阻燃润滑剂氰尿酸三聚氰胺盐的制备

前言随着科学技术的进步和发展,橡胶、塑料等有机高分子材料的应用日益广泛,而这些材料的难燃和防火性能,已成为人们十分关注的问题。进入八十年代,国内阻燃剂开发研究,推广应用步伐喜人,阻燃剂已成为一类具有独特性能和应用范围广的专用品,是精细化工范围内一个很有前途的品种。     

SiO_2改性三聚氰胺氰尿酸盐无卤阻燃剂的制备

在三聚氰胺(MA)与氰尿酸(CA)反应合成三聚氰胺氰尿酸盐(MCA)过程中加入SiO2溶胶,通过调控工艺参数,制备了改性MCA复合阻燃剂。研究发现:当反应体系pH为4.0,在MA和CA反应体系的粘度为5×104mPa.s时加入SiO2溶胶,反应时间为1h,所制备的改性MCA粒径较小,产率最高,实现了SiO2和MCA的有效复合和对MCA粒径的超细控制。     

高分散型三聚氰胺氰尿酸盐阻燃硅橡胶的研究

以自制高分散型三聚氰胺氰尿酸盐（GFMCA）为阻燃剂制备甲基乙烯基硅橡胶（MVQ）阻燃材料,并对阻燃剂粒子形貌及团粒结构、阻燃材料的阻燃性能和物理性能进行研究。结果表明：GFMCA团粒结构松散,在MVQ中表现出优异的分散性和稳定性,无析出。传统三聚氰胺氰尿酸盐（MCA）/MVQ与GFMCA/MVQ硫化胶的阻燃性能相当,当阻燃剂用量为30份时,均可达到UL94 V-O级（1.6 mm）;（JFMCAiMVQ硫化胶的物理性能较好,其拉伸强度和拉断伸长率较MCA/MVQ硫化胶分别提高20%和118%。GFMCA/Mvo硫化胶的综合性能较好     

三聚氰胺氰尿酸盐阻燃尼龙6的机理研究

将蒙脱土(MMT)引入反应性挤出制备三聚氰胺氰尿酸盐(MCA)阻燃尼龙6(PA6)体系中.研究了其阻燃性能及MCA阻燃PA6的阻燃机理,MCA阻燃PA6机理主要是MCA分解产物催化PA6为齐聚物,形成熔滴,带走燃烧产生的热量,使材料自熄.     

聚酰胺表面改性三聚氰胺氰尿酸盐及其阻燃聚酰胺6研究

以聚酰胺树脂的无机酸溶液为介质进行三聚氰胺-氰尿酸分子自组装合成三聚氰胺氰尿酸盐(MCA),并同时实现聚酰胺树脂对阻燃剂的表面包覆改性,集MCA的合成及表面改性于一体。该阻燃剂与目标阻燃树脂聚酰胺6 的相容性良好,阻燃剂粒子与聚酰胺6(PA6)树脂基体之间相界面基本消失。聚酰胺6中添加7％该阻燃剂即达到 UL94-1．6mm V0级别,成功解决了传统MCA阻燃PA6燃烧熔滴易引燃脱脂棉的问题,其极限氧指数高达34％,阻燃效率远高于传统MCA。材料力学性能良好,具有较好的市场应用前景。     

三聚氰胺氰尿酸盐阻燃PA6复合材料性能研究

以三聚氰胺氰尿酸盐(MCA)为阻燃剂,制备了聚酰胺6(PA6)阻燃复合材料,采用氧指数、垂直燃烧和热失重(TG)重点研究分析了MCA对PA6复合材料的阻燃性能的影响,同时,考察了MCA对PA6复合体系力学性能和吸水性能的影响。结果表明,当MCA用量为10份时,PA6复合材料的氧指数达到28%,符合难燃材料的要求;TG分析表明,MCA的加入,使复合体系最大分解速率温度升高44℃,提高了PA6的热稳定性,但MCA的促炭能力不强;MCA的加入,复合材料拉伸强度随MCA的加入先增加后降低,而冲击强度逐渐降低;MCA的加入也降低了复合材料的吸水率。     

