含双DOPO的双酚A-单苯并嗪合成、表征及其与环氧树脂共聚物的阻燃性能

以含双DOPO-双酚A、苯胺和多聚甲醛为原料,合成了含双DOPO的双酚A-单苯并嗪(1DD)。采用红外、核磁(氢谱核磁和碳谱核磁)等分析手段对1DD的化学结构进行了表征;采用DSC对1DD的固化特性进行研究,使用TG分析了所得聚苯并嗪的热稳定性。再将1DD与环氧树脂以0.5/1的质量比进行共混,按照一定的程序进行升温固化,得到共聚物P1DD-ER。采用UL94垂直燃烧实验、极限氧指数仪(LOI)测试了共聚物的阻燃性能。结果表明:含双DOPO的双酚A-单苯并嗪树脂的起始熔点约为185℃,在222℃处有一个很明显的放热峰。固化后的树脂从348℃开始分解,在463℃分解速率达到最快,在800℃时的残碳率为35.78%。制备的苯并嗪可以用作环氧树脂的固化剂,且其共聚物具有很好的阻燃性能,LOI可以达到37,UL94等级为V-0。     

含双DOPO的双酚A-双苯并(口恶)嗪合成、表征及其固化特性

以双酚A-双苯并(口恶)嗪(DBOZ)和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物 (DOPO)为原料,合成了双酚A-双DOPO(2DO),再用其与苯胺、多聚甲醛反应,合成了含双DOPO的双酚A-双苯并(口恶)嗪(2DD).采用红外、核磁共振等分析手段对2DO和2DD的化学结构进行了表征,采用差示扫描量热仪对DBOZ和2DD的固化特性进行研究,使用热重分析仪分析了所得聚苯并(口恶)嗪的热稳定性.结果表明:在N₂气氛中,含双DOPO的双酚A-双苯并(口恶)嗪热分解温度为353℃,在442℃分解速率达到最快,800℃时的残碳率为40.40%,300℃的质量变化为3.97%.与未引入DOPO的双酚A-双苯并(口恶)嗪树脂相比,其热分解温度提高了将近41℃,最大分解速率提高了将近70℃,残碳率提高了将近3.21%.     

含DOPO的双酚A-单苯并(口恶)嗪合成、表征及其固化特性

以双酚A、苯胺、多聚甲醛为原料,合成了双酚A-双苯并(口恶)嗪（DBOZ）,再用其与DOPO（9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物）反应,合成了含DOPO的双酚A-单苯并(口恶)嗪（DBDO）。采用红外、核磁共振（氢谱核磁共振和碳谱核磁共振）等分析手段对DBOZ和DBDO的化学结构进行了表征;采用差示扫描量热仪对DBOZ和DBDO的固化特性进行研究,使用热重分析分析了所得聚苯并(口恶)嗪的热稳定性。结果表明：在N₂气氛中,DBOZ在205℃左右开环聚合,热分解温度为312℃,在373℃分解速度达到最快,在800℃时的残碳率为37.19%;在N₂气氛中,DBDO的热分解温度为353℃,在443℃分解速度达到最快,在800℃时的残碳率为39.60%。     

苯并恶嗪/含磷环氧/二氨基二苯醚体系阻燃性能的研究

分别制备了不同配比的双酚A型苯并恶嗪/含磷环氧树脂二元体系和双酚A型苯并恶嗪/含磷环氧树脂/二氨基二苯醚三元体系的树脂,并进一步制备了浇铸体。通过差示扫描量热(DSC)研究了三元体系树脂的固化反应,通过垂直燃烧测试、锥形量热测试、热重分析(TGA)、热重-红外联用(TGA-FTIR)等手段研究了浇铸体的热降解和阻燃性。结果表明,在双酚A苯并恶嗪/含磷环氧树脂体系中加入10%4,4'-二氨基二苯醚,三元体系浇铸体样条阻燃性提高,达UL94 V-0级;但在锥形量热测试中,三元体系的热释放速率和总热释放量反而高于二元体系。     

