膨胀型环状类磷酸酯蜜胺盐阻燃剂的合成及阻燃聚丙烯的结构与性能

以双季戊四醇、三季戊四醇、多聚磷酸、五氧化二磷和三聚氰胺为原料,合成了膨胀型环状类磷酸酯蜜胺盐阻燃剂,并与聚丙烯共混制成阻燃聚丙烯.红外分析表明该阻燃剂具有环状结构.通过扫描电镜和X射线衍射对阻燃聚丙烯进行了结构分析和表面纹理的表征.实验结果表明：该阻燃剂阻燃性能良好,但在聚丙烯中的分散性较差;用甲基纤维素对该阻燃剂进行表面化学修饰以后,该阻燃剂在聚丙烯中的分散性及阻燃材料的机械性能得到了明显的改善.     

三季戊四醇亚磷酸酯阻燃剂的合成及应用研究

以三季戊四醇(TPE)、亚磷酸三苯酯(TPP)为反应原料,氢氧化钠为催化剂,采用非溶剂酯交换一步法合成了三季戊四醇亚磷酸酯膨胀型阻燃剂。用红外光谱与元素分析初步确定了三季戊四醇亚磷酸酯类的物质。热分析表明,10％的失重所对应的温度为122℃,50％的失重对应的温度为371℃;其失重速率最大时的峰顶温度为329℃;在500℃时的成炭量高达40％。以三季戊四醇亚磷酸酯和三聚氰胺复配阻燃的环氧树脂,添加量为19％时其极限氧指数(LOI)为35％,通过了UL94V-0级,表明该阻燃剂具有优良的阻燃性能。     

二季戊四醇磷酸酯三聚氰胺盐的合成及阻燃性能测试

以磷酸、季戊四醇、三聚氰胺为原料,通过酸醇直接酯化和烘焙中和两步反应合成膨胀型阻燃剂二季戊四醇磷酸酯三聚氰胺盐,并对烘焙中和反应条件及其在聚乙烯中的阻燃性能进行了研究.确定最佳合成条件:n (二季戊四醇磷酸酯):n (三聚氰胺)=1:1;反应温度130-140℃;反应时间3-4h.将此阻燃剂添加到聚乙烯中,样品重量35...     

干法制备磷-氮膨胀型阻燃剂的研究

以磷酸、五氧化二磷、季戊四醇和三聚氰胺为原料,采用干法(不添加任何溶剂)合成了一种磷-氮膨胀型阻燃剂。IR分析发现合成阻燃剂具有与磷酸酯三聚氰胺盐类似的P=O和P-O-C双环结构。反应温度、时间和原料配比对酯化反应有明显的影响。酯化反应温度宜控制在120-130℃之间,反应时间2.5小时,加入五氧化二磷可以提高酯化反应的转化率,磷酸与五氧化二磷的摩尔比控制在2:1为宜。热重分析表明,该阻燃剂的起始分解温度为190℃左右,700℃时的成炭率约为30%。该阻燃剂受热后膨胀倍数约为30-50倍,SEM分析发现,阻燃剂膨胀炭层外表面连续、平滑、颗粒之间连结紧密,炭层为内部为多孔结构,空隙大小分布均匀,孔径约为150-200μm之间,这样的泡层结构能更好的起到隔热的效果。     

磷酸酯双三聚氰胺盐阻燃环氧树脂的燃烧性能和阻燃机理

以季戊四醇、三氯氧磷、三聚氰胺为原料合成了[1-氧-4-亚甲基-2,6,7-三氧-1-磷杂双环(2,2,2)辛烷]磷酸酯双三聚氰胺盐阻燃剂,将该阻燃剂加入到环氧树脂中制成阻燃环氧树脂。用TG、SEM、EDS和FT-IR进行表征,并采用极限氧指数法和垂直燃烧法测试材料的燃烧性能,结果表明,极限氧指数和垂直燃烧性能随阻燃剂含量的增加而提高,当阻燃剂含量达到30%时,氧指数达到36,垂直燃烧性能达到V-0级;阻燃剂对材料的成炭量影响不大,但改变了炭层的组成和物理性质,燃烧过程中形成的含有P、O、N的粘性高聚物将炭层连接在一起,起到了隔热、隔氧作用,发挥了凝聚相阻燃作用。此外,阻燃环氧树脂在燃烧过程中有NH3等不燃气体逸出,有效地稀释了气相中的氧气浓度,发挥了气相阻燃作用,对材料的阻燃有协同作用。     

