环氧/聚磷酸铵/二氧化铈复合树脂的制备与阻燃性能研究

利用聚磷酸铵-聚多巴胺-二氧化铈(APP-PDA-CeO_2)对环氧树脂(EP)阻燃改性,提升EP的阻燃性能,并解决APP与EP相容性差的问题。探究EP/APP-PDA-CeO_2复合材料的力学性能、阻燃性能,并分析阻燃机理。结果表明:APP-PDA-CeO_2颗粒在EP树脂体系中呈现良好的分散性与力学性能。与EP、EP/APP、EP/CeO_2和EP/APPCeO_2体系相比,EP/APP-PDA-CeO_2复合材料展现更好的阻燃性能。当APP-PDA-CeO_2含量为6%,EP/APP-PDACeO_2复合材料的阻燃性能最好,相比EP材料,EP/APP-PDA-CeO_2(6%)的TTI延长51 s,PHRR降低50.6%,THR降低35.7%,LOI值达到30.3%,UL-94为V-0级别,最大烟密度(MSD)降低至89.82,烟密度等级(SDR)降低至69.12%。     

聚磷酸酯膨胀阻燃剂复配有机蒙脱土阻燃改性环氧树脂

以间苯二胺为固化剂,聚苯氧基磷酸210氢9氧杂磷杂菲对苯二酚酯（POPP）、聚磷酸铵（APP）为阻燃剂, 复配质量分数为1 %有机蒙脱土（OMMT）为膨胀阻燃体系,对环氧树脂（EP）进行阻燃改性。通过极限氧指数测定仪、垂直燃烧测定仪同步热分析仪、锥形量热等研究改性EP的阻燃性能、热性能和力学性能。结果表明,当膨胀阻燃体系（2.5 %POPP/APP+1 %OMMT）添加量为3.5 %时,改性EP可达UL 94 V-0级,同时LOI为25.2 %;当膨胀阻燃体系添加量为11 %时,改性EP的LOI值进一步升高到31.7 %;阻燃剂的加入,使EP的初始分解温度略有降低,但残炭量明显增加;POPP/APP/OMMT的加入很大程度上降低了EP的热释放速率、烟释放量和平均热释放速率。     

耐水阻燃透明型环氧树脂的制备及其应用研究

以二苯基次磷酰氯和哌嗪为原料,成功合成了疏水性阻燃剂哌嗪-1,4-二烷基双（二苯基氧化膦）（PPDO）,并将其添加到环氧树脂（EP）中,制备了阻燃EP复合材料。通过垂直燃烧、氧指数、热失重分析、锥形量热分析和力学性能测试对EP复合材料的阻燃性能、热分解行为、燃烧行为和力学性能进行了详细研究。结果表明,阻燃剂含量为17 %（质量分数,下同）时,EP/17 % PPDO复合材料通过了UL 94 V-0级测试,极限氧指数达28.9 %,耐水测试后,EP/PPDO复合材料仍保持着优异的阻燃效率;与此同时,PPDO与EP基体间出色的相容性,使复合材料具有良好的透明性和力学性能。此外,PPDO明显促进了EP基体提前降解成炭,使其在燃烧过程中,形成了致密且坚硬的膨胀炭层,有效降低了总热释放量,从而使EP/PPDO复合材料获得了良好的阻燃性能。     

DIDOPO与POSS/EG协同阻燃环氧树脂泡沫及机理研究

以对苯乙基桥链9,10⁃二氢⁃9⁃氧杂⁃10⁃磷杂菲⁃10⁃氧化物（DIDOPO）、聚甲基倍半硅氧烷（POSS）、膨胀石墨 （EG）为复配阻燃剂对环氧树脂（EP）泡沫进行阻燃改性,研究了复配阻燃剂对EP泡沫材料的阻燃效果和阻燃机理。结果表明,当DIDOPO/POSS=3∶1（质量比,下同）、DIDOPO/EG=1∶3时,复配阻燃体系的阻燃效果最佳;添加20 %（质量分数,下同） DIDOPO/POSS复配阻燃剂的加入可以使EP泡沫的UL 94测试达到V⁃0级; 添加20 %的 DIDOPO/EG复配体系可以使EP泡沫的极限氧指数（LOI）提高至30.8 %,UL 94测试达到V⁃0级;阻燃体系具有一定的抑烟效果。     

