ethylene vinyl-acetate copolymer rubber(EVM)/DBDPP composites were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI) test and UL-94 measurement, respectively. The results showed that the addition of DBDPP enhanced the thermal stability and flame retardancy of EVM significantly. The weight of residues improved greatly with the addition of DBDPP. SEM investigations revealed that a strong charred layer was formed from EVM/DBDPP composites during combustion. It is confirmed that the char structure was a critical factor for flame retardancy of EVM rubber. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The application of a novel flame retardant on viscose fiber

The paper is mainly about a novel organophosphorus flame‐retardant N‐1‐chloroisopropyl alcohol‐3‐dimethylphosphonopropionamide. Dimethyl phosphate, acrylamide and epichlorohydrin were used as raw materials. The mechanisms of synthesis and molecule structure of the flame retardant were discussed. The fiber was treated using the pad‐dry‐cure‐wash method. The limiting oxygen index value of the modified sample was 31%, higher than that of the sample treated with MDPA (Pyrovatex CP). After 50 laundry cycles, it still had some flame retardancy left. Thermogravimetry (TG) and Differentiate TG analyses confirmed that the flame retardant caused fiber to decompose below its ignition temperature and formed carbonaceous residue or char when exposed to fire. The treatment had an obvious effect on the denier of the fiber; the tensile strength of fiber slightly decreased, but that effect could be negligible. Copyright © 2008 John Wiley & Sons, Ltd.     

阻燃仿真发丝聚酯的合成

通过多元共聚及共混手段合成了阻燃仿真发丝的专用聚酯切片。对产品进行限氧指数的测定,探索出阻燃剂含量与限氧指数之间的关系,并由差热分析(DSC)及电子扫描电镜(SEM)对产品进行观察,产品具有发丝的特性。     

Phosphorylation of Kapok Fiber with Phytic Acid for Enhanced Flame Retardancy

Kapok fiber (KF), with the characteristics of a natural hollow structure, light weight, and low density, can be used as acoustic and thermal insulation, buoyancy, adsorption, filling, and composite material. The flame-retardant treatment can expand the functionality and application of KF. In this work, the phosphorylation of KF using phytic acid (PA) in the presence of urea at a high temperature was used to enhance its flame retardancy. The phosphorylation reaction conditions were discussed, and the surface topography, thermal degradation, heat release, and combustion properties of phosphorylated KF were studied. The Fourier transform infrared spectroscopy and ³¹P solid-state nuclear magnetic resonance spectroscopy analyses confirmed the grafting of PA on cellulose by the formation of phosphate ester bonds. Due to the covalent binding of PA, phosphorylated KF exhibited good washing durability. The surface topography, Raman spectroscopy, thermogravimetric (TG), and microcalorimetry analyses revealed the excellent charring ability of phosphorylated KF. In the TG test in nitrogen, the char residue increased to 42.6% of phosphorylated KF from 8.3% of raw KF at 700 °C. In the vertical combustion, raw KF sheet was almost completely burned out within 30 s, while phosphorylated KF was very difficult to catch fire. In the microcalorimetry analysis, the heat release capacity and total heat release of phosphorylated KF decreased to 67 J/g∙K and 3.9 kJ/g, respectively from 237 J/g∙K and 18.1 kJ/g of raw KF. This work suggests that phosphorylated KF is an excellent flame-retardant material.     

环状膦酸酯阻燃PTT纤维及其性能研究

采用自制的环状膦酸酯(MBEP)、三聚氰胺和溴化环氧树脂,按一定配方与聚对苯二甲酸丙二醇酯(PTT)共混造粒、纺丝制备阻燃PTT纤维,研究了阻燃剂对纤维阻燃性能和纺丝性能的影响。结果表明,添加质量分数3．0%的MBEP和4．0%的三聚氰胺时,PTT树脂的阻燃性能较好,极限氧指数达28%以上,磷氮协同阻燃效应明显,其纺丝性能良好,得到的阻燃PTT纤维断裂强度达约3．0 cN/dtex。     

含磷阻燃剂阻燃环氧树脂热降解动力学

以2-二苯基膦酰基-1,4-苯二酚(DPO-HQ)为阻燃剂制备了阻燃环氧树脂,利用动态热重分析法(TGA)研究了纯环氧树脂(EP)和阻燃环氧树脂(FR-EP)在不同升温速率下的热稳定性,建立了EP和FR-EP体系的动力学模型和非模型动力学(MFK),并对比分析了模型动力学和非模型动力学对于描述EP体系和FR-EP体系的适用性.结果表明:阻燃剂的引入降低了环氧树脂初始降解温度,但增加了残炭率.由Flynn-Wall-Ozawa方法和Coats-Redfern方法建立的模型动力学表征EP和FR-EP体系高温降解过程中误差较大,而非模型动力学能更准确地预测和描述EP和FR-EP体系的高温降解行为.     