反应性挤出加工制备无卤阻燃高分子材料

聚合物反应性加工集聚合物加工与化学反应为一体,以聚合物加工装置为反应器,通过聚合物加工过程中的化学反应形成新物质和新结构,实现高分子材料的高性能化和功能化,是高分子材料科学的研究前沿之一.本文简要介绍了我们研究小组近年来采用反应性挤出加工制备高性能无卤阻燃高分子材料方面的研究进展.利用反应性挤出加工剪切力强、温度可控以及易于传质传热的特点实现了常规方法难以合成的高黏阻燃剂三聚氰胺磷酸盐季戊四醇酯（MPP）和三聚氰胺氰尿酸（MCA）的高效合成,制备了综合性能优良的聚丙烯/MPP、尼龙6/MCA等无卤阻燃高分子材料.研究所涉及的化学和物理方法,为聚合物无卤阻燃提供了高效、经济、环保和易于工业化的新技术,并拓宽了聚合物反应性加工的应用领域.     

MPP/PER/APP系统阻燃的PA6/OMMT纳米复合材料的燃烧特性

以聚磷酸蜜胺(MPP)／季戊四醇(PER)／聚磷酸铵(APP)三元膨胀型阻燃剂(IFR)(其中P／PER／三聚氰胺(MA)的摩尔比为4．1／1．0／1．1)对聚酰胺6(PA6)／有机蒙脱土(OMMT)纳米复合材料(wOMMT=0．03)进行阻燃，测定了阻燃PA6／OMMT的极限氧指数(LOI)及垂直燃烧阻燃性(UL94)，以锥形量热仪(CONE)测定了材料诸多与火灾安全性有关的阻燃参数，包括释热速率、有效燃烧热、总释热量、质量损失速率、比消光面积及引燃时间等，并与PA6、阻燃PA6及PA6／OMMT进行了比较，用扫描电镜(SEM)观察了由CONE测试所得残炭的形态。     

软质聚氨酯泡沫塑料用无卤阻燃剂的研究

本文以羟基苯氧膦丙烯酸(CEPP)和三聚氰胺(MA)为原料合成了一种含磷、氮无卤阻燃剂(CMA),采用FT-IR表征了阻燃剂的化学结构,并将该阻燃剂用于软质聚氨酯泡沫(FPUF)的阻燃。用扫描电镜(SEM)研究了阻燃剂的加入对FPUF的形态的影响,通过LO I和垂直燃烧(Cal.117A)测试研究了该阻燃剂对FPUF的阻燃效果。结果表明,CMA可以有效提高FPUF的阻燃性:当CMA的添加量为10%时,FPUF即可通过Cal.117A测试,其LO I值也从17.3提高到23.0;随阻燃剂添加量的增加,FPUF的阻燃性能也逐渐提高。TG测试结果表明CMA的加入对FPUF的热稳定性没有多大影响。     

硅溶胶改性水性超薄型钢结构防火涂料的研究

以过硫酸铵为引发剂,OP-10为乳化剂,在聚乙烯醇保护下,用甲基丙烯酸甲酯、丙烯酸丁酯进行共聚,合成乳液型丙烯酸酯树脂,并用红外光谱表征.用磷酸、五氧化二磷、季戊四醇反应生成的酯型中间体与三聚氰胺混合,制得膨胀型阻燃剂,用红外光谱表征并对其进行热重分析.用自制膨胀型阻燃剂与乳液型丙烯酸树脂及少量硅溶胶按一定比例混合调匀,制备超薄型钢结构防火涂料,根据国家标准对涂料性能进行检测,其基本性能达到防火涂料要求.     

