阻燃ABS及其耐热性研究

研究了常用阻燃体系的ABS在力学性能、耐热性等方面的差异，并就常用增韧剂、增强剂对阻燃ABS性能的影响进行了探讨。结果表明，十溴联苯醚-Sb2O3体系阻燃ABS用量最少：八溴联苯醚-Sb2O3体系阻燃ABS具有较优的冲击强度；四溴双酚A-Sb2O3体系阻燃ABS具有较好的熔体流动性能：耐热性则以乙撑双四溴邻苯二甲酰亚胺阻燃ABS最好；增韧剂的加入使阻燃ABS的冲击强度提高，但耐热性降低：在阻燃ABS中加入玻璃纤维和CaSiO3可较大幅度地提高阻燃ABS的耐热性。     

2,4,6-三溴苯胺对环氧树脂固化物阻燃耐热性的影响

用氧指数 (LOI) ,TG法测定研究了 2 ,4,6-三溴苯胺 (TBA)对环氧树脂酸酐固化物阻燃耐热性的影响 ,结果表明 TBA能较好地阻燃树脂固化物 ,TBA与 Sb2 O3 和磷酸三苯酯 (TPP)配用时具有阻燃协同效应 ,且对环氧树脂酸酐固化物的热稳定性影响较小。     

阻燃ABS及其耐热性研究

比较了几种常用阻燃体系阻燃(丙烯腈/丁二烯/苯乙烯)共聚物(ABS)的力学性能、耐热性能，并就常用增韧剂、增强剂对阻燃ABS性能的影响进行了探讨。结果表明，十溴联苯醚-Sb2O3体系阻燃ABS的用量最少；八溴联苯醚-Sb2O3体系阻燃ABS具有较高的冲击强度；四溴双酚A-Sb2O3体系阻燃ABS具有较好的熔体流动性能；耐热性则以乙撑双四溴邻苯二甲酰亚胺阻燃ABS最好；增韧剂的加入使阻燃ABS的冲击强度提高，但耐热性降低；在阻燃ABS中加入玻璃纤维和硅灰石可较大幅度地提高阻燃ABS的耐热性。     

纳米Sb2O3对聚丙烯阻燃性能的影响

在四溴醚[四溴双酚A-双(2-烯丙基)醚]及八溴醚[四溴双酚A-双(2，3-二溴丙基)醚]的协同作用下，研究了三氧化二锑(Sb2O3)纳米颗粒对聚丙烯阻燃性能的影响。分别使用热重分析法、氧指数法和垂直燃烧法评价了以上阻燃剂的阻燃性能。研究结果表明纳米Sb2O3颗粒的加入，较好地提高了聚丙烯的阻燃性能，相对于普通Sb2O3颗粒，其初始分解温度最大提高27．9℃，氧指数增加1．8％；阻燃级别由V-1上升至V-0。通过热重分析法与垂直燃烧法、氧指数法对塑料阻燃性能的一致评价，表明热重分析是一种评价阻燃材料的较简便直观的方法。     

八溴二苯乙烷及EG对长玻纤增强PP性能的影响

以八溴二苯乙烷(ODOPE)或十溴二苯乙烷(DBDPE)及三氧化二锑(Sb2O3)为阻燃剂,采用熔体浸渍工艺制备阻燃长玻璃纤维增强PP(LGFPP),研究了这两种溴系阻燃剂对阻燃LGFPP的阻燃性能和物理力学性能的影响,并研究了可膨胀石墨(EG)在ODOPE阻燃LGFPP的中的协效效果。结果表明,ODOPE对于LGFPP的阻燃效率高于相同含量下的DBDPE,添加质量分数为14%的ODOPE的阻燃LGFPP垂直燃烧等级为V–0级,极限氧指数(LOI)为23.6%。扫描电子显微镜分析表明,ODOPE均匀分散于阻燃LGFPP树脂基体中,而DBDPE在基体中团聚明显。ODOPE阻燃LGFPP的熔体流动速率(MFR)、拉伸强度、弯曲强度及悬臂梁缺口冲击强度均高于DBDPE阻燃的LGFPP,且其MFR随着ODOPE含量的增加而提高。EG可以略微提升ODOPE阻燃LGFPP的LOI,含3%EG的ODOPE阻燃LGFPP的LOI最高,为24.7%,垂直燃烧等级为V–0级。EG与ODOPE–Sb2O3体系的协效阻燃效果较低,且降低了LGFPP的MFR和力学性能。     

2,4,6-三溴苯胺对环氧固化物阻燃耐热性的影响

用氧指数(LOI)、TG法研究了2,4,6 三溴苯胺(TBA)对环氧树脂酸酐固化物阻燃耐热性的影响,结果表明TBA有较好的阻燃效果,其与Sb2O3和磷酸三苯酯(TPP)配用时具有协同阻燃效应,且对环氧树脂酸酐固化物的热稳定性影响较小。     

