电缆用高阻燃耐热软质PVC的制备及性能研究

以软质PVC为基体,选用氢氧化铝-氢氧化镁(ATH/MDH)为复配阻燃剂、硼酸锌(ZB)为阻燃协效剂及钙锌材料为复合热稳定剂(Ca-Zn),通过共混法对PVC进行改性,制备PVC/ATH/MDH、PVC/ATH/MDH/ZB及PVC/ATH/MDH/ZB/Ca-Zn等软质PVC复合电缆料。分析3种电缆料的阻燃性能、拉伸性能及热稳定性。结果表明:相较纯软质PVC,PVC/ATH/MDH与PVC/ATH/MDH/ZB的阻燃性能提高,拉伸性能显著下降,且热稳定性改善不明显。而PVC/ATH/MDH/ZB/Ca-Zn的阻燃性能显著提升,与纯软质PVC相比,其极限氧指数(LOI)增加34.90%,烟密度等级下降29.50%,复合材料的炭层更连续且致密;PVC/ATH/MDH/ZB/Ca-Zn的拉伸强度和断裂伸长率分别提高1.78%和2.48%。Ca-Zn的添加提高软质PVC的残炭率,热稳定性增强。PVC/ATH/MDH/ZB/Ca-Zn的综合性能最佳。     

Durability of the flame retardance of ethylene-vinyl acetate copolymer cables: Comparing different flame retardants exposed to different weathering conditions

Scientific publications addressing the durability of the flame retardance of cables during their long-term application are rare and our understanding lacks. Three commercial flame retardants, aluminum hydroxide, aluminum diethyl phosphinate (AlPi-Et), and intumescent flame retardant based on ammonium polyphosphate, applied in ethylene-vinyl acetate copolymer (EVA) model cables, are investigated. Different artificial aging scenarios were applied: accelerated weathering (UV-irradiation/temperature/rain phases), humidity exposure (elevated temperature/humidity), and salt spray exposure. The deterioration of cables' surface and flame retardancy were monitored through imaging, color measurements, attenuated total reflectance Fourier transform infrared spectroscopy, and cone calorimeter investigations. Significant degradation of the materials' surface occurred. The flame retardant EVA cables are most sensitive to humidity exposure; the cable with AlPi-Et is the most sensitive to the artificial aging scenarios. Nevertheless, substantial flame retardance persisted after being subjected for 2000 h, which indicates that the equivalent influence of natural exposure is limited for several years, but less so for long-term use. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47548.     

Flame Retardant Synergism of Hydroxy Silicone Oil and Al(OH)3 in EVA Composites

A synergistic effect on flame retardancy was found when hydroxy silicone oil (HSO) was incorporated into ethylene vinyl acetate/aluminum hydroxide (EVA/ATH) composite. The fire performance of EVA and EVA composites was studied by using limiting oxygen index (LOI), UL 94, and cone calorimeter test (CCT). Compared with the EVA/ATH binary composite, the LOI values of the EVA/ATH/HSO ternary composites at the same additive loading are all decreased. The CCT data indicated that the addition of HSO in EVA/ATH system not only reduces the heat release rate, but also prolonged the ignition time of the composite. Thermogravimetric analysis revealed that ATH accelerated the loss of acetic acid, but hydroxy silicone oil assisted to reduce ATH's accelerating effect.     

新型低烟无卤阻燃电缆料的制备及表征

研究了以磷酸三甲苯酯(TCP)、水滑石(LDHs)、氢氧化铝(ATH)复配得到的复合阻燃剂对乙烯-醋酸乙烯酯共聚物(EVM:AV含量大于40%)性能的影响。分别通过氧指数、水平燃烧和拉伸性能测试考察了TCP/LDHs/ATH/EVM复合材料的阻燃性能和力学性能。结果表明,当TCP/LDHs/ATH/EVA为20/35/35/100(质量份数)时,复合材料的极限氧指数(LOI)达到35.2,阻燃级别为FH-1;断裂伸长率达到280%,拉伸强度达到11.0MPa。此复合材料可用于制造阻燃电缆。     