APP/MCA复合阻燃增强聚丙烯的研究

将三聚氰胺氰尿酸盐（MCA）、聚磷酸铵（APP）与聚丙烯（PP）共混,制备了无卤阻燃PP复合材料,采用极限氧指数仪、热失重分析仪、扫描电子显微镜、电子万能试验机等对材料的阻燃性能、热性能和力学性能等进行了表征,研究了APP/MCA的协效阻燃作用及其对材料力学性能的影响规律。结果表明,在材料中添加25份APP/MCA时,材料的极限氧指数随MCA含量的增加先升高后下降,当MCA含量为30 %（质量分数,下同）时,材料的极限氧指数达到最大值24.2 %;材料的力学性能同样随MCA含量的增加而先升高后下降,当MCA含量为30 %时,其拉伸强度比APP单独阻燃PP时提高了50 %,断裂强度和屈服强度均提高10 %以上。     

无卤阻燃连续长玻璃纤维增强PP的性能研究

通过熔融共挤出法制备了阻燃连续长玻璃纤维增强聚丙烯(PP)复合材料,并对其力学性能、腐蚀性、相比漏电起痕指数以及灼热丝起燃温度在玻璃纤维含量相同时,随阻燃剂种类、含量以及玻璃纤维形态的变化规律进行了研究。结果表明,自制复配无卤阻燃剂（OP1120A）和连续长玻璃纤维所制得的复合材料的综合性能最佳,且随着OP1120A含量的增加,材料的力学性能和相比漏电起痕指数值下降,阻燃性能提高;当长玻璃纤维含量为40 %、OP1120A含量为17 %时,材料的拉伸强度为189 MPa、冲击强度为213 J/m、相比漏电起痕指数达到650 V、灼热丝起燃温度达到960 ℃。     

DOPO型无卤阻燃环氧树脂体系的性能研究

采用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和DOPO型含磷环氧树脂(DOPO–EP)对双酚A型EP进行阻燃改性,研究了不同磷含量下两种阻燃剂对EP的改性效果。结果表明,随磷含量增加,EP/DOPO与EP/DOPO–EP体系的玻璃化转变温度均降低,但EP/DOPO–EP体系的降幅较小;DOPO与DOPO–EP均能有效地提高EP的阻燃性能,但DOPO–EP的阻燃效果更佳;EP/DOPO–EP体系的综合力学性能高于EP/DOPO体系。当磷质量分数分别为2.5%和1.5%时,EP/DOPO与EP/DOPO–EP体系的垂直燃烧等级均达到UL 94 V–0级,极限氧指数分别为32%和33%。EP/DOPO体系在磷质量分数为2.5%时的残炭率(700℃)为12.27%,较纯EP提高了17.3%,但其拉伸性能、冲击性能和弯曲强度均大幅下降。而EP/DOPO–EP体系在磷质量分数为1.5%时的残炭率(700℃)为20.07%,较纯EP提高了91.9%,其断裂伸长率和弯曲强度分别为2.32%和92.69 MPa,较纯EP分别提高了13.73%和24.27%,拉伸强度和缺口冲击强度分别为35.34 MPa和1.85 kJ/m2,较纯EP仅下降了1.56%和1.07%,综合性能最佳。     

微胶囊红磷的制备及其阻燃环氧树脂的性能研究

以预先合成的密胺甲醛树脂预聚物为壳,通过原位聚合法制备了微胶囊红磷,采用扫描电镜观察到微胶囊红磷颗粒表面包覆一层网状的壳材料。研究了红磷和微胶囊红磷阻燃环氧树脂(EP)的耐热性能、阻燃性能及力学性能。结果表明,微胶囊红磷阻燃EP的耐热性和质量保持率明显提高,添加质量分数10%的微胶囊红磷的阻燃EP的阻燃性能达到UL 94 V–0级,其阻燃性能优于红磷阻燃EP。微胶囊红磷阻燃EP的拉伸强度为30.3 MPa,冲击强度为11.4 kJ/m2,分别比相同用量红磷阻燃EP提高了6.0%和21.3%,其冲击强度比纯EP提高了17.5%,表明微胶囊红磷与基体树脂间的相容性大大改善,可显著提高材料的韧性。     

