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.     

新型阻燃环氧固化剂的性能

以9,10-二氢-9氧杂-10-磷杂菲-10氧化物(DOPO)和N-羟甲基丙烯酰胺(NMA)为主要原料,合成固化剂10-(4-羟基-3-(羟甲基)氨基-3-氧代丙基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-NMA)。再将制得的阻燃固化剂DOPO-NMA与E-51环氧树脂固化后得到环氧树脂E-51体系,并对其阻燃性能、热稳定性和力学性能进行研究。研究结果表明,固化体系的拉伸、弯曲及冲击强度随树脂体系中磷质量分数的增加呈下降趋势,而其阻燃等级、极限氧指数和700℃下残炭率随树脂体系中磷质量分数的增加逐渐增加。     

新型含磷固化剂的合成与表征

为了提高环氧树脂的阻燃性,本文以苯基膦酰二氯（PPD）、3-氨基-1,2,4-三氮唑（TA）为原料,四氢呋喃作溶剂合成了新型含磷阻燃固化剂PPDTA,通过红外光谱对该化合物结构进行了分析并确认。同时采用三因素三水平正交实验研究反应时间、反应温度、反应物摩尔比对产率的影响。结果表明,当反应时间10 h,反应温度70 ℃,TA与PPD摩尔比为2.2∶1时,在惰性气氛下PPDTA的产率可达到86.4％。将产物用于固化环氧树脂,通过极限氧指数（LOI）测试和垂直燃烧（UL-94）测试表征材料的阻燃性能,当环氧树脂体系中磷的质量分数达到2.5%时,LOI值达到32.7%,并通过V-0等级,证明材料阻燃性能良好。     

含硝基阻燃剂的合成及其在环氧树脂中的应用

以三苯基膦(PPh3)为原料,制备了一种含硝基的阻燃剂3(3-硝基苯基)膦(NPPh3)。并通过红外光谱(FTIR)、核磁共振(~1HNMR)、热重分析(TG)和红外热失重联用(TG-FTIR)对其结构、热稳定性、热降解行为、成炭能力和热降解产物进行研究。结果表明:NPPh3的初始分解温度为291.2℃,800℃下残炭量达28.16%(N2条件下),相比于原料,硝化后阻燃剂的热稳定性和成炭性能明显提高,热降解主要产物为H_2O、CO_2、CO和芳环。为了在阻燃剂添加量少的情况下,达到良好的阻燃效果,以4,4,–二胺基二苯甲烷(DDM)为固化剂,将NPPh3和9,10–二氢–9–氧杂–10–磷杂菲–10–氧化物(DOPO)复合应用于环氧树脂中,研究其协同阻燃环氧树脂的性能。通过极限氧指数(LOI)和垂直燃烧(UL–94)测试结果可知,阻燃剂总添加量(质量分数)为4.7%,当NPPh3和DOPO的质量比为1∶2时,阻燃环氧树脂的极限氧指数为33.8%,材料通过垂直燃烧测试的V-0级,表现出良好的阻燃性。TG的测试结果表明,燃烧过程中,NPPh3和DOPO之间存在反应,并使环氧树脂的初始分解温度略有降低,热分解速率下降,延缓了树脂在高温下的热降解,提高了高温下材料的成炭量。通过FTIR和扫描电镜(SEM)研究炭层的组成和形貌,结果表明,NPPh3/DOPO/EP通过形成含有–P,–NO2基团的均匀致密炭层结构,在聚合物表面产生有效覆盖,保护基体材料,发挥凝聚相阻燃作用,提高体系的阻燃性能。     

