尼龙基MCA母粒的制备及其在阻燃尼龙的应用

针对三聚氰胺氰尿酸盐(MCA)粉体对尼龙(PA)进行阻燃改性时,MCA分散性差,材料阻燃性能不稳定的问题,运用特殊的包覆工艺成功制得了PA基MCA母粒。将制得的MCA母粒及MCA粉体分别与PA6或PA66共混挤出,制得阻燃PA材料。对比分析了MCA母粒及MCA粉体阻燃PA6或PA66的垂直燃烧性能和力学性能。结果表明,与MCA粉体相比,MCA母粒可在MCA含量较低的情况下使厚度为0.8 mm及1.6 mm的阻燃PA6或PA66试样的垂直燃烧等级达到V–0级。MCA母粒及粉体对阻燃PA6的弯曲强度和PA66的拉伸强度影响很小,MCA母粒阻燃PA6的拉伸强度较粉体阻燃的高,而阻燃PA66的弯曲强度低;MCA母粒使阻燃PA的缺口冲击强度降低,而MCA粉体对PA的缺口冲击强度影响较小,当MCA含量较低时,MCA母粒阻燃PA的缺口冲击强度明显高于MCA粉体阻燃的PA。制备的MCA阻燃母粒对PA的阻燃效果不受黑色母料的影响,且具有较好的阻燃稳定性。     

电子电器用MCA阻燃PA66的研制

应用不同厂家的三聚氰胺脲酸盐(MCA)阻燃尼龙(PA)66,筛选出满足PA66加工条件的MCA,考察了其用量及表面处理对PA66阻燃性能和力学性能的影响,并对MCA阻燃PA66进行增韧改性研究.结果表明,E厂家提供的MCA满足PA66的加工条件,且其堆密度和白度较为优良.采用E厂家的MCA,当其用量为12～14份时阻燃...     

改性MCA的固相合成及其在PA6中的应用

本实验选用一种新的方法合成改性三聚氰胺氰尿酸盐(MCA),将三聚氰胺(MA)、氰尿酸(CA)和极少量水混合成膏状物并使其在室温下反应一定时间,再加入少量MCA和二氧化硅(Si O2)溶胶使其继续反应以制备改性MCA(mMCA)阻燃剂。将制备的mMCA与尼龙6(PA6)熔融共混制备阻燃PA6复合材料。用FTIR、XRD和TG对所制mMCA进行了表征,对阻燃PA6复合材料的阻燃性能和力学性能进行了测试。结果表明:所制mMCA的FTIR、XRD特征峰与MCA的特征峰一致;m MCA的最大热失重温度有了较大的提升达到465.2℃。在PA6复合材料中,当阻燃剂含量为13%时,阻燃PA6复合材料的极限氧指数(LOI)达到33%,阻燃性能为UL-94 V0级,锥形量热测试的PHRR降低了26.3%。随着阻燃剂含量的增加,复合材料的力学性能有所提高。与传统大量水体系制备mMCA方法相比,此法具有工艺简单、不需加热、耗水量极低,没有污水排放等优点。     

三聚氰胺氰尿酸盐/聚氨酯复合阻燃剂阻燃PA66的研究

采用三聚氰胺氰尿酸盐(MCA)/聚氨酯(TPU)复合阻燃剂阻燃PA66,解决了单独使用MCA阻燃PA66熔滴引燃脱脂棉问题,可使1．6 mm样条通过UL94V-0级别；研究了MCA/TPU复合阻燃剂阻燃PA66的阻燃机理,考察了阻燃材料的力学性能。     

阻燃增强增韧尼龙66的制备及工艺研究

以十溴二苯醚和氮磷复合物为阻燃剂,以玻璃纤维为增强剂,加入自制增韧剂,制备了阻燃增强增韧尼龙(PA)66材料,并对其阻燃性能和力学性能进行了表征,研究了加工工艺对改性PA66材料性能的影响。     

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     

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     

新型阻燃技术在尼龙6中的应用

将一种新型阻燃促进剂与氮系阻燃剂MCA复配用于尼龙6的阻燃。实验结果表明，当MCA用量为16份时，氧指数可达30％以上，而且对环境无污染。同时阻燃促进剂的加入，克服了燃烧时熔融淌滴现象，且当阻燃促进剂KON3与阻燃剂配比适宜时，燃烧时残留物易形成致密的炭层。     