耐高温阻燃纤维的现状与展望

介绍了几种典型的耐高温阻燃纤维的发展状况及性能特点 ,展望今后耐高温阻燃纤维的开发方向应是低污染、多功能、高性能的新产品 ,同时要降低成本 ,扩大应用领域     

有机膦系阻燃剂改性再生聚酯纺丝及性能研究

采用有机膦系阻燃剂(OP)对再生聚酯(RPET)进行熔融共混挤出造粒,将切片干燥,熔融纺丝制备改性RPET纤维,研究了改性RPET的性能。结果表明:在RPET中加入阻燃剂OP,得到的改性RPET熔点下降,玻璃化转变温度和结晶温度上升,改性RPET纤维强度下降,阻燃性能提高;当阻燃剂OP质量分数为4.7%,拉伸倍数为3.3时,制得的改性REPT纤维的断裂强度为2.2 cN/dtex,断裂伸长率为44%,极限氧指数为27.1%;当OP质量分数为5.9%时,改性RPET纤维的极限氧指数为28.3%。     

皮芯复合阻燃疏水纤维的制备工艺

采用有机膦系G-77阻燃剂对聚对苯二甲酸乙二醇酯(PET)进行共混改性用作芯层料,赋予纤维阻燃性能,采用聚偏氟乙烯(PVDF)和共聚阻燃母粒对自制阻燃母粒进行改性用作皮层料,赋予纤维一定的阻燃性和疏水性;将改性后皮芯料通过皮芯复合纺丝制得多功能阻燃疏水纤维;探讨了芯层料和皮层料阻燃加入量对其阻燃性能的影响,研究了皮芯复合阻燃疏水纤维的制备工艺及其原丝的力学性能。结果表明:当芯层料中的G-77阻燃剂与PET的质量比为7.25/100时,其极限氧指数(LOI)为27.8%;当皮层料中的PVDF的质量分数为6%,自制阻燃母粒与共聚阻燃母粒质量比为7.0/3.0时,其与水的接触角为83.4°,LOI为26.3%;当皮芯复合比为20.0/40.5,卷绕速度为1 200 m/min,拉伸倍数为3.75时,皮芯复合阻燃疏水纤维的可纺性较好,原丝的线密度为2.15 dtex,断裂强度为4.52 cN/dtex。     

合成纤维阻燃改性的技术进展

介绍了聚酯、聚酰胺、聚丙烯腈及聚丙烯等合成纤维的阻燃改性技术现状,主要有添加共混型、共聚反应型阻燃改性。纤维阻燃改性的新技术有超细/纳米技术、微胶囊技术、硅系阻燃、复配技术及功能复合化。指出了今后合成纤维阻燃技术应向多功能化发展。     

无卤阻燃聚乙烯醇缩甲醛纤维的制备与表征

以新戊二醇和三氯硫磷为原料,一步法合成了无卤膨胀型阻燃剂二硫代焦磷酸双新戊二醇酯(BGDTP);采用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(~1H-NMR)对BGDTP的结构进行了表征。将BGDTP添加到聚乙烯醇(PVA)中进行共混纺丝,制备了阻燃聚乙烯醇缩甲醛(PVFM)纤维,并对其力学性能、阻燃性能和热性能进行了表征。结果表明:一步法合成BGDTP的收率为82%;随着纤维中BGDTP添加量的增加,PVFM纤维的极限氧指数(LOI)、高温下的最大分解速率温度和残炭量均增大,但其断裂强度略有下降;当w(BGDTP)为20%时,阻燃PVFM纤维的LOI为30.8%,断裂强度为5.42 cN/dtex,最大热分解温度和残炭率比纯PVFM纤维均有较大幅度增加,燃烧形成连续致密的膨胀炭层。     

可燃工质氨的燃烧及阻燃机理的研究

当前环境问题日益突出,天然工质氨作为环保性制冷剂再次引起科学界的广泛重视。但NH₃存在可燃可爆性问题,在实际应用中存在着一定的安全隐患。采用量子化学密度泛函理论计算方法,在M06-2X/6-311+G（d,p）的计算水平上,对NH₃的燃烧及阻燃机理开展研究,得到反应过程的微观反应路径。研究表明,NH₃可通过三种方式发生燃烧微观反应,一是发生自身裂解反应,生成H自由基;二是与氧气发生碰撞反应,生成OOH自由基;三是与活性自由基发生碰撞反应,生成新的活性自由基,NH₃可与H、O、OH自由基反应,反应能垒较低。此外,还计算了两种典型的阻燃基团F和CF₃对可燃分子NH₃的微观阻燃路径,验证其阻燃效果。本文从微观分子的角度考察了可燃工质氨的燃烧及阻燃机理,为新一代低温室效应工质的燃烧及阻燃机制提供了参考。     

