金属离子改性阻燃尼龙66的性能研究

三聚氰胺聚磷酸盐是一种重要的氮磷复合型阻燃剂,采用溶剂法制备出金属离子改性的三聚氰胺聚磷酸盐(J-MPP),并利用红外光谱分析(FTIR)、X射线衍射分析(XRD)、热失重分析(TGA)、扫描电镜(SEM)进行了产物结构表征。结果表明,J-MPP阻燃尼龙66(PA66)具有良好的阻燃效果,但对力学性能产生一定影响。在添加25%的铝离子改性三聚氰胺聚磷酸盐(Al-MPP)和20%的钙离子改性三聚氰胺聚磷酸盐(Ca-MPP)时,阻燃改性复合材料均可达到UL94 V-0级(3.2 mm);但随着阻燃剂添加量的增加,Al-MPP阻燃PA66体系的力学性能下降严重,Ca-MPP阻燃体系的力学性能先上升后下降,在添加量为20%时,力学性能最优。     

原位聚合无卤阻燃聚酰胺6的结构与性能研究

采用原位聚合添加反应型无卤阻燃剂,是实现聚己内酰胺(PA6)阻燃改性的主要方法。在己内酰胺的水解开环聚合体系中,加入三聚氰胺氰尿酸盐(MCA)的原料单体,原位聚合制备了阻燃PA6(FRPA6),对FRPA6的结构、形貌及性能进行了表征;通过熔融纺丝制备了FRPA6纤维,测试了其力学性能及阻燃性能。结果表明:FRPA6中阻燃剂MCA与PA6基体的相容性良好,MCA自组装反应比较充分,MCA粒子以纳米级均匀分布于PA6基体中;随着MCA含量的增加,FRPA6的熔点、熔融热焓有所降低,结晶温度略有升高,热稳定性下降;当MCA质量分数为7.5%时,FRPA6的阻燃性能达UL94 V-0级,拉伸强度为64.1 MPa,缺口冲击强度为10.4 k J/m2;相比纯PA6纤维,FRPA6纤维具有较好的阻燃性能,极限氧指数达35%以上,但力学性能有所下降。     

包覆型MCA/PA6复合材料的制备及其阻燃性研究

以水为反应介质、无水乙醇为溶剂,将正硅酸四乙酯(TEOS)制备成二氧化硅(SiO_2)溶胶,利用溶胶的网络结构对三聚氰胺氰尿酸盐(MCA)进行表面包覆,制备出包覆型MCA阻燃剂;通过熔融共混方式,将包覆前后MCA与聚己内酰胺(PA 6)切片混合制备成不同阻燃剂含量的阻燃PA 6复合材料;采用红外光谱仪X射线光电子能谱仪、差示扫描量热仪、热重分析仪、垂直燃烧法和极限氧指数法等研究了阻燃PA 6复合材料的结构、热性能及阻燃性能。结果表明:SiO_2溶胶成功接枝在MCA表面,且主要分子结构没有发生改变;随着阻燃剂含量的增加,PA 6复合材料的熔点均有降低,但下降幅度较小;包覆型MCA在材料燃烧过程中能够有效参与成炭,在材料表面形成致密的保护层,增强PA 6复合材料的凝聚相阻燃效果,提高其阻燃性能;随着阻燃剂含量增加,PA 6复合材料的阻燃性逐步提高,添加包覆型MCA质量分数为8%时,PA 6复合材料阻燃性可达到UL-94 V-0等级,极限氧指数为28%。     

花球状锆酸酯改性氢氧化镁/MCA协同阻燃PA6性能

将硬脂酸和硬脂酸钙作为复合改性剂,制得改性氢氧化镁(MH),并用偶联剂(Zr-801)对所得到的粉体进行表面包覆,通过重组自组装合成花球状锆酸酯改性MH。以聚酰胺(PA6)为基体,三聚氰胺氰尿酸盐(MCA)为主阻燃剂,锆酸酯改性MH为协效阻燃剂,制备了PA6复合材料。研究和对比了锆酸酯改性MH的添加量对复合材料阻燃性能和力学性能的影响,并分析了其阻燃机理。结果表明,锆酸酯改性MH的加入能有效提高体系的力学性能,且添加质量分数6%时达到最优;复合材料的氧指数增大,熔滴现象减弱,成炭效果好,综合阻燃性能提高。     

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。     

无机填料对PA6/MCA阻燃复合材料性能的影响

研究了不同种类的无机填料(硅灰石、碳酸钙)对尼龙6(PA6)/三聚氰胺氰尿酸盐(MCA)阻燃复合材料性能的影响。阻燃性能测试结果表明,PA6/MCA/硅灰石阻燃复合材料为UL94 V–0级,比PA6/MCA阻燃复合材料(V–2级)有显著提高;然而PA6/MCA/碳酸钙阻燃复合材料的极限氧指数却有所下降。扫描电子显微镜测试分析表明,PA6/MCA/硅灰石阻燃复合材料燃烧后的表面炭层呈连续、致密状;PA6/MCA/碳酸钙阻燃复合材料的表面炭层有很多孔洞,且孔洞直径大。傅立叶变换红外光谱测试结果表明,PA6/MCA/硅灰石阻燃复合材料的表面炭层与Si O2能很好地结合,形成致密的保护层,致使其阻燃性能显著提高。另外,力学性能测试结果表明,硅灰石能够提高PA6/MCA阻燃复合材料的拉伸强度,但降低了缺口冲击强度,而碳酸钙的加入却使得PA6/MCA阻燃复合材料的综合力学性能有所下降。     

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.     

