聚磷腈材料在航空航天及军工领域的应用研究

简要介绍了聚磷腈的结构和性能,概述了六氯环三磷腈、聚二氯磷腈和聚磷腈的合成方法,综述了其在航空航天及军工领域的应用,包括在耐高温阻燃涂层、阻燃泡沫橡胶、火箭发动机绝热层、密封材料等领域的应用,并指出了我国聚磷腈材料发展存在的问题,最后对聚磷腈的发展前景进行了展望。     

线性聚磷腈的研究进展

文章叙述了关于聚磷腈研究的国内外主要进展,讨论了磷腈取代反应的机理,归纳了各种功能高分子方面应用的线性聚磷腈的聚合方法,对未来聚磷腈功能高分子的发展方向进行了展望。     

聚磷腈的合成及应用研究进展

介绍了聚磷腈及中间体聚二氯磷腈的制备方法:聚磷腈由聚二氯磷腈和亲核取代试剂发生亲核反应制备;聚二氯磷腈由热开环和活性阳离子两种聚合法制备,热开环法又分为溶剂聚合、原位聚合和三氯化磷法。溶剂热开环聚合法由于获得的聚合物分子量分布较窄、分子量大和工艺条件温和等优点,适合于工业化制备。较全面地总结了聚磷腈在阻燃材料、生物医用材料、导电材料、膜材料等领域近期的研究进展和发展趋势。     

新型交联聚磷腈/聚丙烯酸羟乙酯高分子合金的制备与表征

本文首先制备了带有丙烯胺侧基的功能线性聚磷腈,通过侧基的自由基聚合,制备了交联的聚磷腈;将交联的聚磷腈置于丙烯酸羟乙酯和光引发剂的混合液中溶胀,经丙烯酸羟乙酯的光聚合反应,得到交联聚磷腈/聚丙烯酸羟乙酯高分子合金,并对其性能进行了表征。     

聚磷腈合成的研究进展

综述了近年来聚磷腈合成的研究进展。在回顾聚磷腈的主要合成方法的基础上，介绍了出现的室温活性正离子聚合及本实验室利用卤化磷腈与五配位硅络合物反应所取得的一些结果。     

六氯环三磷腈的合成及分离

六氯环三磷腈是非常重要的中间体,是环磷腈、聚磷腈系列衍生物的基础。本文简要介绍了六氯环三磷腈的理化性质、合成及分离方法,并提出了自己的见解。     

聚磷腈

聚磷腈化合物是以磷、氮为基本骨架的一类新型无机聚合物,六氯环三磷腈是非常重要的中间体,是整个聚磷腈衍生物系列的基础,由五氯化磷和氯化铵制备,目前我国还没有工业化生产,国外产品的售价在1000美元/kg以上。聚磷腈化合物可用作特种橡胶与弹性材料、防火阻燃材料、药物与生物化学材料、膜材料、高分子导体等,广泛应用于军事工业、航空航天、石油化工、生物医学等领域。     

聚磷腈的合成及其作为含能黏合剂的应用前景

聚磷腈是一类骨架由磷-氮原子交替排列的具有特殊结构和优异性能的新型功能高分子材料.综述了聚磷腈的合成方法,并对其作为含能黏合剂的应用前景进行了探讨.     

无机聚合物单体六氯环三磷腈的合成

作为具有广泛应用前景的新型无机高分子功能材料。聚磷腈已引起国内外科研工作者的极大关注。笔者对聚磷腈的基本单体六氯环三磷腈的舍成作了详细研究，对制备方法、影响产率因素等作了详细探讨。并对产物进行了结构表征。     

适合于油田环境的氟化磷腈弹性体

Ethgl公司开发了聚磷腈弹性体应用的新领域,发现氟化磷腈弹性体在许多方面特别适合于油田应用。氟化磷腈(Fz)弹性体在Ethgl公司已经获得工业化生产,商标为Eypee—F。以前这类材料由Firestone轮胎橡胶公司生产,商标为     

赤磷阻燃剂及其应用

赤磷作为聚合物用阻燃剂,其应用日益广泛。文章就赤磷的性能、阻燃机理、包覆技术及开发应用作了较为系统的介绍.     