三聚氰胺氰尿酸盐阻燃聚氨酯硬泡

将三聚氰胺氰尿酸盐(MCA)作为阻燃剂,采用一步全水发泡法,制备一系列硬质聚氨酯泡沫/三聚氰胺氰尿酸盐复合材料(RPUF/MCA),采用扫描电子显微镜(SEM)、热重分析(TG)、极限氧指数(LOI)、UL-94垂直燃烧、烟密度测试、傅立叶红外光谱(FT-IR)及拉曼光谱表征,研究了MCA对硬质聚氨酯泡沫(RPUF)泡孔结构、热稳定性、阻燃性及燃烧烟气密度的影响。研究表明,MCA能够显著提高RPUF/MCA的阻燃性能,30份的MCA使RPUF/MCA30达到UL-94 V-1级别,极限氧指数达到22.0%。热重测试结果表明,MCA的添加使成炭率降低;同时发现,MCA的添加降低了RPUF/MCA泡沫复合材料的初始热分解温度和复合材料的燃烧烟气密度,有效地提高了复合材料火灾安全性能。     

次磷酸铝/三聚氰胺氰尿酸盐阻燃热塑性聚氨酯的性能研究

将次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MCA)复配后添加到热塑性聚氨酯(TPU)中制备阻燃TPU材料,通过氧指数(OI)和垂直燃烧(UL 94)测试研究了材料的阻燃性能,通过热重分析(TGA)技术测定了材料的热稳定性及成炭性能,同时还研究了AHP与MCA不同的质量比对TPU材料性能的影响。结果表明:当AHP与MCA的质量比为1:2,阻燃剂的总添加量为11%时,阻燃TPU材料能通过垂直燃烧UL 94V-0级,OI达到了25.2%。TGA测试结果表明:阻燃剂AHP/MCA的加入对TPU材料的起始热分解温度没有影响,但能提高材料在高温时的热稳定性,同时提高材料的成炭性能。增加的炭层能有效地阻止氧气和热量进入到材料内部,抑制内部可燃性气体的逸出,同时AHP与MCA能释放出难燃气体,稀释氧气及可燃性气体的浓度,从而提高了材料的阻燃性能。     

三聚氰胺氰尿酸盐在聚酰胺共聚物中阻燃机理的探索

1介绍因为在机械、热稳定和电学等方面具有独特的综合性能,聚酰胺(PA)在电工产品中发挥了非常重要的作用。无填充物的聚酰胺可燃性较低,通过添加阻燃剂可以强化这种特性,可以是含卤素或含磷的阻燃剂,也可以是无卤无磷类型阻燃剂。在无卤无磷类型阻燃剂中,三聚氰胺氰尿酸盐(MC)作为电工产品中无填充物聚酰胺的阻燃剂被广泛应用,它不会产生含卤及含磷阻燃剂在使用中都会释放出的腐蚀性酸性物质。MC在较低添加量(约10%)时就能发挥作用,因而可以保持无填充物聚酰胺本身的机械性能和电学性能。但是,当用于阻燃有填充物的聚酰胺时,其阻燃效果并…     

MCA阻燃PA66的研究

通过扫描电子显微镜、热重分析–傅立叶变换红外光谱、差示扫描量热等研究了三聚氰胺氰尿酸盐(MCA)阻燃PA66体系的微观形貌与性能。结果表明,MCA在PA66体系中呈片状分布,但随用量的增加有一定的团聚现象;MCA与PA66存在一定的相互作用而使得MCA和PA66的热稳定性均下降,PA66/MCA体系中第二阶段的分解产物与未加MCA的PA66基本相同;MCA具有异相成核作用但会降低结晶速度。同时考察了不同含量MCA、不同加工助剂、着色剂对材料性能的影响。当MCA质量分数为5%~10%时,阻燃等级达到UL 94 V–0级,同时力学性能较好,加工助剂及着色剂中硬脂酸钙、EBS、络合红R297对阻燃性能没有负面影响,但蒙旦酯蜡、PE基黑种、铁红R206对阻燃性能有负面影响。     

