PC/ABS及PC/ABS/PE-g-MAH共混体系相容性的研究

研究了聚碳酸酯与ＡＢＳ（ＰＣ／ＡＢＳ）及ＰＣ／ＡＢＳ与马来酸酐接枝聚乙烯共聚物（ＰＣ／ＡＢＳ／ＰＥ－ｇ－ＭＡＨ）共混体系的力学性能和应力开裂性能。用ＤＳＣ和ＳＥＭ研究了共混体系的相容性。结果表明：ＡＢＳ的加入能提高ＰＣ的冲击强度,ＡＢＳ的含量及品种影响ＰＣ／ＡＢＳ合金的力学性能,ＡＢＳ能提高ＰＣ的耐溶剂应力开裂性能。ＰＣ／ＡＢＳ／ＰＥ－ｇ－ＭＡＨ共混体系的力学性能和相容性优于ＰＣ／ＡＢＳ共混体系,     

含磷/氮/硫协效阻燃剂的合成及对环氧树脂的阻燃作用

本文以DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)、苯甲醛和4,4’-二氨基二苯砜(DDS)为原料,一锅法合成了含磷、氮、硫的化合物PNS。以PNS为阻燃剂,双酚A型树脂DGEBA为基材,DDS为环氧固化剂,制备了阻燃环氧固化物PNS/DGEBA/DDS,研究了PNS对DGEBA阻燃性能的影响,并与商业化有机磷阻燃剂DOPO作对比,同时初步探讨了PNS的阻燃机理。研究结果表明,PNS呈现磷/氮/硫协效阻燃作用,具有比DOPO更优异的残炭生产促进作用、抑烟效果和阻燃作用。在体系磷含量为1.5 wt%时,PNS-1.5/DGEBA/DDS的LOI值高达33.2%,并获UL 94最高阻燃级别V-0级,总烟释放量相较于DOPO-1.5/DGEBA/DDS降低15.4%,DGEBA/DDS降低2.86%,呈现良好的抑烟性能。     

PC/ABS共混物的PGC-MS定量分析

采用裂解/气相色谱-质谱联用方法(PGC-MS)对制备的一系列已知配比的PC/ABS共混物进行分析。实验比较了650、750℃裂解温度下共混物的裂解质谱总离子流图,选择PC/ABS共混物的快速鉴定的裂解温度为750℃;通过对已知PC/ABS配比的共混物的特征裂解碎片进行定量分析,发现当共混物中ABS和PC的质量比不大于20∶100时,特征裂解碎片苯乙烯与苯酚的峰面积之比与共混物中ABS/PC的配比呈线性关系,该现象可作为PC/ABS共混物定量分析的依据。     

红外光谱法对PC/ABS材料共混比例进行半定量

采集不同PC/ABS(聚碳酸酯/丙烯腈-丁二烯-苯乙烯共聚物)共混比例样品的红外谱图形成学习集。将学习集相同共混比样品的红外谱图平均后,得到该共混比样品红外谱图的特征。将待测样品与平均后的特征进行匹配,进行分类从而达到半定量的目的。通过测试未知样品,对模型的准确性进行了验证,实际分析结果表明,该方法可以准确对不同共混比例的PC/ABS样品进行分类。     

新型含磷阻燃剂DOPO-PPO的合成及其阻燃性能

以苯基磷酰二氯,对羟基苯甲醛及9,10-二氢-9-氧杂-10-磷杂菲(DOPO)为原料,合成了一种新型含磷阻燃剂——二[4-(次甲基-羟基-磷杂菲)苯氧基]苯基氧化磷(DOPO-PPO),其结构经1H NMR和IR表征。通过TGA和DTG研究了DOPO-PPO的热稳定性,热降解行为及成炭性能。结果表明:DOPO-PPO的起始热分解温度为210℃,在700℃时残炭为30.4%。以环氧树脂为基材,DOPO-PPO为阻燃剂,二氨基二苯硫砜为固化剂,制备了阻燃环氧树脂(3)。通过极限氧指数(LOI)和垂直燃烧(UL-94)测试了3的阻燃性能。结果表明:当DOPOPPO的添加量为12.0%(质量百分数,即312)时,阻燃级别为V-0级,LOI为34.0%。     