原位聚合型阻燃尼龙6纤维的制备及性能研究

利用原位聚合的方式,在己内酰胺水解聚合体系中引入三聚氰胺氰尿酸盐(MCA)阻燃剂,一次性制备出MCA/尼龙6(PA6)阻燃复合材料。利用这种复合材料进行熔融纺丝,通过扫描电镜(SEM)考察了阻燃纤维的相容性。MCA粒子在PA6基体树脂中均匀分布,没有发生团聚现象。通过测定阻燃纤维的力学性能,发现MCA加入量在7.2%和10.0%的阻燃纤维的断裂强度与断裂强力都有一定程度的降低,但断裂伸长率变大。阻燃剂含量在7.2%和10.0%的MCA/PA6阻燃纤维极限氧指数(LOI)能达到35%以上,具有较佳的阻燃性能。     

阻燃热塑性聚酯弹性体复合材料制备及性能

以二乙基亚膦酸铝盐(AlPi)和三聚氰胺氰脲酸盐(MCA)为阻燃剂,添加到热塑性聚酯弹性体(TPEE)中,采用挤出造粒方法制备出高性价比的阻燃TPEE复合材料。首先采用热失重分析仪研究了两种阻燃剂的热稳定性,进一步采用热失重分析、极限氧指数测试、垂直燃烧测试、力学性能测试以及扫描电子显微镜等对阻燃TPEE材料的热稳定性、阻燃性能、燃烧性能、力学性能以及复合材料的微观形貌进行了研究。结果表明,在相同阻燃剂用量下,添加AlPi的阻燃复合材料的阻燃效果、力学性能均优于添加MCA的阻燃复合材料,采用AlPi与MCA复配使用制备的阻燃TPEE复合材料的阻燃效果、力学性能介于二者之间,当TPEE,AlPi和MCA用量分别为83%,10%和5%时,阻燃复合材料的拉伸强度为24.19 MPa,断裂伸长率为515%,极限氧指数为30%,垂直燃烧测试达到V–0级。AlPi与MCA复配使用可提升阻燃TPEE材料的成炭性能和高温热稳定性。     

SA／CaSt改陛氯氧化镁／MCA阻燃抗熔滴PA6的性能研究

以硫酸镁与氨水为原料,采用硬脂酸／硬脂酸钙作为复合改性剂,合成改性氢氧化镁阻燃剂。将制备的改性氢氧化镁与三聚氰胺氰尿酸盐（MCA）添加到尼龙（PA6）中,通过挤出造粒制备复合阻燃（PA6）。分别研究不同阻燃剂配比对复合材料力学性能、耐热性能、阻燃性能及机理的影响。结果表明：随着MCA／改性氢氧化镁比例的增大,复合阻燃PA6的拉伸性能与冲击性能均先上升后下降,当两者比例为1：1时,力学性能达到最优。同时,两阻燃剂协同作用,使尼龙6阻燃机理由解聚分解转化为直接炭化分解,有效抑制燃烧流滴现象,提高了复合材料的综合阻燃性能。     

Preparation and characterization of flame‐retardant melamine cyanurate/polyamide 6 nanocomposites by in situ polymerization

This article focuses on an improved method, i.e., improved in situ polymerization of ε‐caprolactam in the presence of melamine derivatives to prepare flame‐retardant melamine cyanurate/polyamide 6 (MCA/PA6) nanocomposites. The chemical structures of these synthetic flame retardant composites are characterized by Fourier‐transform infrared spectroscopy and X‐ray diffraction. Morphologies, mechanical properties, and thermal properties also are investigated by the use of transmission electron microscopy, mechanical testing apparatus, differential scanning calorimetry, and thermogravimetric analysis, respectively. Through transmission electron microscopy photographs, it can be found that the in situ‐formed MCA nanoparticles with diametric size of less than 50 nm are nanoscaled, highly uniformly dispersed in the PA6 matrix. These nanocomposites, which have good mechanical properties, can reach UL‐94 V‐0 rating at 1.6‐mm thickness even at a relatively low MCA loading level. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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。     

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     

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。     

Effect of halloysite nanotubes on thermal and flame retardant properties of polyamide 6/melamine cyanurate composites