新型阻燃性氨基树脂鞣剂的合成

现有的阻燃剂产品多数分解温度低,难溶于水,不易渗透皮革纤维。本文合成的季戊四醇二氢酯羟甲基化三聚氰胺树脂具有高效的阻燃作用,又具有三聚氰胺树脂鞣剂独特的鞣革作用。本文考察其合成工艺条件及其对产品性能的影响因素。     

Development of additives possessing both solid-phase and gas-phase flame retardant activities

Effective additives are required to impart a measure of fire retardancy to polymeric materials used in a variety of applications. Traditionally, these have been gas-phase active additives, most commonly organohalogen compounds or solid-phase active agents, often organophosphorus compounds. Organosphosphorus flame retardants are often very effective but may suffer from a cost disadvantage when compared with their organobromine counterparts. Organohalogen flame retardants are usually quite effective but their use is a subject to several environmental concerns. The development of additives that could simultaneously promote both types of fire retardant action could make available flame retardants that are both more cost effective and more environmentally friendly than those currently in use. Several sets of compounds with the potential to display both solid-phase and gas-phase flame retardant activities have been prepared and evaluated.     

添加型磷腈类阻燃剂在高分子材料中的应用

添加型磷腈类阻燃剂具有热稳定性好、耐候性好、低烟、低毒、低添加量和吸潮性低等优点,在阻燃高分子材料领域得到广泛应用。综述了近些年来国内外添加型磷腈类阻燃剂在高分子材料中的应用研究进展,分析了磷腈阻燃剂阻燃高分子材料的研究现状,为新型磷腈类阻燃剂的研发提供参考。     

Thermal degradation of 2,4,6-tri[(bromo)x anilino]-1,3,5-triazines

The need for more efficient and 'greener' flame retardants for polymeric materials is ever present and of increasing intensity as regulatory agencies continue to display concern about the environmental impact of traditional materials. Compounds capable of multiple modes of action would be particularly desirable. Compounds containing both bromine (for good gas-phase activity) and nitrogen (to promote solid-phase activity) should be good candidates for development as flame retardant agents. A series of 2,4,6-tri[(bromo)_xanilino]-1,3,5-triazines have been synthesized and characterized spectroscopically. The degradation characteristics of these compounds have been examined using thermogravimetry. They undergo step-wise decomposition beginning at about 400°C.     

TWO-DIMENSIONAL DISTRIBUTIONS OF TEMPERATURE AND OH, C_2 AND CH RADICALS IN FLAME DETECTED BY LASERINDUCED FLUORESCENCE

The in situ, high spatial resolution, two-dimensional distributions of OH(X), C_2(X) and CH(X) radicals in premixed paraffin/air flames are first reported. The measurements were done with the laser-induced fluorescence spectroscopies (LIFS) of the transitions of OH(A~Σ~+←→X~2Π), C_2(A~3Π←→X~3Π) and CH(B~2Σ←→X~2Π), (A~2△→X~2Π). The results show that OH(X) populated the edge of the outer flame, while C_2(X) and CH(X) the edge of the inner cone of the flame.The local rotational temperature of OH radical for a small zone was detected by the saturated laser-induced fluorescence spectroscopy of A~2Σ~+, v′=0←→X~2Π, v=″0 transition. The two-dimensional temperature distribution for the flame was measured through moving the position of the burner.     

新型单组分磷-氮膨胀型阻燃剂的合成及其阻燃性能

以氯化螺环磷酸酯(1)和对甲苯胺(2)为原料,经亲核取代反应合成了"三源"一体的新型单分子磷-氮膨胀型阻燃剂——季戊四醇螺环磷酰对甲苯胺(3),其结构经1H NMR和IR表征。考察了溶剂、原料配比、反应温度、反应时间和缚酸剂对3产率的影响。合成3的最佳反应条件为:乙腈为溶剂,三乙胺为缚酸剂,1 10mmol,n(1)∶n(2)=1∶3,于80℃反应4 h,产率79.3%。阻燃性能研究结果表明,3的初始分解温度为220℃,500℃成炭率达43.3%。     

A review on potential development of flame retardant kenaf fibers reinforced polymer composites