新型含N和P阻燃剂的合成及其在环氧树脂中的阻燃机理研究

文章以对苯二甲醛、对苯二胺和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）为原料,采用一锅法合成了一种新型含P和N的高效阻燃剂PABD。探究PABD的含量对环氧树脂（EP）阻燃性和力学性能的影响。结果表明：PABD具有较高的热稳定性和成炭率,PABD的加入提高了EP的阻燃性。EP中添加7%PABD可达到V-0级,极限氧指数（LOI）可达到35.5%,热释放速率峰值（PHRR）和总热释放量（THR）相较纯EP分别下降24.8%和28.2%,具备优异的阻燃效率。当PABD的添加量为7%,EP7的拉伸强度可达65.70 MPa,相较于纯EP的57.0 MPa提高15.3%。合成的PABD不仅可提高EP的阻燃性能,还能够提高EP的力学性能,PABD有望在EP中获得广泛应用。     

阻燃抗静电聚烯烃板材的制备与性能研究

在聚烯烃树脂中加入无卤阻燃剂MRP⁃1400、炭黑及聚乙烯基弹性体（POE）制得了阻燃抗静电聚烯烃材料,研究了阻燃剂、炭黑和POE含量对材料性能的影响。结果表明,MRP⁃1400的加入能提高材料的阻燃性能,其含量为20 %（质量分数,下同）时（对应磷含量为8 %）材料达到UL 94 V⁃0 级,可以通过MT 113—1995酒精喷灯测试;当导电炭黑含量为6 %时,材料满足MT 113—1995抗静电要求;POE能进一步优化材料的力学性能,POE含量为5 %时可制得综合性能较好的阻燃抗静电材料,其缺口冲击强度为35 kJ/m²,断裂伸长率为315 %;动态疲劳实验结果表明,所开发材料的耐疲劳性能优异,动态疲劳寿命大于120万次。     

Ionic liquid modified graphene oxide for enhanced flame retardancy and mechanical properties of epoxy resin

In this work, to improve its dispersion and flame retardancy, graphene oxide (GO) was functionalized by silane coupling agent KH550 and 1-butyl-3-methylimidazole hexafluorophosphate (PF₆-ILs), and characteristics of the PF₆-ILs@GO was obtained by transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Then, the synergistic flame retardant of GO or PF₆-ILs@GO and melamine pyrophosphate (MPP) were applied for epoxy resin (EP) materials. Specifically, the limiting oxygen index (LOI) value of EP with 0.1 wt% PF₆-ILs@GO was increased to 29.2% from 27.5% of EP/MPP composites, and the UL-94 test reached the V-0 rating. The CCT results showed that the total heat release (THR) and total smoke release (TSP) of EP/MPP/PF₆-ILs@GO composites were significantly 24.4% and 53.4% lower than that of EP/MPP composites. Besides, the thermal behavior investigated by TGA indicated that the char-forming effect of GO and PF₆-ILs@GO was great, the residual char of EP/MPP/PF₆-ILs@GO composites was as high as 19.5% at 700°C, and its thermal stability was higher than that of EP/MPP composites. On the other hand, the tensile strength of EP/MPP/GO and EP/MPP/PF₆-ILs@GO composites were increased by 15.6% and 28.3% compared with EP/MPP composites. According to SEM analysis, the EP/MPP/GO composites formed a good protective char layer, which can effectively improve flame retardancy of EP. This research represents a new method of flame retardant modified GO to improve the flame retardancy and mechanical properties of polymers.     

纳米层状双羟基化合物阻燃聚合物研究进展

综述了纳米层状双羟基化合物（LDH）的研究及应用现状,详细阐述了其作为聚合物纳米填料对马来酸酐接枝聚乙烯(PE-g-MAH)和环氧树脂(EP)热稳定性和阻燃性的影响,展望了LDP作为阻燃剂和作为聚磷酸铵（APP）的阻燃协效剂的发展前景。     

Effect of gas-condensed phase synergistic system of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and polydopamine on flame retardancy of epoxy resin

Polydopamine (PDA) was prepared by using dopamine which has good charring ability. The PDA was used as an environmentally friendly flame retardant and combined with 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO) to improve the flame retardancy of epoxy (EP) resin. The flame retardancy and thermal stability of EP composites were researched by UL-94 vertical burning, limiting oxygen index (LOI), cone calorimetry tests, and thermal gravimetric analyzer. Adding DOPO alone requires 6% to make EP obtain the UL-94 V0. If DOPO and PDA are combined, only 4% is needed to make EP obtain the UL-94 V0, which suggests that there is good synergistic effect between them. Moreover, the peak of heat release rate of EP/DOPO/PDA composites is less than that of EP/DOPO composites. The reactions among EP, DOPO, and PDA reduce the release of combustible gases at the early stage of degradation; at the same time, DOPO volatilize to the gas phase, quench the free radicals, and the combustion can be stopped. In addition, due to the decrease of the amount of PDA/DOPO, the EP composite can get a higher glass transition temperature, but due to the aggregation of PDA in EP, the tensile property of EP composite decreases.     

