PEPAP合成及其在阻燃SEBS/PP/PP-g-MMA中的应用

以季戊四醇磷酸酯（PEPA）和六氯环三磷腈（HCCP）为主要原料,合成了一种新型的磷腈类阻燃剂PEPAP;探究了其合成工艺,并采用红外光谱（FIR）和热失重（TG）测试对其进行了结构表征和稳定性分析;进一步,探究了以PEPAP作为SEBS/PP/PP-g-MMA的阻燃剂的阻燃作用。结果表明：PEPAP合成的最佳工艺条件为溶剂为无水乙腈,反应温度74℃,反应时间12 h;其热稳定性和成碳能力较高;PEPAP阻燃剂用量为25%时,SEBS/PP/PP-g-MMA的阻燃剂体系的氧指数达29.6%,垂直燃烧达UL-94的V-2级,生成致密炭层。新型阻燃剂的合成为制备高性能聚烯烃阻燃材料打下坚实的基础。     

2-羧乙基苯基次膦酸乙二醇酯的合成研究

阻燃剂2-羧乙基苯基次膦酸(CEPPA)作为聚酯阻燃改性的反应型含磷阻燃剂之一,采用阻燃剂酯化液的方法制备阻燃聚酯已实现产业化,绝大多数学者研究了阻燃聚酯的合成及性能,但酯化液合成没有系统研究。本文通过对阻燃剂CEPPA与乙二醇合成酯化液的工艺进行系统研究,包括温度、时间、配比、压力等,通过分析酯化液的酸值、二甘醇、动力黏度等指标,确定了反应优选工艺:反应温度170℃,反应时间不超过100 min,酯化液样品磷含量为6.4%,反应采用先常压后负压的出水方式,负压为50 kPa。通过此方法合成的酯化液产品指标稳定,可用于工业化生产阻燃聚酯。     

甲基膦酸二甲酯的制备

本文通过分析国内外阻燃剂的行业发展趋势,推出新型阻燃剂—甲基膦酸二甲酯,并进行工艺生产路线的选择,做甲基膦酸二甲脂工艺合成小试。     

环氧植物油基增塑剂的合成工艺进展

环氧植物油(EPO)是一类优良的环保型增塑剂。以合成方法和催化剂为线索,综述了近年来国内外EPO合成工艺的最新进展。同时,对现有的催化体系以及合成工艺进行了简要的分析,并指出了开发新型、高效、绿色且廉价的催化体系,仍将是今后EPO合成领域的研究方向。     

新型膨胀型阻燃剂阻燃聚丙烯的研究

以五氧化二磷、磷酸、季戊四醇和三聚氰胺为原料,合成了一种新型的膨胀型阻燃剂（IFR）并和聚磷酸铵（APP）聚四氟乙烯（PTFE）复配对聚丙烯（PP）进行阻燃,用热重法（TG）对阻燃PP的热性能进行了研究,利用氧指数仪测定了阻燃PP的极限氧指数（LO I）值,用垂直燃烧法测试了其燃烧等级,当阻燃剂含量为24%时,LO I值为30.9%。用锥形量热仪对阻燃PP的燃烧性能进行了分析,并用扫描电镜（SEM）对阻燃聚丙烯（FR-PP）的残炭结构进行了研究,结果表明,该复配阻燃剂能够促进PP的成炭性,具有优良的阻燃PP性能。     

阻燃剂在低烟无卤电线电缆料中的应用

通过对低烟无卤电线电缆燃烧特性和阻燃剂的阻燃机理的分析,论述了无机金属化合物、磷系、氮系、磷氮系阻燃剂等不同类型阻燃剂的阻燃特性、发展动向及新型阻燃技术,指出无卤、高效、低烟、低毒、多功能的新型阻燃剂合成及其新型阻燃技术的研究是阻燃剂的发展方向。     

膨胀阻燃聚丙烯的研究

研究了淀粉、季戊四醇等对PP/阻燃剂体系的膨胀阻燃效果的影响。根据膨胀阻燃原理,合成了一种多功能的新型膨胀阻燃剂MPP,同时利用IR、TGA等手段对合成的膨胀阻燃剂的结构、热稳定性及其在PP中的阻燃效果进行了研究     

新型阻燃剂EBT的合成

采用正交实验的方法,确定了合成新型阻燃剂EBT的最佳工艺条件,并对EBT结构和阻燃性能进行了测试。     

新型无机磷基阻燃剂的研究进展

以黑磷基阻燃剂为代表的纳米级新型无机磷基阻燃剂,在极低的添加量下即可实现高分子材料的阻燃性能和机械性能的同步提高,表现出良好的应用前景。综述了新型无机磷基阻燃剂的研究进展,重点介绍了黑磷基阻燃剂的功能化策略、制备工艺、阻燃机理和应用进展,最后对发展趋势进行了展望。总结并评述了黑磷制备所用的超声剥离、球磨剥离、电化学插层剥离等纳米化工艺和利用阻燃有机/无机物质对黑磷进行共价或非共价的修饰策略,对比分析了溶液共混、熔融共混、原位聚合、涂层等复合制备工艺的利弊,归纳了黑磷基阻燃剂的结构与性能之间的基本规律,提出了今后在科学创新和工程突破两方面的研究重点。     