PC/ABS合金的气相/凝聚相协同阻燃作用

分别选用2种不同阻燃机理的磷系阻燃剂,即以凝聚相阻燃为主的间苯二酚-双(二苯基磷酸酯) (RDP)和以气相阻燃为主的磷酸三苯酯(TPP),采用熔融共混法制备聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯共聚物(ABS)阻燃合金. 通过垂直燃烧测试和锥形量热测试探究RDP/TPP复配对合金阻燃性能的影响,通过扫描电子显微镜(SEM)观察燃烧残炭的微观形貌. 以甲基丙烯酸甲酯-丁二烯-苯乙烯(MBS)为相容剂,通过拉伸性能和冲击性能测试探究MBS对阻燃合金的增韧增容效果,并以SEM观察MBS对合金相界面和相形态的影响. 结果表明,RDP的凝聚相阻燃和TPP的气相阻燃作用具有协同效果,可以在PC/ABS合金中促进磷酸盐结构生成,进而有助于体系生成更连续、致密的炭层.     

环氧树脂含硅固化剂的固化动力学研究

采用化学合成方法,利用甲苯-2,4-二异氰酸酯、羟基硅油和二乙胺合成了新型的环氧树脂含硅固化剂,使用红外光谱分析初步确定了合成固化剂的分子结构,通过差示扫描量热法(DSC)分析了合成固化剂/环氧树脂固化体系的固化动力学,并对固化制度进行了优化计算.采用分析固化动力学常用的Kissinger等分析方法,对体系表现活化能和反应级数进行了分析.计算结果表明,体系的表观固化活化能为57.07 kJ/mol,反应级数为n=0.9203.外推法得到体系理论凝胶温度Tgel =366.51 K、最大固化速率温度Tcure=386.44 K、后固化温度Ttreat=397.30 K.     

新型环氧树脂固化剂的性能

采用亲核取代反应合成了新型含有醚酮键的芳香胺固化剂(BADK),并对其结构进行了表征。选用BADK作为固化剂,对含有联苯结构的环氧树脂和通用型环氧树脂E-51的固化条件、固化物耐热性和吸湿性进行了研究。实验结果表明:新型固化剂的使用提高了通用型环氧树脂E-51的热性能;含联苯结构的环氧树脂固化物与E-51相比,无论是热性能还是耐湿性都有很大的提高。     

无卤阻燃含磷环氧树脂覆铜板的制备

以玻璃纤维布作基体,双氰胺作固化剂、2-甲基咪唑作固化促进剂,研究了制备无卤阻燃含磷环氧树脂覆铜板的阻燃胶料配方.实验结果表明,覆铜板的最佳配方为:磷的质量分数为2.5%的环氧树脂(E-2145)159.8 g,双氰胺4 g,2-甲基咪唑0.06 g,氢氧化铝占体系质量的百分数为20%,丙酮1.2 g.     

胺类环氧树脂固化剂改性研究进展

鉴于使用传统固化剂制备的环氧树脂材料存在力学性能及热性能不佳的问题,使用改性胺类固化剂,可以有效提升环氧树脂体系的综合性能。本文重点对改性胺类固化剂结构及树脂性能提升机理等方面进行了阐述。使用树枝状结构固化剂可以有效提高环氧树脂体系力学性能尤其是树脂韧性;使用苯环改性的固化剂可以很好地提升环氧树脂体系耐热性;而将杂原子改性固化剂引入环氧树脂体系后,树脂在阻燃性大幅提升的同时依旧可以保持较好的力学强度。最后,结合当前环氧树脂使用中的实际问题,对胺类固化剂今后的研究方向进行了展望。     

环氧树脂弹性体的制备及性能研究

通过分子结构设计,采用长柔性链段的端氨基聚醚与端氨基聚氨酯共同作为固化剂固化环氧树脂,得到了系列环氧树脂弹性体.并对协同固化体系的增韧效果进行了分析,研究了固化物力学性能及热性能的变化规律.研究表明,环氧树脂弹性体冲击韧性可达到52.1 KJ/m2,断裂伸长率可达到160%,并具有良好的综合性能.     

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%.     