无溶剂缠绕成型用含磷阻燃环氧树脂的研究

通过有机磷化合物9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）与双酚A型环氧树脂反应合成了一种含磷环氧树脂。通过跟踪测定环氧当量研究了开环反应过程,并用傅里叶红外光谱仪对产物结构进行了表征;采用差示扫描量热法和平板凝胶法表征了树脂体系的固化特性;依据UL94垂直燃烧法研究了磷含量与树脂体系阻燃性能的关系,采用热重分析（TGA）研究了不同含磷量环氧树脂的残炭率及裂解性能;采用差示扫描量热仪和电子万能拉伸试验机研究了阻燃环氧树脂固化物的耐热性和力学性能。结果表明,DOPO与双酚A型环氧树脂在170 ℃下6 h可完成开环加成反应;含磷环氧树脂的固化温度较双酚A型环氧树脂提高;磷含量为2.0 %（质量分数,下同）时,含磷环氧树脂固化物阻燃性能达UL94 V-0级,残炭率为23 %;其固化物的耐热性和力学性能较双酚A型环氧树脂无明显下降。     

苯并恶嗪/环氧树脂/酸酐三元体系固化反应研究

采用重结晶双酚A-苯胺型苯并恶嗪(BA-a)、双酚A型环氧树脂(BPA-E)与聚苯乙烯马来酸酐(EF40)进行共聚反应。通过示差扫描量热分析和红外光谱测试对苯并恶嗪/酸酐、环氧树脂/酸酐二元体系及苯并恶嗪/环氧树脂/酸酐三元体系的固化行为及各阶段固化物结构进行了研究。结果表明:酸酐与苯并恶嗪、环氧树脂均发生反应,分别生成不同类型的酯键结构。在三元体系中,酸酐与环氧树脂首先反应,形成醇酯键;其次,苯并噁恶嗪自聚,聚苯并恶嗪中的酚羟基与少量酸酐、环氧树脂反应,生成酚酯键、羧酸或醚式结构,同时新生成的羧酸结构可促进苯并恶嗪开环聚合。     

取代苯胺对含烯丙基的苯并恶嗪的性能影响

以甲基苯胺和苯胺与多聚甲醛、烯丙基双酚A合成了含烯丙基的苯并恶嗪(BA),采用红外及核磁氢谱对其结构进行了表征。其与单官能度苯并恶嗪(PAF)在溶液中共混并加热固化。通过DSC,TGA及DMA对BA及共混物、固化物的热性能进行了研究。结果表明,BA固化峰值温度>250℃,与PAF共混后固化温度下降,且随PAF加入量的增加而下降。共混后固化后热稳定性较好,其中含间位取代苯胺的烯丙基苯并恶嗪与PAF共混树脂的热稳定和弯曲强度最高,热失重5%和10%时的温度分别为308℃、384℃,玻璃化转变温度为171℃,弯曲强度24 MPa。     

含DOPO的双酚A-单苯并嗪合成、表征及其固化特性

以双酚A、苯胺、多聚甲醛为原料,合成了双酚A-双苯并嗪(DBOZ),再用其与DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)反应,合成了含DOPO的双酚A-单苯并嗪(DBDO)。采用红外、核磁共振(氢谱核磁共振和碳谱核磁共振)等分析手段对DBOZ和DBDO的化学结构进行了表征;采用差示扫描量热仪对DBOZ和DBDO的固化特性进行研究,使用热重分析分析了所得聚苯并嗪的热稳定性。结果表明:在N2气氛中,DBOZ在205℃左右开环聚合,热分解温度为312℃,在373℃分解速度达到最快,在800℃时的残碳率为37.19%;在N2气氛中,DBDO的热分解温度为353℃,在443℃分解速度达到最快,在800℃时的残碳率为39.60%。     