阻燃剂及材料的阻燃处理

阻燃剂是能够保护材料不着火或使火焰难以蔓延的化学物质。介绍了常见阻燃剂的种类、阻燃机理、材料的阻燃处理及新型阻燃剂的发展,以增强人们对阻燃技术领域的认识和了解。     

含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用

采用原位模板法,以六氯环三磷腈(HCCP)和二羟基二苯砜(BPS)为原料合成了一种环状交联型不溶不熔的磷腈大分子——聚环三磷腈-二羟基二苯砜(PZS)微纳米管,研究了PZS对环氧树脂(EP)的阻燃作用及阻燃机理.利用红外光谱(FTIR)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)对PZS微纳米管进行了表征;采用热重分析(TG)考察了EP/PZS阻燃材料的热稳定性,并通过极限氧指数(LOI)和微型量热分析(MCC)测试了EP/PZS的阻燃性能.热降解实验结果表明,PZS微纳米管的加入使环氧树脂热降解温度降低,但残炭率显著提高.PZS微纳米管可以显著提高环氧树脂的阻燃性能,当阻燃剂添加量为5%时,环氧树脂的残炭率提高了46%,热释放速率峰值降低了约40%;LOI值从纯环氧树脂的26.0%提高到了30.6%.PZS微纳米管的加入还增强了环氧树脂的力学强度.阻燃性能的显著提高和力学性能的改善归因于PZS微纳米管在环氧树脂基体中的良好分散,以及燃烧炭化过程中生成的石墨化程度较高的类石墨烯结构的残炭,具有较高的抗氧化能力.研究结果表明,PZS微纳米管是一种优良、高效的具有潜在应用价值的阻燃剂.     

基于固体分散剂制样的裂解/气相色谱-质谱联用定量测定PC/ABS共混物比例

建立了以二氧化硅为分散剂制样的裂解/气相色谱-质谱联用测定聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯共聚物(ABS)共混物比例的分析方法。将样品冷冻破碎成粉末后,以二氧化硅为固体分散剂与样品混合后进样,在600℃裂解温度下裂解得到相应的裂解色谱图,选择PC/ABS共混物裂解色谱图上ABS的特征裂解产物——苯乙烯为定量峰,计算PC/ABS共混物中ABS的质量分数,再进一步推算PC的质量分数。以二氧化硅为固体分散剂制备系列已知含量的PC/ABS分散体,以ABS含量为横坐标,对应的苯乙烯峰面积为纵坐标绘制校准曲线,ABS在分散体中含量在0.06～20 g/kg(对应PC∶ABS=99.7∶0.30～0∶100)范围内的线性良好,相关系数(r²)为0.994,以5倍信噪比(S/N=5)计算得到ABS的检出限为0.06 g/kg(对应的PC∶ABS比例为99.7∶0.30)。采用该方法对已知混合比例的PC/ABS样品进行测定,所得结果的回收率为95.3%～103%,相对标准偏差(RSDs,n=3)为1.1%～3.8%。该方法简便、准确度高,适用于PC/ABS共混物全范围比例的...     

ABS树脂的阻燃化研究：I.添加小分子阻燃剂

系统地研究了ＦＲ－ＴＮＸ、Ｓｂ２Ｏ３、Ｍｇ（ＯＨ）２、Ａｌ（ＯＨ）３等小分子阻燃剂对ＡＢＳ树脂的阻燃效果及其协同效应。结果表明，单一组燃剂的作用不太明显；锑卤复配可取得较好的协同效应；通过测定冲击强度和拉伸性能，考察了阻燃剂对ＡＢＳ树脂的机械性能的影响，并通过ＤＭＡ进一步分析了阻燃剂与树脂的相容性；通过ＴＧＡ等热分析手段探讨了小分子阻燃剂在凝聚相的阻燃行为与作用机理。     

ABS树脂的阻燃化研究Ⅰ.添加小分子阻燃剂

系统地研究了ＦＲ－ＴＮＸ、Ｓｂ２Ｏ３、Ｍｇ（ＯＨ）２、Ａｌ（ＯＨ）３等小分子阻燃剂对ＡＢＳ树脂的阻燃效果及其协同效应。结果表明，单一阻燃剂的作用不太明显；锑卤复配可取得较好的协同效应；通过测定冲击强度和拉伸性能，考察了阻燃剂对ＡＢＳ树脂的机械性能的影响，并通过ＤＭＡ进一步分析了阻燃剂与树脂的相容性；通过ＴＧＡ等热分析手段探讨了小分子阻燃剂在凝聚相的阻燃行为与作用机理。     

PP/尼龙66/聚碳酸酯/ABS共混高聚物的SEM样品制作

讨论了PP／尼龙66／聚碳酸酯／ABS共混高聚物的扫描电子显微镜样品制作中存在的问题,通过实验,探讨了出该材料最佳的样品制作条件。     

新型磷-氮有机金属阻燃剂的合成及其热稳定性

以γ-氨丙基三乙氧基硅烷(1)和二苯基氯化膦(2)为原料,经取代反应制得N-(二苯基膦基)-1,1-二苯基-N-［3-(三乙氧基甲硅烷)丙基］膦氮配体(3); 3与六水合氯化镍(4)反应合成了一种新型的磷-氮有机金属阻燃剂(5),其结构经¹H NMR, ³¹P NMR和FT-IR表征。研究了物料比［r=n(2) : n(1)］、溶剂、反应时间和反应温度对3收率的影响。结果表明：在最佳反应条件［二氯甲烷为溶剂,1 19 mmol, r=2.3,于25 ℃反应14 h］下,3收率89.5%。 TGA测试结果表明：5的初始分解温度为252 ℃, 700 ℃残炭为31.9%。     