Highly dispersed melamine cyanurate flame‐retardant epoxy resin composites

Ultrafine dispersion of flame retardants in polymer matrices favors improving the performance of flame‐retardant polymers, but is still a challenge on most occasions. In the present research, an efficient method was employed to realize satisfactory dispersion of a nitrogen flame retardant, melamine cyanurate (MCA), in epoxy resin (EP) composites, and meanwhile integrated the synthesis of MCA with the preparation of the flame‐retardant composites. In the conventional technology, EP pre‐polymer glue with added MCA powder (synthesized in water, then dried and pulverized) is used to coat glass fabrics, which are compressed into laminated boards. Here, MCA was synthesized in a good solvent for EP, and then EP pre‐polymer was directly dissolved in the MCA suspension to obtain the in situ synthesized flame‐retardant glue. In this way, MCA could keep perfect dispersion whether in the glue or cured resin. Compared with the conventional addition system easily resulting in the aggregation of MCA particles, the in situ synthesized MCA flame‐retardant system exhibited much better stability of the coating glue, and markedly improved flame retardancy and mechanical properties. © 2016 Society of Chemical Industry     

In situ synthesized and dispersed melamine polyphosphate flame retardant epoxy resin composites

The dispersion of flame retardants in polymer matrix has significant impact on the final properties of the final materials. Homogenous dispersion for additive type flame retardant powder in polymer melt or solution with high viscosity is a challenge all the time. In the present research, melamine polyphosphate (MPP) is employed to flame-retard the epoxy resin (EP). Different from direct addition of MPP powder in viscous EP glue like conventional means, MPP is firstly synthesized by melamine and polyphosphoric acid in a good solvent for EP. Keeping fine and even dispersion of the produced MPP particles, EP prepolymer is added into the MPP containing solution. By this way, perfect dispersion of the flame retardant can be achieved both in the glue and the cured resin. A series of tests such as the particle size analysis, flammability evaluation, and mechanical properties tests are conducted to compare the MPP flame retardant EP obtained by this method and the conventional one. It shows that the in situ synthesis and compounding method can endow the MPP incorporated EP glue system with better homogeneity and stability, hence leading to higher flame retardancy and obviously improved mechanical performance of the final composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47194.     

环氧树脂体系阻燃技术的发展

阐述了改善热固性环氧树脂体系阻燃性能的目的和意义，介绍了环氧树脂体系的阻燃方法。以气相机理和凝聚相机理为基础，讨论了几种常用阻燃剂的阻燃机理。分析了环氧树脂体系阻燃技术的研究现状，指出环氧树脂阻燃技术将向着安全化、复合功能化、新技术化和研究系统化的趋势发展。     

Flame retardancy mechanisms of melamine cyanurate in combination with aluminum diethylphosphinate in epoxy resin

A novel flame-retardant (FR) epoxy (EP) composite based on melamine cyanurate (MCA) and aluminum diethylphosphinate (AlPi) was successfully prepared and its flame retardancy was systematically investigated. Firstly, the facile surface modification was adopted to effectively solve the aggregation of FRs in EP matrix during the curing process. The influence of modified MCA/AlPi on the fire behavior and thermal degradation of EP were studied by using limiting oxygen index (LOI), vertical burning (UL94) tests, thermogravimetric analysis and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The experimental results showed that EP/MCA/AlPi composite achieved UL-94V0 rating and LOI value of 33.0% at the optimum mass fraction of MCA/AlPi of 2/1. The chemical composition and structure of residue were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectrometry and scanning electron microscopy. MCA mainly acted in gaseous phase during the initial combustion stage, and therefore to provide enough time for the formation of carbon layer in condenses phase. As a result, the synergistic effect of MCA and AlPi can effectively promote the formation of the char layer and the FR efficiency. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47223.     

电子模块灌封用柔性阻燃型改性环氧树脂研究

选用柔性环氧树脂、活性增韧剂、磷系列阻燃剂FR-P和复合阻燃剂FR-A对环氧树脂CYD128进行改性,提高环氧树脂的柔韧和阻燃等性能,取得良好的改性效果,成功制备出柔性阻燃环氧电子灌封材料, 有利于解决环氧树脂在电子工程应用过程中的问题。     

Preparation of polyamide resin‐encapsulated melamine cyanurate/melamine phosphate composite flame retardants and the fire‐resistance to glass fiber‐reinforced polyamide 6