舰船用辐射交联无卤阻燃电缆护套料的研究

应用γ射线辐射交联技术,制备出以乙烯－醋酸乙烯/茂金属聚烯烃弹性体/纳米级改性氢氧化铝（EVA/POE/ ATH）为基材的舰船用无卤阻燃电缆护套料,探讨了共混物配比、ATH的种类与用量以及辐射剂量对材料力学性能和阻燃性能的影响。结果表明,随着POE用量的增加,材料的拉伸强度和断裂伸长率增加,耐热老化性能提高,但硬度降低;纳米ATH的加入使材料具有较好的阻燃性能;材料的辐射交联工艺可弥补阻燃剂对材料力学性能的影响,在辐射剂量为80 kGy的条件下,采用EVA /POE/ATH ＝90/10/60（质量份数,下同）的共混体系可制备出综合性能优异的护套料。     

交联无卤阻燃LLDPE/EVA电缆料的研制

以LLDPE（线性低密度聚乙烯）、EVA（乙烯醋酸乙烯共聚物）为基体树脂，ATH（氢氧化铝）、MH（氢氧化镁）为主阻燃剂，有机硅为阻燃增效剂，EVA-g-MAH（马来酸酐接枝乙烯醋酸乙烯共聚物）为高分子相容剂，DCP（邻苯二甲酸二壬酯）为交联剂制备了交联无卤阻燃LLDPE／EVA电缆料。研究结果表明，在燃烧时有机硅能促进玻璃态无机炭化层隔氧膜的形成，有效地提高共混物的氧指数。以EVA-g-MAH作为共混体系的相容剂能够改善交联无卤阻燃LLDPE／EVA电缆料的加工性能、力学性能和阻燃性能。     

电子束辐照和氢氧化铝对LLDPE/EVA共混物凝胶含量和力学性能的影响

研究了电子束辐照剂量和氢氧化铝(ATH)的含量对线性低密度聚乙烯(LLDPE)/乙烯-醋酸乙烯酯(EVA)共混物凝胶含量和力学性能的影响。辐照剂量是影响LLDPE/EVA/ATH阻燃体系凝胶含量的主要因素,而ATH对其凝胶含量的影响较小。随着ATH含量的增加,LLDPE/EVA共混物的拉伸强度逐步增加,断裂伸长率迅速下降。所有阻燃体系的拉伸强度均是随着辐照剂量的增加而逐步增大,但辐照剂量对这些阻燃体系的断裂伸长率的影响却比较复杂。     

碱式碳酸镁基复合阻燃剂的制备及其阻燃性能研究

采用硅烷表面处理的碱式碳酸镁纳米片和氢氧化镁以及氢氧化铝为复合阻燃剂,通过密炼模压法制备了一系列复配阻燃剂协效阻燃EVA的复合材料。利用拉伸性能测试仪、熔融指数仪、垂直燃烧测试仪和锥形量热仪分别测试了复合材料的力学性能、加工流动性能和阻燃性能,利用热重分析仪测试了复配阻燃剂的热分解行为。结果表明,复配阻燃剂以适当比例协效阻燃EVA在更宽的燃烧温度范围内发生分解,能够起到更好的阻燃效果。并且复配阻燃剂/EVA复合材料的热释放速率和烟释放率大幅度降低,分别为181.06 kW/m²和0.032 m²/s。另外,复配阻燃剂/EVA复合材料的拉伸强度达到9.73 MPa,断裂伸长率为155.07%,每10 min熔融指数为1.00 g,符合电线电缆行业标准。     

Thermal Properties and Flammability of Ethylene-Vinyl Acetate Copolymer/Montmorillonite/Polyethylene Nanocomposites with Flame Retardants