In this study, polyamide 6 (PA6) with various contents of halloysite nanotubes (HNTs) and melamine cyanurate (MCA) were prepared by a twin‐screw extruder. The flame retardant and physical properties of PA6 composites were examined. X‐ray diffraction (XRD) patterns of PA6/HNTs and PA6/MCA/HNTs composites showed that HNTs as a nanoscale material dispersed in PA6 whether with MCA or not. Thermo gravimetric analyzer (TGA) results showed the presence of HNTs can improve thermal stability of PA6 and PA6/MCA composites. The incorporation of HNTs seemed to result the increase of crystallinity of PA6 and PA6/MCA composites from the differential scanning calorimetry (DSC) results. The combined of HNTs and MCA that leads to further improvements limiting oxygen index (LOI) value of PA6 to 31.7% exerted a positive effect on flame retardancy of PA6. What's more, some mechanical enhancements of PA6 with adding of HNTs were achieved and HNTs also made the tensile properties of PA6/MCA composites improved. POLYM. COMPOS., 36:892–896, 2015. © 2014 Society of Plastics Engineers     

Melamine cyanurate surface treated by nylon of low molecular weight to prepare flame‐retardant polyamide 66 with high flowability

In the present research, a nitrogen‐based flame‐retardant, melamine cyanurate (MCA) was surface‐treated with low‐molecular‐weight nylon through a solvent process to further improve its flowability and dispersion. The surface energy and flow energy of the modified MCA were investigated. The properties of polyamide 66 (PA66) prepared with surface‐treated and with conventional MCA were evaluated and compared. Because of lower surface energy and flow energy for modified MCA, its agglomeration degree and flow resistance are obviously decreased compared with conventional MCA, thus achieving finer and more homogenous dispersion in the PA66 matrix. Moreover, the low‐molecular‐weight nylon resin encapsulating MCA surface will melt at lower temperature during compounding with PA66; hence, it serves as a lubricant and carrier to further improve the flowability and dispersion of the flame retardants. Based on these advantages, the modified MCA flame‐retardant PA66 achieves much better flame retardancy, flowability, and mechanical properties compared with conventional MCA/PA66 under the same loading level of flame retardant (10 wt%).     

三聚氰胺氰尿酸盐/聚氨酯复合阻燃聚甲醛的研究

采用三聚氰胺氰尿酸盐／聚氨酯复合阻燃剂阻燃聚甲醛，阻燃剂粒子超细均匀分散于分散相聚氨酯中，解决了非复合阻燃剂与聚甲醛直接共混相容性差、材料性能劣化的难题．获得了阻燃性能和力学性能优良的阻燃聚甲醛材料，并通过热失重和气质联用分析研究了其阻燃机理。     

水滑石对MCA阻燃PA6性能的影响

研究了水滑石对三聚氰胺氰尿酸盐(MCA)阻燃聚酰胺(PA6)的力学性能、热稳定性和阻燃性能的影响,讨论了水滑石在MCA阻燃PA6热分解历程和燃烧过程所发挥的作用。结果表明,随着水滑石用量从0%增加到15%,MCA阻燃PA6复合材料的拉伸强度从73 MPa下降到65 MPa,降幅约11%,冲击强度从40 J/m下降到34 J/m,降幅为15%。随着水滑石用量增加,MCA阻燃PA6的复合材料的热稳定性能下降,但材料的防火性能得到提高,另外,随着水滑石用量从0%增加到15%,M CA阻燃PA6的极限氧指数从32%升高到36%。     

阻燃玻璃纤维增强PA6的紫外光稳定性

分别将三聚氰胺氰尿酸盐、十溴二苯乙烷、溴化聚苯乙烯和次磷酸盐作为阻燃剂对尼龙6(PA6)进行阻燃玻璃纤维增强改性,采用热失重分析仪、水平垂直燃烧测定仪、分光测色仪对PA6复合材料的热降解行为、阻燃性能和紫外光老化后色差值(△E)进行了分析.结果表明,阻燃剂的引入提升了PA6复合材料的阻燃性能,但是降低了复合材料的热稳定...     

一种高效无卤阻燃PBT复合材料的制备及性能

以次磷酸盐类复合物TF9309为主阻燃剂,三聚氰胺氰尿酸盐(MCA)为协效阻燃剂,采用增韧剂AX8900、偶联剂KH–560和30%的玻璃纤维对聚对苯二甲酸丁二酯(PBT)进行共混挤出改性,研究了无卤阻燃剂用量和不同复配比例对PBT燃烧行为和综合性能的影响,考察了增韧剂和偶联剂对复合材料力学性能的影响。结果表明,当TF9309与MCA两者复配比例为4∶1,总含量为15%,AX8900含量为2%,加入适量偶联剂KH–560时,30%玻纤增强PBT复合材料的阻燃性能和力学性能最佳。