Carbon nanotubes coated with phosphorus-nitrogen flame retardant and its application in epoxy thermosets

ABSTRACT

Carbon nanotubes coated with phosphorus-nitrogen flame retardant (PDAP-CNTs) were produced. The compositions and structures of PDAP-CNTs were systematically characterized, and the flame retardancy of PDAP-CNTs/EP composites were also tested. The results indicated that PDAP-CNTs demonstrated excellent flame retardancy performance on the flame-retardant EP composites (FR-EP), incorporation of 5.0wt% PDAP-CNTs improved the LOI values of EP from 26.0% to 31.8% and reached UL-94 V-0 classification. The analysis of flame-retardant mechanism indicating the flame-retardant ability of PDAP-CNTs was ascribed to the synergism of the phosphorus-nitrogen containing coating layer (PDAP) and CNTs.     

Intrinsic flame-retardant epoxy resin composites with benzoxazine: Effect of a catalyst and a low curing temperature

Three kinds of inherent flame-retardant epoxy resin (EP) composites with 20 wt % benzoxazine (BOZ) were prepared with different curing processes with 2-methyl-1H-imidazole (MI) as a catalyst or/and changes in the curing temperature. The effects of the curing process on the flame retardancy, thermal stability, mechanical properties, and curing behaviors were investigated. The composite with added MI cured at low temperature (EBM–LT) had the best properties. It possessed a 35.3% limiting oxygen index and achieved a UL 94 V-0 rating. Thermogravimetric analysis indicated that EBM–LT had the best thermal stability among the three kinds of EP composites with BOZ. The EP composites with BOZ mainly displayed a condensed-phase flame-retardant mechanism. The mechanical properties improvement was attributed to the formation of a heterogeneous network. Differential scanning calorimetry indicated that MI reacted with EP and catalyzed the homopolymerization of BOZ, and EP reacted with BOZ. Fourier transform infrared spectroscopy analysis indicated that curing at lower temperature caused the formation of more homopolymers of BOZ. The relationship of the curing process, network structure, and properties of EP composites with BOZ was established; this could help with the design of high-performance EP composites with BOZ. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47847.     

Flame retardancy and mechanical properties of ferrum ammonium phosphate–halloysite/epoxy polymer nanocomposites

To recycle the nitrogen (N) and phosphorus (P) from wastewater, ferrum ammonium phosphate (FAP)–halloysite nanotubes (HNTs) were synthesized with simulated wastewater containing N, P, and Fe pollutants as raw materials. The adsorption–chemical precipitation in situ method was used to synthesize the target products, and the optimal conditions for the synthesis of the FAP–HNTs were obtained. Fourier transform Infrared (FTIR) spectroscopy, energy‐dispersive spectroscopy (EDS), scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis were conducted to characterize the samples. The FAP particle size was 20–30 nm in the FAP–HNTs. The FTIR spectra demonstrated that a small amount of water in the FAP–HNTs promoted the curing reaction. The FAP–HNTs and Exolit OP 1230 (OP) were introduced into epoxy (EP) to prepare the polymer nanocomposites. The heat release rate (HRR) and flammability of the EP composites were tested by microscale combustion calorimetry and UL‐94 instruments. The mechanical properties of the EP composites also were tested by a tension testing system. The results indicate that the flame retardancy and mechanical properties of the EP composites were improved by FAP–HNT. The addition of FAP–HNT and OP gave rise to an evident reduction of HRR and a prolonged burning time for the EP. EP/FAP–HNT/OP (20) (where 20 is the loading weight percentage) passed the UL 94 V‐0 rating. The analysis of the char revealed the synergy of the FAP–HNTs and OP in reducing the flammability of the polymers. We concluded that these polymers show potential for applications in wastewater treatment and N/P recycling. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41681.     