In this study, melamine cyanurate (MCA)/melamine phosphate (MP) composite flame retardants were synthesized in the solution of phosphoric acid/polyamide 6 (PA6). Phosphoric acid acted as the solvent of PA6, catalyst of melamine‐cyanurate self‐assembly reaction and reactant of melamine‐phosphoric acid reaction. With the consumption of the acid, the pH value of the system increased, and the solved PA6 precipitated on the surface of the flame retardant particles to form polymeric encapsulation. This technology realized the synthesis and surface modification of the flame retardants in one process. The catalyst and solvent, phosphoric acid, was finally converted into the product MP, and need no an additional removing process. The encapsulated MCA/MP (EMCMP) composite flame retardants were successfully applied in the fire‐resistance to glass fiber (GF)‐reinforced PA6. Because the encapsulated layer of EMCMP was also PA6, good interfacial compatibility and effective dispersion of EMCMP in PA6 resin can be obtained, and the corresponding flame retardant materials showed excellent flame retardancy and mechanical performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1773–1779, 2006     

The effect of morphology on the flame‐retardant behaviors of melamine cyanurate in PA6 composites

Three types of melamine cyanurate (MCA) with micrometer‐size sphere‐like, micrometer‐scale rod‐like, and nanometer‐scale flake‐like morphologies were synthesized by changing the chemical circumstances of the reactions. The microcosmic morphologies of MCA were characterized via scanning electron microscopy and X‐ray diffraction. After the MCAs with different morphologies were incorporated into polyamide 6 (PA6), the flame‐retardant properties of the MCA/PA6 composites were investigated using the limited oxygen index (LOI), UL94, and cone calorimeter tests. The MCA/PA6 composites with nanometer‐scale flake‐like MCA obtained an LOI value of 29.5% and a UL94 V‐0 rating, which were higher than those with micrometer‐size sphere‐like and rod‐like MCAs. However, the different morphologies did not affect the heat release rate, total smoke release, average carbon monoxide yield, and average carbon dioxide yield based on the cone calorimeter. The flame‐retardant mechanism of MCAs with different morphologies was investigated via thermal gravimetric analysis (TGA) and TGA‐Fourier transform infrared spectra. The results show that the different morphologies of MCA resulted in different dispersed evenness of MCA. Further, the nanometer‐scale flake‐like morphology of MCA brought more interactions of hydrogen bond between MCA and PA6, which resulted in the delay of MCA decomposition and the enhancement of MCA flame‐retardant effect. The nanometer‐scale flake‐like MCA had a better performance compared with the other samples because of the delaying and even release of flame‐retardant effect by the decomposition of evenly dispersed MCA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40558.     

环氧树脂纳米阻燃材料研究进展

综述了目前环氧树脂纳米阻燃材料的制备方法,介绍了环氧树脂/层状硅酸盐纳米阻燃材料和环氧树脂/SiO2纳米阻燃材料的优异性能并展望了环氧树脂阻燃材料的应用前景。     

Halogen‐free flame retardant epoxy resins from hybrids of phosphorus‐ or silicon‐containing epoxies with an amine resin

Epoxy–melamine hybrid resins were obtained from in situ polymerization of siliconized (SE500) and phosphorylated (PE690) epoxy resins with hexakis(methoxymethyl)melamine (HMMM). The hybrid resins having HMMM contents less than 15 wt % exhibited high transparency and homogeneity. The compatibilities between SE500 and melamine as well as that between PE690 and melamine were poor than the compatibility between general bisphenol‐A epoxy and melamine. Incorporation of HMMM altered the degradation mechanisms and enhanced the thermal stability of the epoxy resins, especially for PE690 based resins. Excellent flame retardant property was observed with the hybrid resins because of the Si? N and P? N synergisms of flame retardation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1071–1077, 2006     

The investigation on the flame retardancy mechanism of nitrogen flame retardant melamine cyanurate in polyamide 6

Melamine cyanurate (MCA) flame retardant polyamide 6 (PA6) shows good flame retardancy, but the corresponding mechanisms have not been completely understood. In this paper, Fourier transform infrared spectra (FTIR), elemental analysis (EA), scanning electronmicroscope (SEM), energy dispersive scanning (EDS), thermogravimeric analysis (TGA) and pyrolysis-gas chromatogram-mass spectrometer (Py-GC-MS) were conducted to investigate the processes including melt-drip phase, gaseous phase and condensed phase of MCA/PA6 system. Compared with original PA6, it is found that MCA flame retardant PA6 mainly undergoes predominant weak bond-breakage degradation forming oligomers rather than oxidative degradation producing low-boiling point fuel as original PA6 does. The produced oligomers can accelerate the formation of the melt drips which effectively removes the combustion heat and latent fuel, also the self-condensation of these oligomers is advantageous to form stable cross-linking structure, thus greatly consolidating the char layer.