溴系协效阻燃体系对PP阻燃和生烟性能的影响

利用极限氧指数、锥形量热仪和热重分析等方法对比研究了溴–锑和溴–铋协效阻燃体系对聚丙烯(PP)阻燃性能和生烟性能的影响。结果表明,八溴醚–氧化铋和八溴醚–三氧化二锑阻燃体系能明显提高PP的阻燃性能;当溴–锑和溴–铋阻燃剂的质量比为3∶1时,协同阻燃效果最佳,其中八溴醚–三氧化二锑和八溴醚–氧化铋的协同效率值分别为3.96和4.32。与纯PP相比,八溴醚的加入明显增大了PP的生烟速率(SPR)和总生烟量(TSR),但溴–铋阻燃PP的SPR峰值和TSR相比于溴–锑阻燃PP却分别下降了14.94%和14.32%。热重分析表明,溴–铋阻燃体系相比于溴–锑阻燃体系能较早地释放出HBr,并更大程度地降低PP的热裂解速率,从而更有效地提高溴系阻燃PP的协同阻燃效率并降低生烟量。     

紫外光对阻燃聚丙烯阻燃性能的影响研究

研究了三种不同阻燃剂的紫外光稳定性，并采用三种实验方案来分析阻燃聚丙烯(PP)紫外光照射后阻燃性能下降的原因。实验表明，膨胀型阻燃剂的光稳定性最好，八溴醚次之，十溴联苯醚的光稳定性最差；紫外吸收光谱发现十溴联苯醚比八溴醚具有更强的紫外光吸收作用，溴系阻燃剂光照后阻燃效率下降是由于阻燃剂发生了光分解反应，溴从阻燃剂基体中分离，形成自由基，降低了阻燃剂中的溴含量。阻燃聚丙烯紫外光照射后阻燃性能下降是由阻燃剂的光分解和聚丙烯基体树脂的光氧化降解两方面的因素造成的。     

不同阻燃体系PBT工程塑料的热稳定性研究

对四种不同种类阻燃体系的聚对苯二甲酸丁二醇酯(PBT)工程塑料进行热失重分析和高温热老化实验,通过失重率、老化之后色变和拉伸强度保持率来比较不同种类阻燃剂对PBT的耐热性影响。结果表明,不同种类阻燃剂对PBT工程塑料的耐热性能影响差别较大,十溴二苯乙烷阻燃PBT的加工耐热性和老化耐热性优于溴化聚苯乙烯阻燃PBT,溴化聚苯乙烯阻燃PBT优于溴化聚碳酸酯阻燃PBT,溴化聚碳酸酯阻燃优于溴化环氧树脂阻燃PBT。     

溴-锑阻燃体系对β-PP结晶和阻燃性能的影响

通过添加喹吖酮β成核剂和溴-锑阻燃体系获得阻燃β晶型聚丙烯(β-PP)。运用差示扫描量热仪和锥形量热仪研究了溴-锑阻燃体系对β-PP结晶性能和阻燃性能的影响。结果表明:低含量的八溴醚对β晶有较强的抑制作用,随着八溴醚含量的增大,其对β晶的抑制作用减弱,并在质量分数14%以上转变为促进作用,而Sb2O3在各种含量下对β晶都有较强的抑制作用。溴-锑阻燃体系对β晶的影响随体系中溴与锑之比而变化,含量大的起主导作用。此外,β晶的变化对溴-锑并用体系处理β-PP的阻燃效果无影响。     

聚苯基甲氧基硅氧烷改性环氧树脂的阻燃性能研究

采用氧指数(LOI),UL-94,热失重(TGA)等手段考察了聚苯基甲氧基硅氧烷(PPMS)改性对环氧树脂(E-20)固化体系阻燃性能的影响.相比未改性环氧体系,当m(E-20)∶m(PPMS)=73∶时,改性环氧体系的LOI由纯E-20环氧树脂的17.5%上升到21.5%;水平火蔓延速率由36.23 mm/min降低到26.60 mm/min;质量损失为5%时的热分解温度由134.7℃上升到163.0℃,750℃时残炭量由0.21%增加到25.79%.此外,还通过红外光谱对燃烧后的残炭结构进行了分析,探讨了相关阻燃机理.     