Ethylene-vinyl acetate copolymer (EVA)/montmorillonite (MMT) composite was blended with a linear low density polyethylene (LLDPE). X-ray diffraction and transmission electron microscopy (TEM) image of the EVA/MMT composite are in support of an intercalated with partially delaminated nanocomposite. The tensile strength of the nanocomposite is about 20% higher than that without layered silicates, MMT. Furthermore, the incorporation of MMT into polymer blend delays the main thermo-oxidative degradation. Cone calorimeter test points out that the addition of layered silicates into the pristine EVA/LLDPE blend or the blend with a low smoke non-halogen (LSNH) fire retardants, aluminum trihydroxide, and antimony trioxide, can reduce the maximum heat release rate by 30–40%. The smoke suppressing effect of layered silicates is only observed in the nanocomposite containing flame retardants. According to the limiting oxygen index (LOI) data and cone calorimeter test, the addition of the nanodispersed layered silicate and LSNH flame retardants to the EVA/LLDPE exhibits a synergistic effect on the flame retardancy and smoke suppression.     

Cross-linked poly(ethylene vinyl acetate) (EVA)/low density polyethylene (LDPE)/metal hydroxides composites for wire and cable applications

Formulations of chemically cross-linked poly(ethylene vinyl acetate) (EVA) and low density polyethylene (LDPE) blends containing metal hydroxides flame retardants such as aluminum hydroxide (ATH) and magnesium hydroxide (MH) were prepared. Comparison of both type of metal hydroxides in respect of their influence on flammability as well as mechanical, thermal, and electrical properties of EVA/LDPE composites is presented. Most of the investigated properties are better for composites containing MH in comparison with composites containing ATH. Influence of various EVA/LDPE ratios on investigated properties is presented as well. Importance of improving compatibility using compatibilizers to improve some of the investigated properties is described. Polyethylene grafted with maleic anhydride (PEgMA) was found to be better compatibilizer for ATH than vinyl silanes.     

阻燃剂对UP复合材料流变性及磨损性能的影响

制备了含有氢氧化铝(ATH)、三聚氰胺多聚磷酸盐(MPP)及十溴二苯醚(DBDE)等不同阻燃剂的干式不饱和聚酯/玻璃纤维(UP/GF)共混复合材料。研究了不同阻燃剂对UP/GF复合材料的阻燃性能、流动性和磨损性能的影响,并借助SEM观察了采用不同阻燃剂的UP/GF复合材料的磨损面微观形貌。结果表明,ATH的添加质量为30%时,其UP/GF复合材料的阻燃性与DBDE添加量为25%的体系相当,达到UL94 V-0级,OLI值为30.0且具有很好的抑烟和防滴落效果;同时ATH、MPP的加入可适当提高复合材料流动性能,ATH还可以改善复合材料的磨损性能,磨损体积为未添加阻燃剂体系的50%左右。     

Combustion characteristics of halogen‐free flame‐retarded polyethylene containing magnesium hydroxide and some synergists

Halogen‐free flame‐retarded polyethylene materials have been prepared by using magnesium hydroxide (MH) as a flame retardant combined with red phosphorous (RP) and expandable graphite (EG) as synergists. The effects of these additives on the combustion behavior of the filled linear low density polyethylene (LLDPE), such as a limiting oxygen index (LOI), the rate of heat release (RHR), the specific extinction area (SEA), etc., have been studied by the LOI determination and the cone calorimeter test. The results show that RP and EG are good synergists for improving the flame retardancy of LLDPE/MH formulations. In addition, a suitable amount of ethylene and vinyl acetate copolymer (EVA) added in the formulations can increase the LOI values while promoting the char formation and showing almost no effect on the RHR and SEA values. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 206–214, 2001     

