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%.     

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.     

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.     

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.     

无卤阻燃ABS体系的性能

采用氧化锌（ZnO）、二氧化硅（SiO2）包覆改性ZnO及微胶囊红磷（MRP）／酚醛环氧树脂（NE）制备了无卤阻燃ABS．探讨ZnO及SiO2包覆改性ZnO的阻燃增效作用及协同作用机理．IR分析结果表明,包覆改性后在ZnO表面形成了Si-O-Zn键,表明在ZnO表面形成了SiO2包覆层．实验结果表明,ZnO及其SiO2包覆的ZnO可显著提高ABS材料的阻燃性能,并且对ABS的力学性能影响不大,当ZnO的添加量为5％时,阻燃ABS的极限氧指数（LOI）达到36％;当添加5％表面SiO2包覆量为5％的改性ZnO时,阻燃ABS的LOI达到41％．阻燃ABS试样垂直燃烧实验均可达到V-0级别．TG分析结果表明,ZnO及SiO2表面包覆改性ZnO可以促进材料成炭,增加残炭含量,提高ABS的阻燃性能     

无卤阻燃增韧尼龙1313/POE/MCA复合材料的研究

以马来酸酐功能化的乙烯/辛烯共聚物(POE-g-MA)为弹性体,三聚氰胺氰尿酸盐(MCA)为阻燃剂,在SHJ-36双螺杆挤出机中制备了无卤阻燃增韧尼龙1313/POE/MCA复合材料.测定了无卤阻燃尼龙1313/POE/MCA复合材料的极限氧指数(LO I),用扫描电镜(SEM)观察了经锥形量热仪燃烧的该复合材料残炭的形貌.实验结果表明,当POE-g-MA,MCA的质量分数分别为15%和12%时,复合材料的LO I为32%,垂直燃烧通过UL94V-0级,缺口冲击强度是纯尼龙1313的5.5倍,实现了在不使用卤元素阻燃剂并且保证尼龙1313/POE/MCA复合材料力学性能的前提下,大幅度提高该材料阻燃性能的要求.     

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。     

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)     

氧化锌与膨胀型阻燃剂对聚丙烯的协效阻燃

采用磷酸、季戊四醇和三聚氰胺为原料合成了一种新型膨胀型阻燃剂(IFR)。并以IFR为阻燃剂,氧化锌(ZnO)为协效阻燃剂,聚丙烯(PP)为基体树脂制备了膨胀型阻燃PP复合材料,重点研究ZnO与IFR之间的协效阻燃作用。采用氧指数测定仪、UL-94测定仪和锥形量热仪等手段研究阻燃PP复合材料的燃烧性能,用动态傅里叶变换红外光谱(FTIR)研究阻燃PP复合材料在不同温度下凝聚相的结构变化,初步揭示其热降解特性。实验结果表明:ZnO与IFR之间存在明显的协效阻燃效果;复合材料在240～330℃时,结构变化最剧烈;ZnO添加质量分数为1.6%时,炭层完整性最好,热释放速率峰值最低,降低幅度可达80%,UL-94为V-0级;ZnO添加质量分数为3.2%时,氧指数(LOI)最大为25.6%,UL-94为V-0级。     

可膨胀石墨在膨胀阻燃体系中协同阻燃作用的研究

采用氧指数(LOI)、扫描电镜(SEM)、热重分析(TG)等技术手段对可膨胀石墨(EG)与膨胀型阻燃剂(IFR)协同阻燃线性低密度聚乙烯(LLDPE)体系进行了研究.结果表明,EG与IFR复配,体系氧指数明显提高,其热稳定性增强,热降解速率降低,残炭率提高,燃烧炭层连续致密,EG与IFR具有很好的协同阻燃作用.热分析及扫描电镜结果证明,EG与IFR的协同阻燃作用机理的关键在于凝聚相成炭.     

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)     

超支化聚膦酸酯改性环氧树脂的研究

以苯膦酰二氯（BPOD）为A2单体,三羟甲基丙烷（TMP）为B3单体,采用熔融缩聚法合成了超支化聚膦酸酯.利用动态力学热分析（DMA）、热失重分析（TGA）对环氧树脂固化体系的热性能进行了表征,研究了超支化聚膦酸酯的用量对环氧树脂固化体系的力学性能和阻燃性的影响.结果表明：加入15%的超支化聚膦酸酯,环氧树脂固化体系的拉伸强度和冲击强度分别提高了11.26%和306%,氧指数从22提高到33,说明超支化聚膦酸酯具有良好的阻燃性.     