Kenaf fibers have been extensively explored from the past few decades in polymer composites industries owing to its extensive adaptations, excellent properties together with its comparable mechanical properties to traditional glass fibers polymer composites. The combustibility or lowered flame retardancy hampered the diverse applications of kenaf fibers reinforced polymer composites, as it affects the mechanical strength and stiffness of composites during fire. Current review article intended to be a comprehensive source of published literature involving the flame retardants (FRs), types and applications of FRs and the fabrication of kenaf fibers reinforced polymer composites. This article will also provide a perfect data on the recent development of the FR kenaf fibers polymer composites with different FRs and explored its structural and semi‐structural industrial application for performing further research in this topic. Copyright © 2016 John Wiley & Sons, Ltd.     

磷系阻燃共聚酯的结构与性能

采用磷系阻燃剂2-羧乙基苯基次磷酸（CEPPA）作为第3单体,通过聚合反应制备了含磷的阻燃共聚酯。采用核磁共振、DSC、元素分析和极限氧指数仪表征阻燃共聚酯的化学组成、序列分布、结晶性能、磷含量和极限氧指数。结果表明：大部分CEPPA单元以无规分布的形式共聚到聚酯分子链中,小部分CEPPA单元以短嵌段的形式共聚在聚酯分子链中,且随着阻燃剂含量增加,无规系数变小。由于分子链的规整性下降,与聚对苯二甲酸乙二酯（PET）相比,阻燃共聚酯的Tg和Tm下降,结晶度减小。随阻燃剂含量的增加,极限氧指数值增加,当阻燃共聚酯中的磷含量达到9．08mg／g时,极限氧指数值达到33％以上。     

Potential For Qualitative Analysis Using Organic Emission Spectra In Flames

Abstract

A preliminary investigation into the potential of using the emission spectra of organic molecules arising from a hydrogen-entrained air flame to obtain structural information has been made. Results for several alcohols show that the technique can be used to distinguish between geometrical isomers.     

The Underlying Chemistry to the Formation of PO2 Radicals from Organophosphorus Compounds: A Missing Puzzle Piece in Flame Chemistry

Reactive species, such as ^.PO₂ and HOPO, are considered of upmost importance in flame inhibition and catalytic combustion processes of fuels. However, the underlying chemistry of their formation remains speculative due to the unavailability of suitable analytical techniques that can be used to identify the transient species which lead to their formation. This study elucidates the reaction mechanisms of the formation of phosphoryl species from dimethyl methyl phosphonate (DMMP) and dimethyl methyl phosphoramidate (DMPR) under well-defined oxidative conditions. Photoelectron photoion coincidence techniques that utilized vacuum ultraviolet synchrotron radiation were applied to isomer-selectively detect the elusive key intermediates and stable products. With the help of in situ recorded spectral fingerprints, different transient species, such as PO₂ and triplet O radicals, have been exclusively identified from their isomeric components, which has helped to piece together the formation mechanisms of phosphoryl species under various conditions. It was found that ^.PO₂ formation required oxidative conditions above 1070 K. The combined presence of O₂ and H₂ led to significant changes in the decomposition chemistry of both model phosphorus compounds, leading to the formation of ^.PO₂. The reaction ^.PO+O₂→^.PO₂+O: was identified as the key step in the formation of ^.PO₂. Interestingly, the presence of O₂ in DMPR thermolysis suppresses the formation of PN-containing species. In a previous study, PN species were identified as the major species formed during the pyrolysis of DMPR. Thus, the findings of this study has shed light onto the decomposition pathways of organophosphorus compounds, which are beneficial for their fuel additive and fire suppressant applications.     

Flame Emission Spectroscopy of Aqueous and Nonaqueous Solutions in the Nitrous Oxide-Acetylene Flame

Abstract

The relative emission intensities and detection limits for 183 lines and bands of 52 elements in the nitrous oxide-acetylene flame have been determined. Linearity of the emission intensity with concentration was investigated and detection limits of the elements in 80 percent acetone were also obtained and compared with those of aqueous solutions. Emission was observed for all the elements in acetone solution, and only selenium did not give a measureable emission in aqueous solution.