氢氧化铝无卤阻燃乙烯醋酸乙烯共聚物的结构与性能

以表面修饰的氢氧化铝（ATH）作为无卤阻燃剂,以线形低密度聚乙烯接枝物为相容剂制备了阻燃性能和力学性能优良的无卤阻燃乙烯醋酸乙烯（EVA）复合材料。通过扫描电子显微镜、力学性能测试、动态热力学分析、极限氧指数、垂直燃烧测试表征了AHT阻燃EVA复合材料的结构与性能。研究了表面处理及相容剂的引入对ATH在EVA中的分散性和界面相容性的影响,以及AHT粒径大小、添加量对EVA阻燃性能和力学性能的影响。结果表明,界面相容剂和表面处理剂同时使用,能显著提高ATH与基体之间的界面相容性,从而提高了EVA的力学性能和阻燃效果,ATH尺寸越小,阻燃性能越好。     

A novel phytic acid based flame retardant to improve flame retardancy,hydrophobicity and mechanical properties of linear low-density polyethylene

Exploiting high phosphorus content of phytic acid, it was grafted onto magnesium hydroxide (MH) by neutralization reaction to obtain MGPA, a flame retardant. A current study investigated the effect of MGPA on hydrophobicity, flame retardancy, and mechanical properties of MGPA-linear low-density polyethylene (LLDPE) composites. The LLDPE composite with 50 parts of MGPA has the better flame retardancy and thermal stability with a limiting oxygen index of 23.3%, which is higher than that of neat LLDPE (17%). In addition, MGPA could effectively promoted LLDPE to form a continuous and compact char residue during combustion, which reduce the peak of heat release rate and total smoke production value of LLDPE composite by 70% and 36%, respectively, and the char residue rate increase to 67.5%. Furthermore, the maximum of loss-rate showed by LLDPE composite with MGPA reduce to 1.25%/min while the value of LLDPE composite with MH is 1.8%/min. Meanwhile, the LLDPE composite with MGPA show remarkable elongation at break and hydrophobicity, which are 398% and 99°, respectively. In addition, this study presents a substantial flame retardancy and interfacial compatibility of MGPA for extending the applications of flame-retardant LLDPE composites.     

科琴黑对聚乙烯/氢氧化铝材料热稳定性和阻燃性能的影响

将具有独特支链状的科琴黑(KB)与聚乙烯(PE)和氢氧化铝(ATH)通过熔融共混的加工方式得到聚乙烯/氢氧化铝/科琴黑复合材料,并对复合材料的热稳定性、阻燃性能和力学性能进行研究。科琴黑的加入提高了复合材料的初始分解温度,降低了复合材料的热释放速率,延缓了聚乙烯的燃烧过程。在提高复合材料热稳定性能和阻燃性能的同时,科琴黑同时还提高了材料的拉伸性能。     

OMMT和EG/MH协同阻燃LLDPE的研究

采用氢氧化镁(MH)、膨胀石墨(EG)和有机蒙脱土(OMMT)为阻燃剂制备了无卤阻燃线性低密度聚乙烯(LLDPE),研究了OMMT对LLDPE/EG/MH阻燃性能和力学性能的影响。结果表明:少量OMMT的加入,可以有效改善LLDPE/EG/MH的力学性能、阻燃性能和热稳定性。当OMMT质量分数为3.0%时,LLDPE/EG/MH/OMMT的拉伸强度和冲击强度分别为1.4 MPa和26.5 kJ/m~2;极限氧指数为35.0%,符合UL-94 V-0级;其热释放速率峰值、平均热释放速度、生烟速率和总生烟量比LLDPE/EG/MH的低。     

Effects of silicon additive as synergists of Mg(OH)2 on the flammability of ethylene vinyl acetate copolymer

The present work dealt with the effects of nine kinds of silicon additives on flame retardancy of ethylene‐vinyl acetate copolymer (EVA)/magnesium hydroxide [Mg(OH)₂] composites, as well as mechanical properties. The limiting oxygen index (LOI) test, horizontal fire test, vertical fire test, and cone calorimeter test were employed to evaluate flame retardancy of the composites. It was found that different silicon additives had different synergistic effects with Mg(OH)₂ on flame retardancy of the EVA matrix and exerted different influences on mechanical properties of the composites. The incorporation of organic montmorillonite (MMT) clay or silicone rubber not only made the composite reach FH‐1 rating in the horizontal fire test and FV‐1 rating in the vertical fire test, respectively, but also dramatically reduced the peak rate of heat release (Peak RHR) and increased the fire performance index (FPI) and ignition time (IT). The composites filled with precipitated SiO₂ exhibited the longest IT, the highest FPI, and FV‐1 rating. However, only the composites filled with silicone rubber could attain a balance between mechanical properties and flame retardancy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synergistic effects of aluminum hydroxide on improving the flame retardancy and smoke suppression properties of transparent intumescent fire-retardant coatings

