磷系阻燃剂阻燃聚碳酸酯研究进展*

磷系阻燃剂具有阻燃效率高、低烟、低毒、与基质材料相容性好等优点,在阻燃高分子材料领域得到广泛应用。本文介绍了磷系阻燃剂的分类及阻燃机理,综述了近年来磷酸酯阻燃剂、膦酸酯阻燃剂、DOPO磷杂菲类阻燃剂、磷腈类阻燃剂和无机磷阻燃剂在阻燃聚碳酸酯领域的研究进展,为新型磷系阻燃剂的研发提供参考。     

环氧树脂中磷系阻燃剂协效体系的研究进展

近年来,出于环保等方面的考虑,一些卤系阻燃剂被逐渐淘汰,磷系阻燃剂作为卤系阻燃剂的替代品备受关注。然而,高效的磷系阻燃剂通常会在提高阻燃性能的同时产生更多的烟雾,因此需要与协效剂搭配使用。本文介绍了磷系阻燃剂在环氧树脂中的阻燃机理,综述了环氧树脂中磷系阻燃剂的协效体系的研究进展,包括无机协效剂、有机协效剂及有机-无机杂化协效剂等,并对环氧树脂体系中磷系阻燃剂的协效体系的未来发展趋势进行了展望。     

低烟无卤阻燃聚烯烃的研究进展和应用前景

结合近几年来在低烟无卤阻燃聚烯烃研究的系列工作，综述了该领域国内外研究的最新进展，重点论述了聚合物纳米插层化合物、可膨胀石墨体系、硅胶、碳酸钾体系、氢氧化镁和硼酸锌、有机磷系和磷－氮系膨胀型阻燃剂在无卤阻燃聚烯烃中所取得的主要成果，展望了其应用前景。     

阻燃改性尼龙研究进展

综述了近年来阻燃改性尼龙材料的研究成果,尤其是现今适用于尼龙阻燃的各类阻燃体系的研究现状,包括溴系阻燃剂、磷系阻燃剂、氮系阻燃剂、磷-氮协效膨胀型阻燃剂、无机阻燃剂以及纳米阻燃协效剂等,并展望了未来阻燃尼龙的发展趋势.卤系阻燃剂将逐渐被替代,无卤环境友好型阻燃剂和膨胀型阻燃体系是未来重点的发展方向,综合改性、复配技术的应用也是未来研究和应用的热点.     

有机磷系及石墨烯阻燃环氧树脂研究进展

环氧树脂作为一种优异的树脂基体,被广泛地应用于众多领域,但因其极易燃烧,所以常常需要对其进行阻燃处理。本文简要综述了近几年有机磷系化合物及石墨烯阻燃环氧树脂的研究进展,其中有机磷系化合物阻燃部分重点介绍了以阻燃剂中间体9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)及其衍生物和聚磷酸铵(APP)为代表的含磷阻燃剂在环氧树脂中的阻燃机理和阻燃进展;同时也介绍了石墨烯及其衍生物在环氧树脂阻燃领域的最新研究进展,并对其发展前景进行了展望。     

核壳结构型阻燃剂研究进展

通过微胶囊化技术可赋予阻燃剂以特殊的核壳结构,从而有效减小阻燃剂吸湿性,增加与基体相容性,明显提高阻燃高分子复合材料力学、耐水、阻燃等性能.本文扼要论述了核壳结构型卤系、氢氧化镁、红磷、无机磷系、有机磷系以及膨胀阻燃体系的研究现状,并阐述了该特殊阻燃剂的研究重点与发展趋势.     

聚氨酯硬泡无卤阻燃研究进展

首先对聚氨酯分解和燃烧规律的研究进展进行综述,根据文献中聚氨酯在不同条件下的分解规律的研究结果,给出聚氨酯硬泡分解和燃烧过程的一般规律。在此基础上,通过文献报道结合本课题组的研究结果,考察了磷系阻燃剂和功能填料对聚氨酯泡沫燃烧性能,主要包括氧指数、燃烧热释放速率等指标的影响,总结出聚氨酯硬泡体系中磷系阻燃剂的作用机理和规律,以及磷系阻燃剂与功能性填料复合应用的阻燃效果,并进一步提出了聚氨酯硬泡无卤阻燃的实现方案。     

阻燃剂的复配协效技术及纺织品的阻燃整理

环保型纺织品阻燃剂对人体和环境危害较小,符合绿色发展的理念.传统的阻燃剂如卤素阻燃剂阻燃效率较高,但在使用时会释放大量有毒及腐蚀性气体.氮系、磷系、硼系、硅系等阻燃剂在单独使用时,阻燃效果并不理想,而且成本高,因此需与其它阻燃剂复配协效使用才能达到阻燃效果.复配协效技术避免了使用单一阻燃剂的缺陷,综合了各种阻燃剂的优势...     