二茂铁对DOPO/环氧树脂体系燃烧性能及固化反应动力学的影响

为研究二茂铁对磷杂菲(DOPO)/环氧树脂(EP)体系燃烧性能及固化反应动力学的影响,将不同比例的二茂铁与DOPO/EP体系复配制备了阻燃EP复合材料,通过氧指数(LOI)测试、UL94垂直燃烧测试、烟密度测试和热重分析研究了阻燃EP复合材料的燃烧性能和热氧稳定性,并通过非等温DSC法研究了二茂铁对DOPO/EP体系固化反应动力学的影响。结果表明,二茂铁和DOPO在阻燃EP复合材料中表现出明显的阻燃协效作用,添加了二茂铁的阻燃EP复合材料的LOI最高可达34.8%,烟密度等级(SDR)最低降至71.43。热重分析表明,二茂铁会降低阻燃EP复合材料的热氧稳定性,但是可以显著增加热解残炭量。固化反应动力学研究结果表明,二茂铁的添加使阻燃EP体系固化反应的活化能E_a和指前因子A均减小。研究工作可以为高性能阻燃EP复合材料的开发提供参考。     

含PEPA基团苯并噁嗪的合成与性能

以水杨醛、对氨基苯酚和PEPA的衍生物为原料,合成了含笼型膦酸酯结构的苯并噁嗪单体(PEPA-Bz),用FTIR和1HNMR对其结构进行了表征。PEPA-Bz均聚物热失重分析(TGA)结果表明,该聚苯并噁嗪具有较好的热稳定性和成炭性能,起始热分解温度235℃,700℃时残炭率为53%,氧指数达到38.7。采用FTIR和TGA分别考察了PEPA-Bz与双酚A型苯并口恶嗪树脂(Ba)的开环共聚行为及共聚物的热性能。结果表明,含PEPA-Bz苯并噁嗪共聚物的阻燃性和成炭性明显优于不含PEPA-Bz的双酚A型苯并噁嗪树脂。     

Synthesis of a novel phosphorus‐containing dicyclopentadiene novolac hardener and its cured epoxy resin with improved thermal stability and flame retardancy

A novel phosphorus‐containing dicyclopentadiene novolac (DCPD‐DOPO) curing agent for epoxy resins, was prepared from 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and n‐butylated dicyclopentadiene phenolic resin (DCPD‐E). The chemical structure of the obtained DCPD‐DOPO was characterized with FTIR, ¹H NMR and ³¹P NMR, and its molecular weight was determined by gel permeation chromatography. The flame retardancy and thermal properties of diglycidyl ether bisphenol A (DGEBA) epoxy resin cured with DCPD‐DOPO or the mixture of DCPD‐DOPO and bisphenol A‐formaldehyde Novolac resin 720 (NPEH720) were studied by limiting oxygen index (LOI), UL 94 vertical test and cone calorimeter (CCT), and differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. It is found that the DCPD‐DOPO cured epoxy resin possess a LOI value of 31.6% and achieves the UL 94 V‐0 rating, while its glass transition temperature (T_g) is a bit lower (133 °C). The T_g of epoxy resin cured by the mixture of DCPD‐DOPO and NPEH720 increases to 137 °C or above, and the UL 94 V‐0 rating can still be maintained although the LOI decreases slightly. The CCT test results demonstrated that the peak heat release rate and total heat release of the epoxy resin cured by the mixture of DCPD‐DOPO and NPEH720 decrease significantly compared with the values of the epoxy resin cured by NPEH720. Moreover, the curing reaction kinetics of the epoxy resin cured by DCPD‐DOPO, NPEH720 or their mixture was studied by DSC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44599.     

新型磷／氮协同阻燃环氧树脂的合成与性能

以双酚A环氧树脂E－51与DOPO（9,10-dihydrooxa-20－phosph henanthrene－10-oxide）合成含磷环氧树脂（ED）,以三聚氰胺与苯酚反应制备含氮的酚醛固化剂MFP。采用红外光谱对产物进行分析表征,采用热失重分析和UL94V垂直燃烧测试考查树脂的热性能和阻燃性能,同时探讨了阻燃环氧树脂的力学性能。结果表明,随着含磷量的增加,环氧树脂的热稳定性和阻燃性能得到改善,当含磷量为3％时,环氧树脂的初始分解温度高达330℃以上,在700℃下的残炭率达到30％以上,阻燃性能均达到了UL－94 V—0级。而试样的力学性能则随含磷量的增加而降低。     

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     

A phosphorus‐containing phenolic derivative and its application in benzoxazine resins: Curing behavior,thermal, and flammability properties

