无卤环保型阻燃环氧树脂的研究进展

综述了目前国内外无卤阻燃环氧树脂(EP)的研究发展状况,重点介绍了磷、氮、硅等阻燃元素对EP的阻燃处理及其有关的阻燃机理和存在的一些问题,如相容性差、耐热性不好和添加量受限等,并介绍了相应的解决方法;最后,对无卤阻燃EP的发展趋势进行了展望,并为国内相关企业提出了一条绿色、高效、复合的发展道路.     

磷氮阻燃固化剂对环氧树脂阻燃性能的影响

为了提高环氧树脂固化体系的阻燃性能,以1,3-丙二胺(DPAN)和苯膦酰二氯(PPDC)为主要原料合成一种新型磷氮反应型阻燃固化剂(PPDPA),对合成化合物的组织结构和热性能进行了表征.以不同比例PPDPA为固化剂,制备一系列具有不同磷含量的阻燃环氧树脂,并对其进行热性能分析和阻燃性能测试.结果表明,添加PPDPA的环氧树脂体系的500 ℃残炭明显高于EP/DPAN体系,且残炭表面磷碳层具有明显的发泡现象.当磷的质量分数达到2.12%时,EP-2样品成功通过UL94 V-0阻燃等级测试,LOI值达到28.3%,PPDPA在环氧树脂材料中表现出了良好的阻燃性能.     

水镁石/硼酸锌复合阻燃环氧树脂的制备与性能

针对环氧树脂在添加普通水镁石阻燃剂后力学性能恶化的问题,通过对水镁石的改性和复配制备了一种新型阻燃剂.通过SEM观察水镁石粉体及阻燃环氧树脂断面的表面形貌,利用弯曲强度测试考察阻燃环氧树脂的力学性能,测定氧指数考察其阻燃性能.结果表明,水镁石用量为30%时阻燃EP性能最好.用硅烷偶联剂Ⅰ和Z6173改性,阻燃EP的弯曲强度和氧指数分别为5.21 M Pa、28.9%和4.82 M Pa、29.1%.用6份的硼酸锌与硅烷偶联剂Ⅰ改性的水镁石复配制得的复合阻燃剂,其制备成的阻燃EP的弯曲强度和氧指数最高达到4.85 MPa和29.3%.     

水性氨基阻燃涂料的研究

以改性氨基树脂为主要成膜物质，以自制阻燃剂及其它助剂配制而成了水性阻燃涂料。论述了合成改性氨基树脂的反应机理及反应条件，阐述了阻燃剂的阻燃机理。该涂料阻燃性好，无毒无污染，工艺简单，成本低，可用于纸张、木材等的阻燃。     

Study on effect of crosslink structure on decomposition of epoxy resins in nitric acid

One chemical approach using nitric acid as the solvent to decompose thermosetting epoxy resin was discussed. The samples were prepared by using different kinds of curing agents, namely polyamide (PA651), isophorone diamine (IPDA), 4,4’-diaminodiphenylmethane (DDM) and 2-ethyl-4-methy-imidazole (EMI-2,4) and different kinds of epoxy resins, namely bisphenol-A epoxy resin(E-44), bisphenol-A epoxy resin(E-51), N,N,N’,N’ teraglycidy 4,4’ diaminodiphenyl methane (AG-80) and diglycidyl-4,5-epoxycyclohexane-1,2-dicarboxylate (TDE-85). Their effects on decomposition rate were investigated and the decomposition products were analyzed by Infra-red (IR) spectra, and Gas Chromatography-Mass Spectrometry (GC-MS). Based on conclusions drawn from experiments, the mechanism of degrading thermosetting epoxy resin with nitric acid was envisaged tentatively.     