A series of novel aluminum phosphate ester (APEA) flame retardants were synthesized by the salification of cyclic phosphate ester acid (PEA) with different mass ratios of aluminum hydroxide (ATH) and thoroughly characterized by Fourier transform infrared (FTIR) spectroscopy and ¹H nuclear magnetic resonance spectroscopy. The PEA and APEAs were thoroughly mixed with melamine formaldehyde resin to produce five kinds of transparent fire-retardant coatings. The synergistic effects of ATH on the thermal stability, flame retardancy, and smoke suppression properties of the coatings were investigated by different analytical instruments. The results show that the incorporation of ATH greatly decreases the weight loss, char index, flame spread rating, heat release rate, total heat release, smoke production rate, total smoke release and specific optical density in the coatings applied to plywood boards, which is ascribed to a more compact and intumescent char formed during burning, as determined from digital photographs and scanning electron microscopy images. The synergistic effects of ATH in the coatings depend on the content of ATH, and an excessive amount of ATH diminishes the synergistic effects on the flame retardancy and smoke suppression properties based on fire protection tests and cone calorimeter test. Thermo-gravimetric analysis reveals that the thermal stability and char-forming ability of the coatings gradually improve with increasing loading of ATH. FTIR analysis demonstrates that the incorporation of ATH forms a more phosphorus-rich crosslinked char and aromatic char during burning, thus effectively reducing the mass loss, heat release, and smoke production and exhibiting excellent synergistic flame retardant and smoke suppression effects in the coatings.     

Dielectric behavior of aluminum hydroxide‐filled oil‐extended ethylene‐propylene‐diene‐monomer rubber composites in microwave fields

Oil‐extended ethylene‐propylene‐diene rubber composites were prepared with aluminum hydroxide (ATH) and high abrasion furnace carbon black. The dielectric properties at microwave frequencies of the samples were measured in the S (2–4 GHz) band using cavity perturbation technique. The thermal stability of the composites was studied using thermogravimetric analysis. The morphology of the composites was investigated by scanning electron microscopic studies. The fire retardancy of the composites was identified through the limiting oxygen index and horizontal burning test (UL94 HB). The dielectric permittivity, AC conductivity, and absorption coefficient of the highly ATH loaded systems are much greater than the unfilled and lower systems. At higher loading, the dielectric heating coefficient and skin depth were found to decrease significantly. The incorporation of ATH was found to improve the thermal stability and flame retardancy of EPDM. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

基于磷杂菲衍生物多组分无卤阻燃天然橡胶的制备及性能

将磷杂菲/三嗪双基协同阻燃剂（TGD）、甲基膦酸二甲酯（DMMP）、可膨胀石墨（EG）及氢氧化铝（ATH）复配添加到天然橡胶（NR）中制备阻燃NR硫化胶,考察了TGD/DMMP/EG/ATH复配阻燃剂对NR硫化胶的阻燃性能、热稳定性及物理机械性能的影响。结果表明,TGD/DMMP/EG/ATH复配阻燃剂可有效提升NR硫化胶的阻燃性能和热稳定性,并降低燃烧过程中的热释放速率。当TGD/DMMP/EG/ATH复配阻燃剂的用量为60份（质量）时,NR硫化胶的极限氧指数可达28.4%,残炭质量分数可达25.61%,热释放速率可降低95%,总热释放量可降低21%。TGD/DMMP/EG/ATH复配阻燃剂对NR硫化胶的物理机械性能影响不大。