聚乙烯醇无卤阻燃研究进展

鉴于环保的压力,无卤阻燃剂逐渐替代含卤阻燃剂,用在聚乙烯醇(Polyvinyl alcohol,PVA)阻燃处理中。本文综述了近年来无卤阻燃PVA的最新研究进展,总结分析了无机型阻燃剂、磷系阻燃剂、氮系阻燃剂、膨胀型阻燃剂及反应型阻燃剂对PVA的阻燃研究现状,介绍了不同类型阻燃剂的阻燃机理、优缺点以及典型阻燃剂对PVA阻燃性质和力学性质的影响;在此基础上讨论了PVA阻燃的独特性,充分利用PVA的结构特征,研制出适合PVA加工方式的阻燃剂复配配方是PVA阻燃研究的主要发展方向。     

环三磷腈类阻燃剂的合成及应用研究进展

简要介绍了制备环三磷腈类阻燃剂所需起始原料六氯环三磷腈的合成方法、合成及取代反应机理;介绍了环三磷腈阻燃剂的阻燃机理;着重阐述了近20年间反应型的羟基/氨基环三磷腈、环氧基环三磷腈、含不饱和双键的环三磷腈、羧基环三磷腈阻燃剂,以及添加型烷氧基环三磷腈、芳氧基环三磷腈的合成及阻燃应用,同时综述了其应用材料的热稳定性能和阻燃性能,并对其发展趋势作了总结和展望。     

Solubilities,thermostabilities and flame retardance behaviour of phosphorus-containing flame retardants and copolymers

Thirteen phosphorus-containing flame retardants were synthesized in this work. The solubilities of flame retardant [(6-oxide-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-methyl]-butanedioic acid (DDP) in selected solvents are measured. TGA measurements of the 13 phosphorus-containing flame retardants were carried out and thermal stabilities of three flame-resistant PET (FRPET) resins were investigated. A FRPET incorporated by DDP with terephthalic acid and ethylene glycol reported in literature was also discussed and compared. The thermal stability of the FRPET is improved by the incorporation of phosphorus-containing flame retardants. The LOI values of all phosphorus-containing polyesters are higher than 27%. The improvement of the flame-resistant ability is due to the formation of the char that is not only caused by the existence of phosphorus elements in the resin but also by the relative large number of carbon atoms of the phenyl group in the flame retardants.     

Solubilities of Hexaphenoxycyclotriphosphazene and Tri(2-cyanoethyl)phosphine in Selected Solvents: Measurement and Correlation

Solubilities of hexaphenoxycyclotriphosphazene and tri(2-cyanoethyl)phosphine in selected solvents were measured in this work using a static analytical method. The solubilities of a series of phosphorus-containing flame retardants in organic solvents and water were recently measured in our laboratory. Based on these data and the solid?Cliquid equilibrium equation for the solute, the activity coefficients of these flame retardants were derived in pure solvents. The Scatchard?CHildebrand activity coefficient model was used to correlate these activity coefficients and the solubility parameters of the solutes were obtained. With the help of the analysis of the solubility parameters for the solute and solvents, solubility enhancement can be achieved due to the occurrence of the synergetic effect of the mixed solvent.     

聚合法制备无卤阻燃尼龙的研究进展

在全球阻燃材料无卤化的推进过程中,氮系、磷系、硅系等阻燃剂以及其复配物受到各国研究人员的广泛关注。利用聚合法(原位聚合法和共聚法)制备阻燃尼龙,可有效解决共混法中常存在的阻燃剂在基体中分散不均匀而导致的材料性能下降的问题。原位聚合法和共聚法是根据阻燃成分在基体中的存在方式而区分的,通常前者以物理均匀分散为主,后者多以化学键结合。本文在不同制备方法的背景下,根据阻燃剂类别进一步细分,综述了用原位聚合法和共聚法制备无卤阻燃尼龙的相关研究,并探讨了该领域中亟待解决的问题及未来发展方向。     

EVA基无卤阻燃复合材料的研究进展

分别介绍了采用金属氢氧化物阻燃剂、蒙脱石型阻燃剂、磷系阻燃剂、氮系阻燃剂、膨胀型阻燃剂、有机硅阻燃剂、碱式硫酸镁晶须（MOS）阻燃剂和辐射交联技术制备的无卤阻燃乙烯―乙酸乙烯共聚物（EVA）复合材料的研究开发现状,并展望了无卤阻燃EVA复合材料的发展趋势。     

New Phosphorus-Containing Flame Retardants for Poly-Urethanes and Polyesters

Abstract

New phosphorus - containing monomers and oligomers from tetrakis(hydroxymetyl)phosphonium chloride and dialkylphosphites are synthesized. On the basis of new products phosphorus-containing polyesters, polyurethanes and polyuretanesemicazbazides with improved fire resistance are obtained. The dependence of fire resistance of the polymers on the structure of the use flame retardants is investigated.     