热塑性聚烯烃弹性体/磷酸二氢铵阻燃复合体系的性能

以热塑性聚烯烃弹性体(TPO)为基体,设计了以磷酸二氢铵(ADP)同时为气源、酸源阻燃剂的TPO/ADP阻燃复合体系。重点研究了该体系的阻燃性能和膨胀层结构,并研究了复合阻燃体系的力学性能。结果表明,ADP使体系的LOI数值和垂直燃烧测试等级得到提高。当ADP用量达到70份时,LOI达到25.9%,垂直燃烧测试达到FV-0级,体系成为难燃材料。光学显微镜(OM)分析表明,ADP是良好的气源,能够促进体系生成多孔的膨胀层,并且体系产生了具有一定阻隔作用的炭层结构。力学性能研究表明,ADP的加入使复合阻燃体系的拉伸强度得到一定提高,但断裂伸长率有所降低。当ADP的加入量为80份时,复合体系的断裂伸长率为300%,仍能够满足建筑防水材料要求。     

一种无卤阻燃乙烯-醋酸乙烯酯共聚物的热分解动力学研究

通过极限氧指数法（LOI）和垂直燃烧（UL-94）测试考察了一种无卤阻燃乙烯-醋酸乙烯酯共聚物（EVA）的阻燃性能;利用热重分析法（TG）研究了纯EVA及阻燃EVA在不同升温速率下的热稳定性及热分解动力学,并采用Kissinger及Flynn-Wall-Ozawa方法计算了纯EVA和阻燃EVA的热分解表观活化能。结果表明,添加40%复合膨胀阻燃剂的EVA复合材料,极限氧指数达到28.6%,UL-94测试达到V-0级,残炭量相对纯EVA明显提高;随着升温速率增大,EVA和阻燃EVA的起始失重温度和各阶段的失重峰温均向高温方向移动;二者在第一阶段的热分解活化能均低于第二阶段,阻燃剂的添加使EVA的最大失重速率明显降低,热分解表观活化能提高,增强了材料的热稳定性和阻燃性。     

含哒嗪酮结构生物基环氧树脂本征阻燃机制研究

通过树脂烧蚀实验和扫描电子显微镜、X射线光电子能谱仪、热重-红外同步热分析仪等表征手段探究了含哒嗪酮结构的生物基环氧树脂的本征阻燃机制。结果表明,相对于目前最常用的石油基双酚A型环氧树脂,所制备的生物基环氧树脂在燃烧时更易形成大量膨胀型的炭层结构,同时释放出大量CO₂和NH₃等不可燃性气体和更少的可燃性气体;含哒嗪酮结构的本征阻燃生物基环氧树脂呈现出凝聚相-气相协同阻燃机理。本研究为构筑高性能的本征阻燃环氧树脂提供了新的思路。     

热塑性聚烯烃弹性体/磷酸二氢铵阻燃复合体系的性能

以热塑性聚烯烃弹性体(TPO)为基体,设计了以磷酸二氢铵(ADP)同时为气源、酸源阻燃剂的TPO/ADP阻燃复合体系。重点研究了该体系的阻燃性能和膨胀层结构,并研究了复合阻燃体系的力学性能。结果表明,ADP使体系的LOI数值和垂直燃烧测试等级得到提高。当ADP用量达到70份时,LOI达到25.9%,垂直燃烧测试达到FV-0级,体系成为难燃材料。光学显微镜(OM)分析表明,ADP是良好的气源,能够促进体系生成多孔的膨胀层,并且体系产生了具有一定阻隔作用的炭层结构。力学性能研究表明,ADP的加入使复合阻燃体系的拉伸强度得到一定提高,但断裂伸长率有所降低。当ADP的加入量为80份时,复合体系的断裂伸长率为300%,仍能够满足建筑防水材料要求。     

两种溴阻燃剂对聚乙烯阻燃性能的研究

讨论了十溴二苯醚(DBDPO)和八溴二苯醚(OBDPO)对低密度聚乙烯(LDPE)的阻燃性能和拉伸强度的影响。通过热分析法(DSC)和热重法(TG)比较了DBDPO和OBDPO分解行为的差异。结果表明，DBDPO对LDPE拉伸强度下降的影响比OBDPO大。极限氧指数(LOI)测试表明：Sb2O3能够与溴阻燃剂产生协同作用，显著增强阻燃剂的阻燃性能；DBDPO对LDPE的阻燃性能优于OBDPO；用DBDPO为阻燃剂时，其最佳用量约为12％(质量分数)，DBDPO与Sb2O3的最佳比例是3：1；以OBDPO为阻燃剂时，最佳用量约为16％，与Sb2O3的最佳比例是2．5：1。     

磷系阻燃聚酯纤维的研制

采用共混聚合法制备磷系阻燃聚酯．重点考查了阻燃剂的加入量对切片及其纤维的热性能、物化性能、可纺性和阻燃性能的影响通过聚合、纺丝、织造和阻燃性能的测试,表明该制备工艺可行,可纺性良好;添加3％～5％的阻燃剂就可获得较高的阻燃效果,织物的抗氧指数［LOI］可达35％．     

Decomposition behavior and decomposition products of epoxy resin cured with MeHHPA in near-critical water

A kind of chemical method that used water as the liquid reaction medium to decompose epoxy resin was studied. The thermosetting epoxy resin was decomposed successfully under the condition of near-critical water. The decomposition rate of epoxy resin raised rapidly as the reaction time and reaction temperature increased. The decomposition reaction products were characterized by infra-red spectra and gas chromatography-mass spectrometry. The phenol, isopropylphenol, 4, 4′-(1-methylethylidene) bis-phenol were found as the main compounds in liquid products, which were common monomers from epoxy resin. When reaction was carried out at the temperature of 260 °C–300 °C, the decomposition mechanism of epoxy resin was envisaged as the ether and ester bonds cracking.