酸碱处理蒙脱土与磷酸酯阻燃剂复配阻燃PC/ABS合金

采用酸碱处理法对蒙脱土进行有机化改性, 再将酸碱处理的蒙脱土与磷酸酯阻燃剂复配, 作为聚碳酸酯/丙烯腈-丁二烯-苯乙烯三元共聚物(PC/ABS)合金的阻燃体系, 并表征了酸碱处理蒙脱土对合金的热稳定性和阻燃性能. 结果表明, 间苯二酚双(二苯基磷酸酯)改性的蒙脱土(BDP-MMT)使阻燃PC/ABS合金的起始分解温度降低, 而酸碱处理蒙脱土却使合金的起始分解温度有所提高; BDP-MMT的加入会恶化碳层的阻隔性能, 而酸碱处理蒙脱土却可以增加碳层的稳定性, 使第二热释放峰值出现的时间延迟, 且适合的酸浓度处理蒙脱土可以使合金通过UL-94 V-0级检验.     

新型大分子磷氮阻燃剂的合成及其在阻燃聚碳酸酯中的应用

以苯基膦酰二氯和哌嗪为原料合成了一种新型大分子含磷氮阻燃剂——聚苯基磷酰哌嗪(1),其结构经1H NMR,31P NMR和IR表征。对阻燃聚碳酸酯(2)的极限氧指数(LOI)测试结果表明:添加7%的1时,2的LOI值为34.8%。     

Flame retardancy mechanisms of phosphorus‐containing polyhedral oligomeric silsesquioxane (DOPO‐POSS) in polycarbonate/acrylonitrile‐butadiene‐styrene blends

The flame retardancy mechanisms of a novel polyhedral oligomeric silsesquioxane containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO‐POSS) in polycarbonate/acrylonitrile‐butadiene‐styrene (PC/ABS) blends are discussed. The thermal stability of PC/ABS composites with different DOPO‐POSS loadings are investigated by TGA and the enhancement of the thermal stability could be found at high temperature range. Their fire behavior is tested by the LOI, UL‐94, and cone calorimeter. Excellent flame retardancy of PC/ABS composites have been discovered with 10 wt% DOPO‐POSS loading. TGA‐FTIR, FTIR, XPS, and SEM, respectively, are used to characterize the gaseous products and the condensed residue in thermal decomposition, and the micro‐structure of the chars from cone calorimeter tests. The decomposition of PC/ABS with 10 wt% DOPO‐POSS shows significant changes compared with PC/ABS by TGA, FTIR, TGA‐FTIR, and XPS analysis. The enhancement of the thermal‐oxidative stability of PC/ABS with DOPO‐POSS is attributed to the interaction between DOPO‐POSS and PC/ABS at high temperature, which might be the key for improvement of the flame retardancy. Copyright © 2011 John Wiley & Sons, Ltd.     

Experimental investigation and modeling of the mechanical behavior of PC/ABS during monotonic and cyclic loading

The purpose of this work is to characterize the mechanical behavior of blends of polycarbonate (PC) and acrylonitrile-butadiene-styrene (ABS) during monotonic and cyclic loading. Compression experiments were performed using a SHIMADZU universal testing machine (10⁻⁴ to 10⁻² s⁻¹) and a split Hopkinson pressure bar (1600–5000 s⁻¹), with, the test temperatures ranging from 293 to 353 K. The influence of the rate and temperature on the deformation of PC/ABS is discussed in detail. Based on the investigation of numerous constitutive models, a phenomenological model called DSGZ was chosen to describe the compression behavior of PC/ABS. This model could not accurately reproduce the deformation of polymers at high strain rates when utilizing the same material coefficients for the low and high strain–rate deformations. In addition, this model was unable to capture the deformation features during unloading and subsequent reloading when adopting the original stress–strain updating algorithm. Hence, some improvements to the model have been implemented to better predict the deformation. Finally, the model predictions are shown to be consistent with the experimental results.     

‘Tail’ phenomenon and fatigue crack propagation of PC/ABS alloy

The fatigue crack propagation (FCP) behavior of the alloy of polycarbonate (PC) and acrylonitrile-butadiene-styrene (PC/ABS) is experimentally investigated in this paper. An improved compliance method is employed to measure the fatigue crack length and optical and scanning electron microscopes (SEM) are used to observe the features of crack tip deformation in situ. ‘Tail’ phenomenon has been observed at the initial stage of fatigue for each specimen, which is regarded as a reflection of the transition process of accumulation of damage and plastic deformation during FCP. The law of FCP from low to high crack growth rate (10⁻⁶-10⁻³ mm/cycle) is obtained and described with Paris law. Porous or dimple features govern the fatigue crack surfaces and coarse features have been seen on the crack surfaces with higher crack growth rate, while smooth features have been observed on the crack surfaces with lower crack growth rate. A stretched band appears when the crack growth transforms from lower to higher region of FCP rate.     

Synthesis of a Novel Phosphorus-Containing Curing Agent and Its Effects on the Flame Retardancy,and Thermal Stability of Epoxy Resins

Russian Journal of Applied Chemistry - A novel curing agent containing phosphorus and carboxyl group compound diphenyl(2,3-dicarboxylpropyl)phosphine oxide (DPDCPPO) was synthesized and used as a...     

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%。