棉用无醛阻燃剂的合成及其整理工艺

以亚磷酸和乙二醇为反应原料合成了一种羟基磷酸酯型低聚物阻燃剂.该阻燃剂与交联剂丁烷四羧酸和催化剂次亚磷酸钠构成了阻燃整理体系,用于织物整理,得到无甲醛耐久阻燃整理棉织物,合成和应用时不需要特殊的工艺和设备.探讨了阻燃剂用量,交联剂用量,焙烘温度,焙烘时间对阻燃效果的影响.对整理织物的热解质量分析结果表明,该阻燃剂可大大降低棉织物的热裂解温度,阻燃效果具有一定的耐久性,可满足多领域对纺织品的阻燃要求.得到纯棉织物最佳整理工艺:阻燃剂用量400 g/L,交联剂用量80 g/L,焙烘温度180℃,焙烘时间3 min.整理后织物的损毁长度为123 mm,具有较好的阻燃性和耐久性.     

Synthesis,characterization and flame-retardant properties of epoxy resins and AACHH composites

Flame retardant epoxy resins were prepared by a simple mixed method using ammonium aluminum carbonate hydroxy hydrate (AACHH) as a halogen-free flame retardant. The prepared samples were characterized by X-ray diffraction, thermogravimetric and differential scanning calorimetry, scanning electron microscope and limiting oxygen index(LOI) experiments. Effects of AACHH content on LOI of epoxy resins/AACHH composite and flame retardant mechanism were investigated and discussed. Results show that AACHH exhibites excellent flame-retardant properties in epoxy resin(EP). When the content of AACHH was 47.4%, the LOI of EP reached 32.2%. Moreover, the initial and terminal decomposition temperature of EP increased by 48°C and 40 °C, respectively. The flame retarded mechanism of AACHH is due to the synergic flame retardant effects of diluting, cooling, decomposition resisting and obstructing.     

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.     

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)     

Influence of aliphatic epoxy monomer on the blowing-out effect in the flame retardant epoxy resins

An aliphatic epoxy monomer "polypropyleneglycol-diglycidylether (PPGDGE, YF878)" is loaded in the epoxy resins (EP) to evaluate the influence of epoxy structure on the blowing-out effect, which is caused by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and octaphenyl silsesquioxane (OPS). The flame retarding properties of these EP composites were tested using the LOI and UL-94 procedures. The pyrolytic gases produced and the thermal stability of the EP composites with different flame retardants were detected by TGA-FTIR in air. The negative effect of YF878 was detected from the TTI, HRR, and p-HRR results after the cone calorimeter test. The char produced by the EP composites after the cone calorimeter test was investigated by FTIR. It is proposed that the aliphatic chain of the YF878 is easy to break down and produce combustible gases, so it does not easily form a crosslinked structure in the condensed phase. These results are very helpful for investigation of the conditions under which the blowing-out effect in epoxy resins can be caused by synergy of phosphorous and silicon.     

COMPARISON OF THE E44 EPOXY RESINS IN DIFFERENT CONTENTS OF CURING AGENT BY MICROWAVE AND THERMAL CURING METHODS

This paper discusses the fundamental principle of microwave heating, and based on the advantages of microwave heating, use maleic anhydride as curing agent. The technology of microwave curing E44 epoxy resins is investigated, the mechanical properties of cured epoxy resin samples in different contents of curbing agent by microwave and thermal curing methods are measured respectively, and then some experimental results for which are obtained. At last, this paper analyses why microwave curing can improve mechanical property of epoxy resin.     

植酸铜/聚丙烯腈改性膜的制备及阻燃性能

针对聚丙烯腈高易燃性且产生大量有毒气体的缺点,利用植酸铜阻燃改性聚丙烯腈.首先选取植酸与乙酸铜制备植酸铜螯合物,并利用共混法制备植酸铜/聚丙烯腈改性膜;采用燃烧测试、X射线荧光光谱仪、傅里叶红外光谱和热重分析等方法分别对改性膜的阻燃性能、元素组成、结构和热稳定性能进行研究,探讨植酸铜在聚丙烯腈膜燃烧时的阻燃机理.结果表...     

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.