阻燃剂三聚氰胺磷酸盐的合成研究

开发了一种氮磷系环保型阻燃剂新品种。即以三聚氰胺、磷酸为原料,合成了新型高效阻燃剂三聚氰胺磷酸盐(MP),考查确定了MP较佳合成工艺条件,产品合成收率≥95.0%;将产品应用于玻纤增强PA66中的阻燃性能测试,阻燃效果达到国外同类产品水平。     

聚烯烃阻燃母料的研制

本文介绍了聚烯径阻燃母料的配方设计、制造工艺及应用技术。对阻燃母料的各项性能进行了测试，并系统研究了阻燃母料对ＰＰ、ＨＤＰＥ力学性能和阻燃性能的影响，为聚烯烃阻燃母料的工业化生产提供了参考数据。     

一种新型复合阻燃剂的制备

将蜜胺焦磷酸盐(MPP)与乙二胺二磷酸锌(EDAZP)及低水硼酸镁或低水硼酸铝组成的新型无卤复合阻燃抑烟剂用于聚烯烃树脂,具有优异的阻燃抑烟性能,一般添加量在20%~31%时极限氧指数超过30%,可达到UL94V-0级阻燃效果,而且具有抑烟作用。     

Preparation and characterization of aluminum hypophosphite/reduced graphene oxide hybrid material as a flame retardant additive for PBT

Aluminum hypophosphite/reduced graphene oxide (AHP/RGO) hybrid flame retardant with high thermal stability was successfully prepared by a one‐step method consisting of the simultaneous reduction of graphene oxide and the deposition of AHP on graphene. The as‐prepared sample was characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X‐ray photoelectron spectroscopy. The obtained sample was used as a flame retardant for polybutylene terephthalate, and the flame retardancy of the composites was investigated by a limiting oxygen index test, a UL‐94 test, and cone calorimetry. The results showed that AHP/RGO exhibited improved flame retardancy when compared with bare AHP. The addition of AHP/RGO to polybutylene terephthalate led to a significant reduction in the heat release rate and resulted in excellent anti‐dripping properties for the composites. Copyright © 2016 John Wiley & Sons, Ltd.     

一种含磷-氮聚合型膨胀阻燃剂的合成与表征

用二甲苯作溶剂,二氯磷酸苯酯与二乙烯三胺共聚合成了二氯磷酸苯酯-二乙烯三胺共聚物阻燃剂。采用正交设计方法对物料摩尔比、反应温度、溶剂用量进行了考察。结果表明:最佳n(二乙烯三胺)∶n(二氯磷酸苯酯)=1.21∶1,最佳反应温度为100~110℃,溶剂用量50 mL,反应时间9 h,最高产率72.4%。通过FTIR、1HNMR对共聚物的分子结构进行了表征,并通过TGA考察了其热稳定性。当w(聚磷酸铵)=10%,w(共聚物)=15%应用于低密度聚乙烯(LDPE),可使氧指数达到26,垂直燃烧达到UL-94 V-0级,满足了聚烯烃电线电缆及管材的阻燃要求。     

常用阻燃剂对氯化橡胶涂料阻燃性的比较

用作者设计的涂料阻燃试验方法结合热重分析法，研究比较了氯化石蜡、三氧化二锑、氧化锌、氧化铁红和二氧化锡等阻燃剂对氯化橡胶涂料的阻燃效果。结果表明，在氯化橡胶涂料体系中，用少量氧化铁红代替部分三氧化二锑，漆膜阻燃性不下降；氯含量５２％的氯化石蜡，其阻燃性高于氯含量７０％的氯化石蜡。     

Thermal degradation behaviors and flame retardancy of PC/ABS with novel silicon‐containing flame retardant

A novel flame retardant (DVN) containing silicon, phosphorus, and nitrogen has been synthesized from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), vinylmethyldimethoxy silane (VMDMS) and N‐β‐(aminoethyl)‐γ‐aminopropyle methyl dimethoxy silane (NMDMS), then incorporated into polycarbonate/acrylonitrile butadiene styrene (PC/ABS) alloy. The flame retardancy of PC/ABS/DVN is evaluated by cone calorimeter and limited oxygen index (LOI) and the thermal degradation behavior is investigated by thermogravimetric analysis under nitrogen and air. The PC/ABS/DVN sample was thermally degraded at 400°C for different amounts of time and studied by Fourier transform infrared spectroscopy to better understand the mechanism of flame retardancy. The results show that the thermal stability and flame retardancy of PC/ABS are improved by incorporation of DVN. Scanning electric microscopy results show that the outer surface of the char layer of PC/ABS/DVN after the LOI test is smooth and the internal structure is like swollen cells, which benefits the flame retardancy of PC/ABS. Copyright © 2007 John Wiley & Sons, Ltd.     