含磷聚合物阻燃剂研究进展

含磷聚合物显示出优良的热稳定性和优秀的阻燃性能,作为添加型阻燃剂,其可应用为聚酯、聚烯烃等领域的塑料、纤维等阻燃助剂,而得到广泛的关注和应用。通过对含磷聚合物类阻燃剂的结构和性能及其近年来研究进展的综述,展望了其发展方向。     

电子塑封材料用环氧树脂的进展

介绍塑料封装材料用环氧树脂的特性、组成及应用，论述了封装技术的发展对环氧树脂的要求、发展趋势以及环氧树脂改性的研究情况。     

含磷高分子阻燃剂HMPP的合成及应用研究

以三氯氧磷、乙醇及1,4-丁二醇为主要原料,二氯乙烷为溶剂,辛酸亚锡为催化剂,三聚氰胺为缚酸剂,制备了含磷高分子阻燃剂HMPP。研究了主要反应因素,确定适宜的反应条件为n(三氯氧磷)∶n(乙醇)∶n(1,4-丁二醇)为1∶1∶1,0℃滴加入乙醇,反应依次在25、45、65℃分别保温反应2、2、1 h。反应产率94.2%,产物数均分子量19 769,多分散指数1.88。用FTIR、1H-NMR和GPC表征了产物结构。在聚氨酯软质泡沫中应用表明HMPP具有良好的阻燃性。     

新型有机硅阻燃剂的合成及其表征

以氨基硅烷和苯基硅烷为原料,在酸性条件下以不同的配比合成了有机硅树脂.同时以有机硅树脂与中间体DOPO衍生物(10-丙酸-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)为原料,合成了兼含P、N、Si三种元素的有机硅阻燃剂.通过红外光谱和核磁共振氢谱对其结构进行了表征,证明了有机硅阻燃剂的成功合成.将阻燃剂应用于PP(聚丙烯)材料中,当加入量为25%时,阻燃体系的LOI(极限氧指数)值达25.7%,UL-94(垂直燃烧)阻燃级别可以提高到V-0级.     

四官能基环氧树脂／蒙脱土纳米复合材料的制备及表征

采用阳离子交换的方法对蒙脱土进行了有机化改性,并制备了环氧树脂／蒙脱土纳米复合材料．用FT-IR和XRD研究了环氧树脂／蒙脱土纳米复合材料的结构,并测试了纳米复合材料的性能．实验结果表明,改性使蒙脱土层间距变大,纳米复合材料的力学性能与纯环氧树脂相比提高了50％．     

有机磷系阻燃剂文献计量学分析

用文献计量学的方法对1986至2011年科学引文索引、工程索引、科技会议录索引、中国知网数据库收录的有机磷系阻燃剂文献数量进行了系统分析,对有机磷系阻燃剂研究的学科发展及地域分布有了较全面的掌握.结合我国1995年至2011年以来的次磷酸盐及亚磷酸盐进出口量统计分析,认为未来10年有机磷系阻燃剂工业在世界范围内将进入空前发展的时期,中国有机磷系阻燃剂的总生产量将进入一个指数增长期.     

Effect of flame retardant containing phosphorus and silicone on thermal performance of PC/ABS

A flame retardant (DPA-SiN) containing phosphorus, nitrogen and silicon elements was synthesized. The halogen free flame retardant was incorporated into PC/ABS to improve its flame retardancy. The flame-retardant properties of the PC/ABS/DPA-SiN blends were estimated by limiting oxygen index (LOI) values and CONE Calorimeter, while thermal stabilities were investigated through thermo gravimetric analysis (TGA). The PC/ABS/DPA-SiN blends were thermally degraded at 400 °C for different amounts of time and studied by Fourier transform infrared spectroscopy (FTIR) to better understand the degradation behavior of PC/ABS/DPA-SiN. Funded by Shanghai Science and Technology Commission of China (No. 05dz22303)     

Research on the effect of the common flame retardant in reducing the flammability of the bitumen

The bituminous defect that the binder is flammable will bring road safety risk.Once it catches fires,large quantities of heat,smoke and poisonous gas are produced,released and spread quickly,which seriously hinder escape and rescue and harms heavily traffic safety.The common flame retardant system is used to modify the asphalt.Cone Calorimeter is adopted to evaluate the burning property of asphalt.The performance of the flame retardant is evaluated by limiting oxygen index and orthogonal design method.The paper analyzes the synergism of the asphalt and flame-retardant,and analyzes the effect of the flame on preventing the smoke to spread and demonstrates that the use of common flame retardants which is added into binder is good at reducing the flammability of the binder.This way can increase the safety of asphalt pavement when fire occurs in the tunnel.The study suggests that flame retardancy of asphalt can be evaluated by Limit Oxygen Index (LOI) and the flame retardancy property of asphalt has marked change according to the content of flame retardant.SB has perfect flame retardancy property,and ATH is better than MH in the effect of flame retardant.     