Polyamide‐enhanced flame retardancy of ammonium polyphosphate on epoxy resin

An attractive intumescent flame retardant epoxy system was prepared from epoxy resin (diglycidyl ether of bisphenol A), low molecular weight polyamide (cure agent, LWPA), and ammonium polyphosphate (APP). The cured epoxy resin was served as carbonization agent as well as blowing agent itself in the intumescent flame retardant formulation. Flammability and thermal stability of the cured epoxy resins with different contents of APP and LWPA were investigated by limited oxygen index (LOI), UL‐94 test, and thermogravimetric analysis (TGA). The results of LOI and UL‐94 indicate that APP can improve the flame retardancy of LWPA‐cured epoxy resins. Only 5 wt % of APP can increase the LOI value of epoxy resins from 19.6 to 27.1, and improve the UL‐94 ratings, reaching V‐0 rating from no rating when the mass ratio of epoxy resin to LWPA is 100/40. It is much interesting that LOI values of flame retardant cured epoxy resins (FR‐CEP) increase with decreasing LWPA. The results of TGA, FTIR, and X‐ray photoelectron spectroscopy (XPS) indicate that the process of thermal degradation of FR‐CEP consists of two main stages: the first stage is that a phosphorus rich char is formed on the surface of the material under 500°C, and then a compact char yields over 500°C; the second stage is that the char residue layer can give more effective protection for the materials than the char formed at the first stage do. The flame retardant mechanism also has been discussed according to the results of TGA, FTIR, and XPS for FR‐CEP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

环氧磷酸的合成及对环氧树脂固化物的阻燃耐热性研究

将环氧树脂和磷酸直接反应,制得了含磷11%、与环氧树脂相容性较好的新型含磷阻燃剂(EPH),用氧指数测定、热重法等方法研究了其对环氧树脂二乙烯三胺固化物阻燃耐热性的影响。实验结果表明该阻燃剂对环氧树脂固化物有较好的阻燃作用,能明显提高树脂固化物的残炭量,主要发挥凝聚相阻燃作用。     

Phosphorus‐containing epoxy resin for an electronic application

A phosphorus‐containing epoxy resin, 6‐H‐dibenz[c,e][1,2] oxaphosphorin‐6‐[2,5‐bis(oxiranylmethoxy)phenyl]‐6‐oxide (DOPO epoxy resin), was synthesized and cured with phenolic novolac (Ph Nov), 4,4′‐diaminodiphenylsulfone (DDS), or dicyandiamide (DICY). The reactivity of these three curing agents toward DOPO epoxy resin was found in the order of DICY > DDS > Ph Nov. Thermal stability and the weight loss behavior of the cured polymers were studied by TGA. The phosphorus‐containing epoxy resin showed lower weight loss temperature and higher char yield than that of bisphenol‐A based epoxy resin. The high char yields and limiting oxygen index (LOI) values as well as excellent UL‐94 vertical burn test results of DOPO epoxy resin indicated the flame‐retardant effectiveness of phosphorus‐containing epoxy resins. The DOPO epoxy resin was investigated as a reactive flame‐retardant additive in an electronic encapsulation application. Owing to the rigid structure of DOPO and the pendant P group, the resulting phosphorus‐containing encapsulant exhibited better flame retardancy, higher glass transition temperature, and thermal stability than the regular encapsulant containing a brominated epoxy resin. High LOI value and UL‐94 V‐0 rating could be achieved with a phosphorus content of as low as 1.03% (comparable to bromine content of 7.24%) in the cured epoxy, and no fume and toxic gas emission were observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 353–361, 1999     

环氧多聚磷酸铵的合成及其对环氧树脂固化物性能的影响

将环氧树脂和多聚磷酸直接反应后用氨水中和,制得了含磷18.5%且与环氧树脂相容性较好的新型环氧多聚磷酸铵(EPPA)阻燃剂。用极限氧指数、冲击强度、硬度、热失重等测试方法研究了EPPA对环氧树脂二乙烯三胺固化物阻燃性以及其它各种性能的影响。实验结果表明该阻燃剂对环氧树脂固化物有较好的阻燃作用,适量添加EPPA可大幅提高固化物的韧性,并且对固化物的硬度以及热稳定性影响不大。     

新型含磷阻燃剂(PPOHQ)的合成及其在环氧树脂中的应用

以磷酰二氯和对苯醌为初始原料,合成一种新型的含磷阻燃剂双(2-对二苯酚基)-苯基氧磷(PPOHQ),并通过红外光谱对该化合物的结构进行了表征。利用该阻燃剂对环氧树脂进行固化,并对固化物进行了极限氧指数(LOI)、垂直燃烧(UL-94)、SEM以及锥形量热仪(CONE)等测试。结果表明,阻燃剂用量达到40%时,阻燃级别能通过UL-94V-0级,LOI的值为30.5。CONE测试结果表明,使用该阻燃剂固化的环氧树脂PHRR和THR等参数与EPO/PDA体系相比都有明显的降低。通过对残炭的SEM和FT-IR分析可知,燃烧后,固化的环氧树脂会产生磷酸类物质,促进形成致密的炭层,从而提高了阻燃性能。     