Preparation and investigation of flame‐retardant epoxy resin modified with a novel halogen‐free flame retardant containing phosphaphenanthrene,triazine‐trione,and organoboron units

In this article, a novel flame retardant (coded as BNP) was successfully synthesized through the addition reaction between triglycidyl isocyanurate, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and phenylboronic acid. BNP was blended with diglycidyl ether of bisphenol‐A to prepare flame‐retardant epoxy resin (EP). Thermal properties, flame retardancy, and combustion behavior of the cured EP were studied by thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the flame retardancy and smoke suppressing properties of EP/BNP thermosets were significantly enhanced. The LOI value of EP/BNP‐3 thermoset was increased to 32.5% and the sample achieved UL94 V‐0 rating. Compared with the neat EP sample, the peak of heat release rate, average of heat release rate, total heat release, and total smoke production of EP/BNP thermosets were decreased by 58.2%–66.9%, 27.1%–37.9%, 25.8%–41.8%, and 21.3%–41.7%, respectively. The char yields of EP/BNP thermosets were increased by 46.8%–88.4%. The BNP decomposed to produce free radicals with quenching effect and enhanced the charring ability of EP matrix. The multifunctional groups of BNP with flame retardant effects in both gaseous and condensed phases were responsible for the excellent flame retardancy of the EP/BNP thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45291.     

Diffusion of additives and deterioration with passage of time in polypropylene

The diffusion of additives and the deterioration with the passage of time in polypropylene (PP) were studied by using the UL flaming test and the oxygen index test to measure the flame retardancy. The weight change was also measured. The decreases with the lapse of time were observed for multiple flame retardants. Aliphatic brominated compounds showed the best result for flame retardancy in the initial stage of combustion. The best flame retardants for PP to inhibit the deterioration of flame retardancy with the passage of time were brominated hydrocarbon with more than two aromatic rings connected by a functional group or isocyanurate, and phosphates connected with a branching aliphatic hydrocarbon. The weight of the loss was plotted as a function of aging time and temperature to elucidate why the flame retardancy deteriorated. The apparent diffusion constant depends on the temperature and the rate was expressed with the Arrhenius equation. The concentration of flame retardant in PP was calculated by the constant and the equation at arbitrary time after thermal aging. The relation between the performance and chemical structure of the additives was also discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Development of heat shrinkable and flame‐retardant EVA/CSM blends

A plastic (EVA) was blended with elastomer (CSM) with and without curatives. The elastomer phase (amorphous) contributed markedly to the shrinkability and most important is, took up a major amount of additive flame‐retarding agent thus not affecting much the heat shrinkability of the plastic i.e. as a whole the blend. When the elastomer phase was crosslinked the flame‐retardancy, due to a reduction of combustible volatile product, was increased. Additive flame‐retardants hamper the heat‐shrinkability of the blend to some extent depending on various factors such as blend composition, temperature, curing etc. The depression of shrinkability in the presence of flame‐retarding agent was less for the cured sample and elastomer‐rich blend compared with the uncured and plastic‐rich blend, respectively. It was found that with an increase in the cure time and elastomer content the shrinkability as well as flame‐retardancy was increased. At high temperature the sacrifice of the shrinkability in the presence of flame‐retardants increased, for a particular blend. The shrinkability and flame‐retardancy of a cured sample was higher than that of an uncured sample. The highest flame‐retardancy was obtained in the presence of Sb₂O₃/Chlorohor. Copyright © 2002 John Wiley & Sons, Ltd.     

Flame retardancy in fabric consisting of cellulosic fiber and modacrylic fiber containing fine‐grained MoO3 particles

Flame retardancy of fabrics consisting of modacrylic fiber containing with various dispersed metal compounds and cellulosic fiber has been investigated by means of flame test (ISO15025 procedure A) and limiting oxygen index (LOI). It has been found that excellent flame retardancy is achieved by fine‐grained MoO₃ particles. The afterflame time in flame test and the LOI value are improved with decreasing particle size of MoO₃. The flame retardancy of MoO₃ (particle size; 0.1 µm) is comparable to that of Sb₂O₃. On the other hand, significant improvement in flame retardancy is not observed for other metal compounds although some metal oxides and a hydroxide in the present study are known as flame retardant or smoke suppressing agent in halogen containing polymer in previous studies. In order to clarify the mechanism of the observed flame retardancy by the addition of fine‐grained MoO₃, we have carried out X‐ray fluorescence spectrometry (XRF) measurement of the fabric specimen after the flame test and thermogravimetric analysis (TGA) of various types of samples. These analytical data indicated that MoO₃ works as halogen synergist in solid phase and the char of modacrylic fiber formed by addition of MoO₃ suppresses decomposition of the cotton blended in the fabric in the range of the ignition temperature. Copyright © 2015 John Wiley & Sons, Ltd.