Flame-retardant mechanism of magnesium oxychloride in epoxy resin

Flame-retardant mechanism of magnesium oxychloride (MOC) in EP was investigated by limiting oxygen index (LOI), XRD, SEM, TG-DTG and DSC. The results show that MOC performed well as an inorganic flame-retardant in EP. When the content of MOC is 50%, the LOI of EP reaches 29.6% and mass of residual char reaches 9.6%. The flame retarde mechanism of MOC is due to the synergies of diluting, cooling, catalyzing char forming and obstructing effects. Funded by the Defense Pre-research Project of the Eleventh-Five-Year-Plan of China (No. 51312040404)     

Statistical deduction and experimental verification on kinetic equations for the curing reactions of epoxy resins／amines

Based on three typical mechanisms (second-order, third-order and competitive mechanisms) for the curing reactions of the epoxy resins with amines, a pair of the kinetic equations ( for primary and secondary aminations) was presented to explain the uniformity and relationship among the three different kinetic mechanisms of the reactions. The presented macro-equations were deduced from the kinetic micro-equations by the statistics method. And the constitutive equations were verified by experimental data at different reaction times and temperatures (95℃, 60℃ and 39℃), taking diglycidyl ether of bisphenol A (DGEBA) /ethyleneamine (EA) as a model.     

等离子体与电子束接枝法对聚合物阻燃性能的影响

研究了以EVA共聚物为基础 ,采用等离子体和高能电子束辐照接枝丙烯酸类单体样品的阻燃性能 .在相同接枝率条件下 ,等离子体接枝样品的点燃时间及极限氧指数要小于高能电子束接枝样品的点燃时间及极限氧指数 .这是由于高能电子束辐照聚合物样品可以引起聚合物底材的交联作用 ,并产生凝胶 ;而等离子体辐照聚合物不对聚合物体相产生交联作用、不产生凝胶所致     

棉织物的绿色阻燃整理工艺的研究

采用适合于棉织物的绿色阻燃剂A对织物进行阻燃整理。运用数理统计中的正交试验及极差分析法对所得结果进行分析，确定了棉织物绿色阻燃整理的最佳工艺参数：阻燃剂质量浓度250g／L。交联剂质量浓度90g／L，柔软剂质量浓度9g／L．温度160℃。时间3min．结果表明。整理后的织物具有良好的阻燃性能和耐水洗性。织物的甲醛含量较低．     

棉织物的绿色阻燃整理工艺的研究

采用适合于棉织物的绿色阻燃剂A对织物进行阻燃整理,运用数理统计中的正交试验及极差分析法对所得结果进行分析,确定了棉织物绿色阻燃整理的最佳工艺参数:阻燃剂质量浓度250 g/L,交联剂质量浓度90 g/L,柔软剂质量浓度9 g/L,温度160℃,时间3 min.结果表明,整理后的织物具有良好的阻燃性能和耐水洗性,织物的甲醛含量较低.     

阻燃性丙烯酸酯粘合剂的合成及性能研究

本文研究阻燃性丙烯酸酯粘合剂的制法、性能及试用结果。     

Thermal and Thermo-oxidative Degradation of Flame Retardant High Impact Polystyrene with Triphenyl Phosphate and Novolac Epoxy Resin

Thermal and thermo-oxidative decomposition and decomposition kinetics of flame retardant high impact polystyrene （HIPS） with triphenyl phosphate （TPP） and novolac type epoxy resin （NE） were characterized using thermo-gravimetric experiment. And the flammability was determined by limited oxygen indices （LOI）. The LOI results show that TPP and NE had a good synthetic effect on the flame retardancy of HIPS. Compared with pure HIPS, the LOI values of HIPS/NE and HIPS/TPP only increased by about 5%, and the LOI value of HIPS/TPP/NE reached 42.3%, nearly 23% above that of HIPS. All materials showed one main decomposition step, as radical HIPS scission predominated during anaerobic decomposition. TPP increased the activity energy effectively while NE affected the thermal-oxidative degradation more with the help of the char formation. With both TPP and NE, the materials could have a comparable good result of both thermal and thermal-oxidative degradation, which could contribute to their effect on the flame retardancy.