Construction of novel silicon‐phosphorus linear polymers with DDSQ and DOPO derivatives for effective flame retardancy of PC/ABS

Two kinds of novel silicon‐phosphorus linear polymers were synthesized by the hydrosilylation reaction of double‐decker‐shaped silsesquioxane (DDSQ) and 9,10‐dihydro‐9‐oxa‐10‐ phosphaphenanthrene‐10‐oxide (DOPO) derivatives and characterized using ¹H NMR, ³¹P NMR, and ²⁹Si NMR. Flame‐retardant polycarbonate/acrylonitric‐butadiene‐styrene (PC/ABS) blends were prepared with different contents of silicon‐phosphorus linear polymers. The flame‐retardant properties of silicon‐phosphorus linear polymers as well as the morphology were investigated in detail by using thermogravimetric analysis (TGA), limiting oxygen index (LOI), (Underwriters Laboratory) UL‐94, microscale combustion calorimetry (MCC), and scanning electron microscopy (SEM), respectively. The silicon‐phosphorus linear polymers containing DDSQ and DOPO units can synergistically improve the flame retardancy and thermal stability of PC/ABS blends. Flame‐retardant polymers with different linkers between DDSQ and phosphate units show comparable effect on the flame retardancy of PC/ABS.     

含磷多孔有机聚合物的合成及其在多相催化中的应用

含磷多孔有机聚合物不仅具有发达的孔隙和表面结构,还具有很强的可调变性和可修饰性,在多相催化中有着广泛的应用前景。目前还没有概述含磷多孔有机聚合物的制备及其在多相催化中应用的综述,本文对该领域近十年来的研究进展进行了归纳和梳理。指出含磷多孔有机聚合物的合成方法发展十分迅速,包括偶联缩聚、锂盐参与的缩聚、Friedel-Crafts缩聚、溶剂热烯烃聚合、Scholl缩聚、酚醛聚合、醛胺缩合、聚吡喃盐的磷代以及多段式聚合等。基于其骨架中含有大量膦配体,含磷多孔有机聚合物能负载一系列金属化合物制成负载型金属纳米颗粒催化剂,甚至单原子或单位点金属催化剂。表明聚合物基催化剂中,膦配体不仅能诱导金属在聚合物中均匀分布,并且在调控金属的表面电子性质和位阻性质等方面发挥重要作用,进而对催化剂的活性和选择性产生影响。     

Flammability studies of thermally resistant polymers using cone calorimetry

The effectiveness of a set of thermally resistant polymers was evaluated for aircraft applications using the cone calorimeter (ASTM E1354/ISO 5660) under heat fluxes simulating real scale fires. This study included eight developmental and commercial thermally resistant polymers available in the literature and/or marketplace. The polymers included were aromatic polyester, polyetherimide, fluorine‐containing polyetherketone, phosphorus and fluorine‐containing co‐polyetherketone, fluorine and phosphorus‐containing polyether, fluorine‐containing polyester, poly(dimethylsiloxane)etherimide and polysulfone. The effects of fluorine, phosphorus, silicon and sulfone group in polymers were examined. This evaluation was based on time to ignition, peak, average and total heat release rates obtained at an external heat flux of 50 kW/m². Other parameters such as effective heat of combustion, mass loss and rate of smoke and toxic gas evolution were collected during the cone calorimeter test. Copyright © 2000 John Wiley & Sons Ltd.     

含磷聚合物阻燃剂的研究进展

综述了含磷聚合物阻燃剂近年来的研究进展,介绍了其主要分类,按照磷元素的位置不同可以分为主链含磷聚合物和侧链含磷聚合物.指出目前含磷聚合物阻燃剂的研究开发主要集中在以下几个方面:(1)多种元素协同高效阻燃聚合物的开发,协效阻燃机理以及聚合物链结构和阻燃性能之间规律的探讨;(2)通过聚合物结构设计,合成出超支化、液晶等结构...     