氮–磷协效阻燃聚酰胺66制备与性能

为改善聚酰胺66(PA66)的阻燃性能,以氮系阻燃剂三聚氰胺氰尿酸盐(MCA)和磷系阻燃剂9,10–二氢–9–氧杂–10–磷酰杂菲–丁二酸(DDP)协效,将原位聚合法与共聚法结合,经熔融缩聚制备氮-磷协效阻燃PA66树脂。利用傅立叶变换红外光谱仪、差示扫描量热仪、万能材料试验机、垂直燃烧仪和极限氧指数仪等研究阻燃PA66树脂的结构与性能。结果表明:随DDP含量的增加,阻燃PA66的相对黏度、熔点、结晶度和力学性能均呈下降趋势。当MCA含量为2%,DDP含量为4%时,阻燃PA66(FRPA66–4)的熔点、结晶温度和结晶度分别降至250.78℃,203.74℃,29.21%,FRPA66–4的拉伸强度和断裂伸长率分别下降为68.8 MPa和69.5%,比PA66降低了17.01%和17.46%。但PA66的阻燃性能得到改善,FRPA66–4的垂直燃烧测试达UL94 V–0级,极限氧指数为30.6%,阻燃效果良好。     

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。     

Thermal stability,flame retardance,and mechanical properties of polyamide 66 modified by a nitrogen–phosphorous reacting flame retardant

Flame‐retardant polyamide 66 (PA66) was prepared by the polymerization between PA66 prepolymer and N‐benzoic acid (ethyl‐N‐benzoic acid formamide) phosphamide (NENP). Compared with the pure PA66, the flame‐retardant PA66 exhibited better thermal stability, as indicated by thermogravimetric analysis results. The limiting oxygen index was 28% and the UL‐94 test results of the flame‐retardant PA66 indicated a V‐0 rating when the content of the NENP prepolymer was 5 wt %. The flammability and flame‐retardant mechanism of PA66 were also studied with cone calorimetry and scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, respectively. The mechanical properties results show that the flame‐retardant PA66 resin had favorable mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43538.     

Preparation of microencapsulated red phosphorus through melamine cyanurate self‐assembly and its performance in flame retardant polyamide 6

A novel technology was developed to prepare microencapsulated red phosphorus (RP) with a coating of melamine cyanurate (MCA) serving as both a nitrogen‐containing flame retardant and as a solid lubrication agent. We took advantage of the self‐thickening effects during the MCA self‐assembly process to realize effective encapsulation on the surface of predispersed RP powder. The technology described in this article can overcome several drawbacks of current microencapsulation processes including (1) relatively complicated preparation processes, (2) use of formaldehyde or other noxious modifiers, and (3) poor compatibility with flame retardant fillers and polymer matrix resulting in poor physical properties. Additionally, this novel technology can also modify various properties of RP with regard to lubrication performance, ignition point, moisture absorption ratio, and color. As a composite system of flame retardant phosphorus encapsulated by a nitrogen‐containing flame retardant, the microencapsulated RP showed nitrogen‐phosphorus (N‐P) synergism with further improved flame retardancy. The action and mechanisms of the microencapsulated RP flame retardant polyamide 6 (PA6) were investigated by limiting oxygen index, vertical burning experiment (UL94), thermogravimetric analysis, and scanning electron microscope observations. The results indicated that the flame retardant PA6 possessed desired flame retardancy because of effective char‐formation of the condensed phase and it also showed satisfactory mechanical properties as the result of the good compatibility between flame retardant and PA6 resin. POLYM. ENG. SCI., 46:1548–1553, 2006. © 2006 Society of Plastics Engineers     

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.     

改性三聚氰胺氰尿酸盐阻燃环氧树脂研究

采用分子复合技术合成了改性MCA(M-MCA)阻燃环氧树脂,采用UL94垂直燃烧测试及微型量热分析对其性能进行了研究,同时采用热失重分析方法研究其降解历程和阻燃机理。结果表明,该材料实现了阻燃剂粒子在环氧溶液及基材中超细及均匀分散,解决了常规MCA阻燃剂在环氧树脂胶液中分散困难、易团聚等问题,改性MCA阻燃树脂比传统MCA具有更佳阻燃效果,该体系阻燃机理以气相阻燃为主。     

水滑石对PBS/Sb2O3阻燃PA6/GF性能的影响

研究了聚溴化苯乙烯(PBS)对玻纤增强尼龙6(PA6/GF)阻燃和力学性能的影响,并采用锥形量热仪研究了改性水滑石(HT)对PBS/Sb2O3阻燃PA6/GF抑烟作用和燃烧时热释放速率的影响。结果表明,随PBS用量增加,PA6/GF的氧指数增加,阻燃性提高,当PBS质量分数为20%时,PA6/GF的垂直燃烧达到FV-0级;HT燃烧后形成多孔、大比表面积的镁铝复合氧化物,能够有效吸附材料燃烧过程中产生的炭微粒,对PBS/Sb2O3阻燃PA6/GF具有显著的抑烟作用。当HT质量分数为5%时,烟释放速率降低27.6%,且对阻燃PA6/GF的力学性能影响不大。另外,HT使PA6/GF的氧指数和相比漏电起痕指数(CTI)提高。     