In this work, flame‐retardant benzoxazine resins were prepared by copolymerization of bisphenol A based benzoxazine (BA‐a) and a phosphorous‐containing phenolic derivative (DOPO‐HPM). The curing behavior, thermal stability, and flame resistance of BA‐a/DOPO‐HPM composites were studied by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 test, and cone calorimeter. The DSC results indicated that DOPO‐HPM catalyzed the curing reaction because of its acidity. The TGA results revealed that the BA‐a/DOPO‐HPM thermosets possessed higher decomposition temperatures (T_5%) and char yields than that of BA‐a. The combustion tests indicated that the flame retardant properties of BA‐a/DOPO‐HPM thermosets were enhanced. The BA‐a/DOPO‐HPM‐20 sample acquired the highest LOI value of 32.6% and UL94 V‐0 rating. Moreover, the average of heat release rate (av‐HRR), peak of heat release rate (pk‐HRR), average of effective heat of combustion (av‐EHC) and total heat release (THR) of BA‐a/DOPO‐HPM‐20 were decreased by 24.6%, 53.1%, 14.9%, and 22.1%, respectively, compared with BA‐a. The attractive performance of BA‐a/DOPO‐HPM blends was attributed to the molecular structure of DOPO‐HPM composed of DOPO group with excellent flame‐retardant effect and phenolic hydroxyl group with catalysis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43403.     

新型含硼苯并噁嗪的合成及其与环氧树脂共混热性能

以乙醇胺、硼酸为原料合成硼酸乙醇胺酯（BAE）,再用所得硼酸乙醇胺酯与多聚甲醛、苯酚反应,合成含硼苯并噁嗪（BAE-BOZ）。将所得BAE-BOZ高温固化,BAE-BOZ和环氧树脂E-51按照不同的质量比进行熔融共混,并经高温固化。采用FT-IR,¹H NMR 和¹³C NMR等分析了BAE-BOZ的化学结构,证明了产物为目标产物;采用DSC对BAE-BOZ的固化特性进行研究;采用TG 分析了含硼乙醇胺型苯并噁嗪poly（BAE-BOZ）和BAE-BOZ/E-51共聚物的热稳定性。结果表明：BAE-BOZ在218℃出现了固化峰;BAE-BOZ的硼含量达到8.67%,在N₂条件下,poly（BAE-BOZ）的热分解温度为302℃,在426℃时热分解速率最快,800℃的残炭率为58.08%,与未经硼改性的乙醇胺型苯并噁嗪（E-BOZ）相比,热分解温度提高40℃,残炭率提高了16.28%;BAE-BOZ/E-51共聚物的热分解温度达到343℃,热性能得到进一步提高。     

新型潜伏性固化剂的合成及性能

利用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）的亲核特点,将其与双氰胺进行加成反应,合成了一种潜伏性固化剂,并将其与环氧树脂进行固化反应。用FTIR、¹H NMR分析了固化剂的结构;用DSC、TG分析了固化剂和固化体系的热性能。结果表明,与双氰胺相比,固化剂的熔点降低了近100℃,固化温度下降近 40℃;优化了固化工艺参数;考察了体系的潜伏性和难燃特性,其储存期超过100 d,LOI达到22。     

Preparation and properties of halogen-free flame retardant epoxy resins with phosphorus-containing siloxanes

Novel epoxy resin modifiers, DOPO–TMDS and DOPO–DMDP were synthesized by addition reaction of divinylsiloxane with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Halogen-free flame retardant epoxy resins were obtained through modification of o-cresol novolac epoxy resin cured by phenol novolac resin using DOPO–TMDS and DOPO–DMDP which were characterized by ¹H NMR, ¹³C NMR, ³¹P NMR and FT-IR measurements. Effects of the phosphorus-containing siloxanes on thermal stabilities, mechanical properties and flame retardant properties of the epoxy resins were investigated. The cured epoxy resins exhibited better mechanical properties and greatly improved flame retardant properties due to the presence of phosphorus-containing siloxanes. The cured epoxy resins with phosphorus loading of 2.0 wt% showed LOI values of 32–33 and achieved UL94V-0 ratings.