Synthesis,characterization, thermal,and flame retardant properties of phosphate-based epoxy resins

A new phosphorus-containing oxirane bis-glycidyl phenylphosphate (BGPP), and a diamine, bis(4-aminophenyl)phenylphosphate (BAPP), were synthesized. Both of these two phosphorus-containing compounds lead to phosphate-containing epoxy resin via curing reaction. The kinetics of the curing reaction of BGPP with various curing agents, including BAPP, were studied. The introduction of electron-withdrawing group into the compounds increases the BGPP and decreases the BAPP reactivity in the curing reaction. The thermal and the weight loss behavior of the cured epoxy resins were studied by TGA. High char yields (32–52%) as well as high limiting oxygen index (LOI) values (34–49) of these phosphorylated resins were found, confirming the usefulness of these phosphorus-containing epoxy resins as flame retardants. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 565–574, 1997.     

A review on flame retardant technology in China. Part I: development of flame retardants

This paper provides an insight into some developments in flame retardants for different polymeric materials in China, primarily based on the publications that have appeared in the last 15 years. It focuses on the following aspects: halogen‐containing flame retardants, inorganic flame retardants (e.g. metal oxides and hydroxides, silicon‐containing materials, ammonium polyphosphate, red phosphorus, and expandable graphite), and organic flame retardants (e.g. aliphatic and aromatic phosphonates, nitrogen‐containing organics, and multi‐element organics). The inherently flame‐retardant polymer systems are also reviewed. The exploration of the novel flame retardants and flame‐retardant systems provides a powerful basis for the construction of flame‐retardant technologies and industrial applications in China. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermal stability of phosphinated diethyl tartrate

Organohalogen flame retardants, particularly brominated aromatics, are popular, effective, low cost, and widely used in the plastics industry. However, an increasing concern about persistence in the environment and potential negative health effects of these materials has generated intense interest in the development of alternatives. Ideally, these should have all the positive attributes of the materials that will be replaced. In addition, it is desirable that the new materials be as “green” as possible, e.g., based on renewable resources and be degradable to nontoxic products in the environment. A series of new, non-halogenated flame retardants based on tartaric acid is being developed. Tartaric acid is a by-product of the wine industry and is readily available locally on an annual basis (Michigan is the thirteenth largest producer of wine in the U.S.). It can be readily converted to the corresponding diethyl ester. This ester may serve as the base for the development of a series of new, non-halogenated flame-retarding agents. The presence of the reactive hydroxyl groups allows the introduction of a variety of phosphorus-containing moieties. For example, treatment of diethyl tartrate with diphenylphosphinyl chloride generates diethyl 2,3-di(diphenylphosphinato)-1,4-butanedioate. This material may serve as a monomer for the preparation of various phosphorus-containing polymers and oligomers via step-growth transesterification. The thermal stability of this compound has been assessed by thermogravimetry.     

Flame retardant chemical mechanisms of flame retardant viscose fibres and blends with polyester

A systematic investigation of structurally identical flame retardant viscose, modal and polyester blended fabrics and fibres was carried out in order to develop a chemical basis for more effective products based on organic and inorganic flame retardants. The oxygen indices and chemical compositions of phosphorus-nitrogen flame retardants (P-N) were used in efficiency and synergy evaluations. A new flame retardant viscose fibre containing silicid acid was included in the comparative evaluation procedure. Thermal gravimetry and X-ray diffractometry were used for determine physical factors during pyrolyzing of fibres. Charred residues were analyzed by applying elementary and solid 13-C NMR (CPMAS) spectrometry. The pyrolysis gas-liquid chromatographer connected with a gas phase FT infrared spectrometer was applied to identify the decomposition products of P-N-containing fabrics.     

Synthesis and properties of phosphorus polyesters with systematically altered phosphorus environment

Monomers with phosphorus-containing substituents were incorporated into aromatic-aliphatic polyesters to develop polymeric halogen-free flame retardants as additives for poly(butylene terephthalate) (PBT). They were built into the polyester backbone of PBT substituting 1,4-butane diol as monomer by phosphorus-containing aromatic-aliphatic diols. Starting from 10-(2,5-bis(2-hydroxyethoxy)phenyl)-9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO-HQ-GE), the chemical structure of the phosphorus monomers was systematically varied resulting in new polymers with diphenyl phosphine oxide substituents and bridged phosphine oxide units. The polymers were prepared by transesterification polycondensation in the melt in lab-scale as well as in a 2.4 l-autoclave. The properties of the polyesters were determined and compared to the DOPO-based polyester with respect to the achieved molar mass and polydispersity, solid state structure, glass transition temperature, thermal stability and combustion behavior.It was found that the different phosphorus substituents lead to different glass transition temperatures. The polymers containing bridged phosphorus structural units showed higher glass transition temperatures T_g and resulted in higher char yields after thermal decomposition. Both phosphine oxide structures showed only one-step decomposition with a shoulder at the end of the step. In contrast, two separate steps were observed in the polyesters with DOPO-substituents. The results indicated that the phosphorus polyesters under discussion are suitable to adjust the flame retarding mechanism.