木质素与含磷阻燃剂对环氧树脂固化物阻燃性能的影响

利用不同质量比的木质素、苯酐（PA）、环氧树脂（EP）、2-（二苯基磷酰基）琥珀酸（DPPOSA）共固化制备出一系列环氧树脂固化物,采用极限氧指数测试、UL-94垂直燃烧评级测试、锥形量热仪热释放速率和总热释放量测试、空气条件下的热重分析测试和扫描电镜对环氧固化物进行测试和分析。当EP为90.0%、PA为6.5%、DPPOSA为2.0%、木质素为1.5%时制备的环氧固化物（P-12）的热稳定性能和阻燃性能得到了明显的改善。阻燃性能测试表明：其极限氧指数（LOI）达到34.6%,垂直燃烧测试通过UL-94的V-0级,热释放速率和热释放总量也有效降低;热降解测试结果表明：DPPOSA和木质素的加入可以使材料的降解时间提前,成炭能力增强;扫描电镜结果显示：添加DPPOSA和木质素的环氧固化物燃烧后形成连续、均一、紧密的炭层,进一步证明DPPOSA和木质素的加入使环氧固化物的成炭能力得到增强。     

Synthesis and Properties of a Novel Flame-Retardant Epoxy Resin Containing Biphenylyl/Phenyl Phosphonic Moieties

A novel reactive diol, bis-biphenyloxy (4-hydroxy) phenyl phosphine oxide (BBPHPPO) which contains both biphenylyl and phenyl phosphonic groups was synthesized. Flame retardant advanced epoxy resin was obtained by chain extension of diglycidyl ether of bisphenol-A (DGEBA) with the phosphorus-containing diol (BBPHPPO). The thermal properties and flame retardancy of cured epoxy resin were studied. The resulting BBPHPPO containing epoxy system exhibited higher glass transition temperature than that of advanced epoxy resins prepared from bisphenol-A (BA) and tetrabromobisphenol-A (TBBA). The high char yield and the high LOI value were observed to prove the excellent flame retardancy of this phosphorus-containing epoxy resin.     

有机硅改性松香基环氧树脂的制备及阻燃性能

制备了聚甲基苯基硅氧烷（PMPS）改性松香基乙二醇二缩水甘油醚AR-EGDE。红外光谱(IR)、核磁共振（¹³C NMR）和环氧值测试结果表明有机硅成功接枝至环氧树脂。同时,将PMPS与AR-EGDE充分混合得到物理改性树脂。通过力学性能和极限氧指数测试探讨了改性方法对改性树脂力学及阻燃性能的影响：化学改性优于物理改性及未改性的AR-EGDE。热失重、炭层分析表明,PMPS改性的树脂在受热和燃烧过程中,都能形成含硅炭层,该炭层可延缓内部材料热分解,同时阻止可燃裂解气体的释放和熔滴发生,从而提高材料的耐热和阻燃性能。物理改性松香基环氧,燃烧时无法形成有效富硅炭层覆盖于底部材料,从而使其阻燃性劣于化学改性。     

Aromatic phosphorodiamidate curing agent for epoxy resin coating with flame-retarding properties

Two organophosphorus-based diamines containing aromatic moieties has been synthesized and used as a curing and flame retarding agent for epoxy resin coatings. This agent functions not only as a crosslinking materials in the Epon 828 epoxy resin curing process but also as a fire retarding compound to produce thin films or composites upon curing. Phenyl phosphonic ethylene diamine diamide (PPEDD) was synthesized via condensation of phenylphosphonic dichloride (PPDC and ethylenediamine (EDA)). Likewise, phenyl phosphonic p-phenylene diamine diamide (PPPDD) was synthesized via condensation of PPDC and p-phenylenediamine (PDA). Kinetics studies of the curing reaction of the two phosphorodiamidates were carried out in comparison with the corresponding non-phosphorus containing reference crosslinking agents, EDA and PDA. Thermal stability of the cured epoxy were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Moreover, flame retardant properties of the materials was investigated by limiting oxygen index (LOI) measurements. The results show that epoxy resin cured with phosphorodiamidate possesses higher thermostability than that of the non-phosphorus containing counterpart. This is evident by a significantly higher amount of char formed upon burning. More importantly, the LOI of 27 and 31 was observed in the PPEDD-cured epoxy resin and PPPDD-cured epoxy resin compared with those prepared from non-phosphorus curing agents (20 for EDA and 21 for PDA). This was obtained only with approximately 2–3 wt.% of phosphorus content.