EP/MOC复合材料热分解动力学与阻燃性能研究

采用Kissinger法和Crane法对环氧树脂/氯氧镁(EP/MOC)阻燃复合材料在空气中不同升温速率下的热重(TG)和差热(DTA)曲线进行了热解动力学研究。测定了EP/MOC复合材料中EP起始分解和终止分解放热峰的特征温度。结果表明:EP/MOC复合材料中的EP活化能高于纯EP,说明MOC增强了EP的热稳定性,提高了热解温度;EP/MOC中的EP热分解反应级数和纯EP基本相同,说明同条件下的EP和MOC对热分解速率的影响是相同的;另外,该EP/MOC复合材料具有良好的阻燃性能。     

Flame retardant and mechanical properties of epoxy composites containing APP−PSt core−shell microspheres

Ammonium polyphosphate (APP)–polystyrene (PSt) core–shell microspheres (CSPs) were synthesized via in situ radical polymerization. The core–shell structure was confirmed by transmission electron microscope (TEM). The results of optical contact angle measurements demonstrated a significant improvement in hydrophobicity of the modified APP. The obtained APP–PSt CSPs were added into epoxy (EP) system with various loadings. Effects of CSP on flame retardancy, thermal properties, heat release rate (HRR), smoke production, and mechanical properties of EP/CSP composites were investigated by limiting oxygen index (LOI), UL‐94 tests, thermogravimetric analysis (TGA), cone calorimeter, and tensile test. LOI and UL‐94 indicated that CSP remarkably improved the flame retardancy of EP composites. TGA showed that the initial decomposition temperature and the maximum‐rate decomposition temperature decreased, whereas residue yields at high temperature increased with the incorporation of microspheres. Cone calorimetry gave evidence that HRR, peak release rate, average HRR, and smoke production rate of EP/CSP composites decreased significantly. The morphology of char residues suggested that CSP could effectively promote EP to form high‐quality char layer with compact outer surface and swollen inner structure. Tensile strength of EP was enhanced with the addition of CSP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40218.     

Flame retardant performance of a carbon source containing DOPO derivative in PET and epoxy

The combination of gas‐phase and condensed‐phase action will contribute to high quality flame retardant. A novel 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO)‐based flame retardant (DOPO‐DOPC), which contains carbon source was synthesized in favor of conducting the effect of gas‐phase as well as promoting the char formation in condensed‐phase. The chemical structure of DOPO‐DOPC was characterized by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). DOPO–DOPC was used as an additive in poly(ethylene terephthalate) (PET) and epoxy resin (EP). The flame retardancy of PET/DOPO‐DOPC and EP/DOPO‐DOPC composites were studied by limiting oxygen index (LOI) and UL‐94 test. The results showed that the incorporation of DOPO–DOPC into PET or EP could obviously improve their flame retardancy. The LOI values of modified PET or EP, which contained 10 wt % DOPO‐DOPC reached 42.8 and 31.7%, respectively. The thermogravimetric analysis (TGA) results revealed that DOPO–DOPC enhanced the formation of char residues. The Laser Raman spectroscopy (LRS) was used to investigate the carbon structure of thermal oxidation residues. Because of the combination of the gas phase flame retardant effect of DOPO moiety and the promoting formation of char residues in condensed phase, the PET and EP composites exhibited significant improvement toward flame retardancy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44639.     

Zirconium-Embedded Polyhedral Oligomeric Silsesquioxane Containing Phosphaphenanthrene-Substituent Group Used as Flame Retardants for Epoxy Resin Composites

A zirconium hybrid polyhedral oligomeric silsesquioxane derivative (Zr–POSS–bisDOPO) is synthesized by the corner-capping and Kabachnik–Fields reactions. It is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and then used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) to endow epoxy resin (EP) with flame retardancy. The flame retardancy, thermal stability, and mechanical properties of the cured EP/Zr–POSS–bisDOPO composites are investigated. The results show that when Zr–POSS–bisDOPO is added by 5–7 wt%, the EP/Zr–POSS–bisDOPO composites pass the UL-94 V-0 rating test. In addition, they have a better flame-retardant effect than pure EP. The combination of Zr atom embedded in the Si O cubic cage and the two phosphaphenanthrene substituent groups in one corner of cubic cage is expected to realize the Zr/Si/P ternary intramolecular hybrid synergistic effect and achieve the possibility of dispersing metal–POSS cages at a sub-micrometer-scale level into polymer matrix. It also proves that Zr–POSS–bisDOPO produces phosphorus-containing free radicals and terminates the chain reactions in gas phase. Meanwhile the Si O Si and Zr O units are retained in the solid phase, which promote the char formation and enhance the flame retardancy. This kind of Zr-doped POSS will be helpful for developing the new metal–POSS hybrid flame-retardant and polymer composites.