无卤阻燃增强PA66的研制及其应用

以包覆红磷和三聚氰胺氰尿酸(MCA)作为协效阻燃剂,玻璃纤维作为增强体系,加入增容剂和其它添加剂,制备了一种无卤阻燃增强尼龙(PA)66材料.从阻燃性能、热性能、力学性能等方面表征两种阻燃剂的协效作用;探讨了增容剂的加入对复合体系性能的影响.结果表明,当PA66增强料、包覆红磷、MCA、增容剂的质量比为100∶15∶5∶6时,复合材料具有较好的阻燃性能和力学性能.该材料已广泛应用于电子、电器领域.     

阻燃增强尼龙66表面质量改善的研究

采用溴化聚苯乙烯(BPS)作为阻燃剂,短玻纤和玻璃微珠作为增强体系,与尼龙66(PA66)共混,经双螺杆挤出机挤出,制备了高表面质量、力学性能优良的阻燃增强PA66复合材料.研究结果表明,添加19份BPS后,PA66可以达到V-0级别的阻燃效果.使用0.8份硅酮润滑剂对PA66的表面质量有一定改善,并且对力学性能影响很小.将玻璃微珠与短玻纤复配,一定程度上可以改善PA66的表面质量,但玻璃微珠对PA66力学性能有不利影响,因此用量不能太大,控制在5份以内.     

阻燃低气味增强尼龙的研究

制备了阻燃低气味的增强尼龙。分析了玻纤加入、尼龙类型和尼龙处理方式对尼龙力学性能的影响;并研究了阻燃剂种类和用量对玻纤增强尼龙性能的影响,最后研究了除味剂种类和用量对玻纤增强尼龙性能的影响。结果表明:短纤增强PA66具有较高的刚性和韧性;PA66经烘烤后所得玻纤增强PA66的刚性较高,而PA66不经烘烤所得玻纤增强PA66的韧性较高;红磷对玻纤增强的PA66阻燃效果好,且不对其力学性能产生影响;随着红磷阻燃母粒用量的增加,玻纤增强PA66的阻燃性能先变好后变差,在红磷用量为21份时达到最佳;凹凸棒石和红磷对玻纤增强PA66有优异的协同阻燃作用,当凹凸棒石用量为在4份时,达到最佳。SW-120和尼龙塑料除味剂同时使用,对玻纤增强PA66的气味有显著的改善。     

硼酸锌对氮磷协效阻燃玻纤增强尼龙66性能的影响

为提高三聚氰胺聚磷酸盐(MPP)和二乙基次膦酸盐(OP)协效阻燃玻纤(GF)增强尼龙66(PA66)的综合性能,引入少量的无机阻燃剂硼酸锌(ZB)作为协效剂,系统研究了不同添加量的ZB对阻燃材料的阻燃性能、热稳定性、力学性能和白度的影响。结果表明,当MPP和OP的总添加量为15%,复配0.5%的ZB时,阻燃GF增强PA66的垂直燃烧阻燃等级达到UL94 V–0级,且热释放总量由MPP/OP体系的15.4 k J/g降为13.7 k J/g;ZB的引入促进了连续、致密炭层的形成,增强了凝聚相阻燃;ZB增强了阻燃材料的热稳定性,ZB复配量为1.0%的阻燃材料的初始降解温度提高到了301℃,有效避免了加工过程中的降解;当ZB添加量为1.0%时,阻燃材料的拉伸强度和缺口冲击强度分别为100.9 MPa和4.22 k J/m~2,均优于未添加阻燃剂的纯GF增强PA66;同时,样品的白度得到了明显提升,有利于阻燃GF增强PA66的工业化应用。     

Preparation and Combustion Properties of Flame Retardant Nylon 6/Montmorillonite Nanocomposite

Flame retardant Nylon 6 (PA6)/montmorillonite (MMT) nanocomposites have been prepared using direct melt intercalation technique by blending PA6, organophilic clay and conventional fire retardants, such as the melamine cyanurate (MCA) and the combination of decabromodiphenyl oxide (DB) and antimony oxide (AO). Their morphology and combustion properties are characterized by XRD, transmission electron microscopy (TEM), UL‐94 test and Cone Calorimeter experiments. The flame retardant nanocomposites with MCA or DB and AO show lower heat release rate (HRR) peak compared to that of conventional flame retardant PA6. Meanwhile, the synergetic effect was studied between clay and DB‐AO.

TEM of PA‐n nanocomposite.