聚苯胺及其导电阻燃涤纶的制备

采用氧化聚合的方法合成聚苯胺,并考察了不同温度下聚苯胺的产率和电导率,探讨了阻燃涤纶碱减量处理条件,用原位聚合的方法制备聚苯胺/阻燃涤纶导电纤维。结果表明,在-20℃下合成的聚苯胺产率较高为84%,电导率为124 S/cm。阻燃涤纶碱减量处理的适宜条件为:温度80℃,碱浓度为5%,处理时间15-20 min,低温下制备的聚苯胺/阻燃涤纶失重为2.50%-5.25%时,纤维的电导率提高得较快,为0.07-0.13 S/cm。     

新型硅硼磷阻燃剂的合成以及在防火涂料中的应用

以9,10⁃二氢⁃9⁃氧杂⁃10⁃磷杂菲⁃10⁃氧化物（DOPO）、二甲氧基甲基乙烯基硅氧烷（DTTLL）和硼酸［B（OH）₃］合成了一种分子结构中含有硅硼磷的阻燃剂（SiBP）。分别用傅里叶变换红外光谱仪（FTIR）和氢核磁共振光谱仪（¹H⁃NMR）表征了SiBP 的化学结构。用热失重分析仪（TG）表征了SiBP的热稳定性,在氮气氛围下SiBP的起始分解温度为110 ℃,并且在氮气气氛下800 ℃的残炭率高达40 %。以硅丙乳液为基体,通过加入多聚磷酸铵（APP）为协效阻燃剂,SiBP为主阻燃剂,双季戊四醇（Di⁃PE）,三聚氰胺（MEL）,无机填料硅微粉进行复配制备一种防火涂料。利用极限氧指数测定仪（LOI）,UL 94垂直燃烧测试、TG、大木板燃烧实验对其防火性能进行详细的表征和分析,利用扫描电子显微镜观察炭层燃烧后的微观和宏观形貌。通过压缩性能测试仪、电子万能试验机对炭层强度和涂料剥离强度进行表征。结果表明,当APP为10份（质量份,下同）、SiBP为20份、Di⁃PE为4份、MEL为8份、硅微粉为25份时,极限氧指数提高到29.2 %,UL 94达到V⁃0级,残炭率为38.5 %,剥离强度提高到0.325 kN/m,炭层压缩强度增加到1.4 MP,亲水性增加。     

聚氨基环磷腈的合成及其在PVA纤维中的应用

将六氯环三磷腈进行氨基取代,高温自聚得到不溶于水的聚氨基环磷腈(PHACTPA);PHACTPA通过粉末化后与聚乙烯醇(PVA)溶液共混纺丝得到阻燃PVA纤维。结果表明:PHACTPA在湿热条件下不稳定,但其干热稳定性好,在400℃高温氮气环境下稳定而不分解。PHACTPA在纤维中的质量分数小于22．5％时,对纤维的强度影响不大;含PHACTPA质量分数为15％的阻燃PVA纤维极限氧指数可达40％。     

二硫代焦磷酸酯微胶囊阻燃PVA纤维的制备及性能

采用原位聚合的方法制备了以新戊二醇二硫代焦磷酸酯(DDPS)为核、三聚氰胺甲醛树脂(MF)为壳的阻燃微胶囊(MDDPS),分别将DDPS和MDDPS无卤阻燃剂与聚乙烯醇(PVA)共混纺丝,制备了无卤阻燃PVA纤维;表征了MDDPS的结构及形貌,研究了纯PVA纤维、DDPS/PVA纤维、MDDPS/PVA纤维的力学性能、阻燃性能、热稳定性、燃烧前后的形貌。结果表明:微胶囊MDDPS的平均粒径增大至7.82μm,仍能满足共混纺丝要求;DDPS及MDDPS的加入,PVA纤维力学性能下降;MDDPS/PVA纤维阻燃性能较好,极限氧指数达31.3%,燃烧时膨胀较为明显,且600℃时残炭率达到19.1%,炭层较为致密,有气泡产生,释放不燃性气体阻止了燃烧。