水性含磷聚合物在涂料中的应用研究进展

水性含磷聚合物具有良好的热稳定性、耐腐蚀性等优点,是一种重要的环境友好型材料。本文主要介绍了水性含磷丙烯酸类和聚氨酯类等重要的水性含磷聚合物,并对这两种聚合物的合成及其在水性防火涂料和防腐涂料中的应用进行了讨论。分析结果表明：以水性含磷聚合物为基料的防火涂料热稳定性较好,成炭率明显增加,阻燃性能大大提高;以水性含磷聚合物为基料的防腐涂料,漆膜附着力增强,防腐性能提高。提出今后的研究方向是：①将磷与卤素、氮、硅等元素同时引入水性聚合物中,以协同阻燃;②将含磷基团引入聚合物分子内,作为基料来提高阻燃性能。     

Synthesis and thermal characterization of chemically modified cardanol polymers

Cardanol was functionalised to incorporate elements such as phosphorus and bromine and polymerised with formaldehyde or hexamethylenetetramine (HMTA) to get flame retardant polymers. Thus, monocardanyl phosphoric acid (MCPA), its bromoderivative (BrMCPA), and their formaldehyde condensates (MCPAF and BrMCPAF) and cross-linked polymers were prepared and characterized by IR, NMR, and GPC. Flammability and thermal stability of these polymers were evaluated by LOI and TGA, respectively, and compared with those of conventional cardanol-formaldehyde (CF) resin and its bromoderivative. TGA of MCPAF showed that although it is initially less stable than that of CF, its stability increases above 500°C over that of CF. Char yields of MCPAF and BrMCPAF are 21 and 27, respectively, and corresponding LOI values are 27 and 49. The present data do not support any synergism nor any additive effect between phosphorus and bromine, but a positive interaction between them is indicated with phosphorus mainly contributing in the condensed phase and bromine in the vapour phase mechanism. The activation energies in the range 20–30 kcal/mol for MCPAF suggest an ionic mechanism for its decomposition, whereas mainly a free radical type of decomposition is inferred for BrMCPAF with an activation energy in the range of 35–50 kcal/mol. © 1993 John Wiley & Sons, Inc.     

Functional modification of poly(vinyl alcohol) through phosphorus containing nitrogen heterocyclic moieties

Functional modification of poly(vinyl alcohol) (PVA) with phosphorus containing nitrogen heterocyclic has been believed to have extensive thermal and biological applications in the area of polymers. Efforts have been taken for the synthesis of phosphorus‐containing N‐heterocyclic (5,6 member and fused ring) based PVA. The synthesized compounds were characterized using UV, FTIR, and NMR spectral studies. Thermal studies (DSC‐TGA) scans display phosphorus‐containing five membered and fused heterocyclic‐based PVA has less thermal stability than six‐membered compounds. Modified polymers infer to have excellent bacterial response against micro‐organisms. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

几种成炭性聚合物与红磷对HIPS/OMMT复合材料阻燃性能的影响

选取成炭性聚合物聚苯醚(PPO)、聚碳酸酯(PC)、聚醚酰亚胺(PEI),分别添加到高抗冲聚苯乙烯(HIPS)/有机蒙脱土(OMMT)复合体系中,极限氧指数(LOI)及水平垂直燃烧试验结果表明,复合体系的阻燃性能变化很小。将传统阻燃剂红磷(RP)与成炭性聚合物并用,可使HIPS/OMMT复合体系阻燃性能特别是水平垂直燃烧性能大幅提高。试验结果表明:红磷用量适中,添加较少量的成炭性聚合物,便能使复合体系分别达到水平燃烧FH-1级和垂直燃烧FV-0级。     

Selective Chlorination of Side-chains in Friedel-Crafts Polymers

Aralkyl polymers with ethyl side-chains were prepared by Friedel-Crafts reactions. Ethylbenzene and bis(p-chloromethyl)benzene (BCMB) were reacted together in the presence of stannic chloride to produce polymers of various molecular weights. A study was then carried out of the chlorination of these polymers, using (a) molecular chlorine, (b) molecular chlorine with a peroxide catalyst and phosphorus pentachloride, (c) sulphuryl chloride. The objective was to determine the best conditions for chlorination to occur selectively at the α-carbon atom of the ethyl group, with minimal chlorination at either the β-position or the main-chain methylene groups. Analysis of ¹H nuclear magnetic resonance spectra of the chlorinated polymers suggests that in most cases chlorination occurs extensively both in the side-chain and in the main-chain methylene groups. Conditions were found, however, which favour chlorination at the α-position. The greatest selectivity was achieved when molecular chlorine, a peroxide catalyst and phosphorus pentachloride were used in benzene solvent.