膨胀型阻燃剂在橡胶中的应用

介绍了膨胀型阻燃剂的组成及功能改进,总结了膨胀型阻燃剂在天然橡胶、三元乙丙橡胶、丁苯橡胶及氯丁橡胶中的应用进展,并对膨胀型阻燃剂的发展方向做了展望。     

茶皂素基膨胀型阻燃剂的制备及其在涂料中的应用

采用多羟基、多羧基的活性天然产物茶皂素为原料,与聚磷酸铵和季戊四醇在一定条件下反应,制备一种聚磷酸酯类茶皂素基三位一体新型环保膨胀型阻燃剂。采用傅里叶红外分析技术对阻燃剂进行了结构表征,采用综合热分析仪对阻燃剂的热降解性能进行了研究。结果表明,茶皂素与聚磷酸铵、季戊四醇发生反应,生成聚磷酸酯类茶皂素基膨胀型阻燃剂,且该阻燃剂具有良好的热稳定性,降解热释放较小,高温残留率高,最终的质量残留率高达30.77%。将制备阻燃剂用于阻燃涂料中,并采用氧指数测试仪和锥形量热仪研究了阻燃涂料的阻燃性能和热解性能。研究表明,茶皂素基三位一体膨胀型阻燃剂能显著提高涂料的阻燃性能,阻燃涂料的氧指数值高达34.2%,耐火时间为11.1 min,且锥形量热实验中,该阻燃涂料试样的平均热释放速率（m-HRR）为36.18 kW/m2,总热释放量（THR）为5.25 kJ/m2,平均有效燃烧热（m-EHC）为5.11 kJ/kg,与含复合型阻燃剂的阻燃涂料试样相比,阻燃性能得到极大提高。该制备阻燃剂不含卤素,集三源一体,具有阻燃性能优越,相容性能良好,高效环保等优点。     

Synthesis and characterization of bio-based intumescent flame retardant and its application in polyurethane

A novel bio-based P-N containing intumescent flame retardant melamine starch phytate (PSTM) was prepared via the reaction of phytic acid starch ester with melamine and characterized by Fourier transform infrared, scanning electron microscopy and thermogravimetric analysis (TGA). The effects of PSTM on thermal properties and flammability of rigid polyurethane (PU) foams were analyzed by TGA, limit oxygen index (LOI), vertical burning tests (UL-94) and cone calorimeter measurement. The TGA results demonstrated that the thermal stabilities of PU/PSTM foam at high temperature was enhanced with the increasing additive amount of PSTM. The results showed that PU foam with 30 php PSTM (PU/PSTM-30%) observed an LOI value of 25.9 and a UL-94 rating of V-0. Cone calorimetry data showed that peak heat release rate, total heat release and smoke production rate of PU/PSTM-30% were distinctly lower than that of pure PU. Further experimental results demonstrated that PSTM promotes well charring of PU which could protect the foam from combustion. This work developed a novel bio-based intumescent flame retardant by suing phytic acid and starch as the acid source and carbon source, respectively, which is of great significance to the preparation of environmental-friendly flame retardants.     

膨胀型阻燃剂在聚丙烯中的应用研究

使用磷酸、季戊四醇、三聚氰胺合成了一种膨胀型阻燃剂。采用热重分析（TGA）、红外光谱分析（FTIR）、氧指数晨6定和垂直燃烧实验，研究了所合成的膨胀型阻燃剂对聚丙烯的阻燃作用。与普通的膨胀型阻燃剂和包覆型膨胀阻燃剂的对比研究表明，该阻燃剂对聚．丙烯的阻燃性能优良，达到相同的阻燃效果（聚丙烯氧指数达到34％）时，用量较其它两种膨胀型阻燃剂明显减少。抗析出和防湖性能较其它两种膨胀型阻燃剂也有明显改善。     

硼酸锌在膨胀型无卤阻燃ABS中的协同作用

采用熔融共混法制备了丙烯腈-丁二烯-苯乙烯共聚物(ABS)/膨胀型阻燃剂(IFR)/硼酸锌(ZB)无卤阻燃复合材料。利用热重分析仪、氧指数测定仪、扫描电子显微镜等研究了ZB对复合材料热失重行为、阻燃性能、微观结构及力学、加工性能的影响。较低含量的ZB与IFR存在较好的阻燃协同作用,且ZB可促进IFR成炭,使ABS/IFR复合材料的氧指数及其残炭量分别由未加ZB时的27.4%、21.29%提高到30.1%和23.05%。ZB的加入能够提高ABS/IFR复合材料的弯曲性能和加工性能,但对复合材料的冲击、拉伸性能产生了不利影响。     

Synthesis of novel triazine charring agent and its effect in intumescent flame‐retardant polypropylene

A novel charring agent (CNCA‐DA) containing triazine and benzene ring, using cyanuric chloride, aniline, and ethylenediamine as raw materials, was synthesized and characterized. The effects of CNCA‐DA on flame retardancy, thermal degradation, and flammability properties of polypropylene (PP) were investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), and cone calorimeter test (CCT). The TGA results showed that CNCA‐DA had a good char forming ability, and a high initial temperature of thermal degradation; the char residue of CNCA‐DA reached 18.5% at 800°C; Ammonium polyphosphate (APP) could improve the char residue of APP/CNCA‐DA system, the char residue reached 31.6% at 800°C. The results from LOI and UL‐94 showed that the intumescent flame retardant (IFR) containing CNCA‐DA and APP was very effective in flame retardancy of PP. When the mass ratio of APP and CNCA‐DA was 2 : 1, and the IFR loading was 30%, the IFR showed the best effect; the LOI value reached 35.6%. It was also found that when the IFR loading was only 20%, the flame retardancy of PP/IFR can still pass V‐0 rating in UL‐94 tests, and its LOI value reached 27.1%. The CCT results demonstrated that IFR could clearly change the decomposition behavior of PP and form a char layer on the surface of the composites, consequently resulting in efficient reduction of the flammability parameters, such as heat release rate (HRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), and mass loss (ML). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synergistic effects of molybdenum disulfide on a novel intumescent flame retardant polyformaldehyde system

A novel intumescent flame retardant (IFR) composed of ammonium polyphosphate (APP), benzoxazine containing trialkoxysilane (BA-a-Si) and melamine (ME), is compounded with different specifications of MoS₂ as synergist to flame retard polyformaldehyde (POM). The flame retardancy and mechanism of the composites are analyzed by limiting oxygen index (LOI), vertical combustion (UL-94) and cone calorimeter. At the same time, the mechanical properties and lubricating properties are tested by electromechanical testing machine and wear testing machine. The experimental results show that MoS₂ has a good synergistic effect with IFR, and the smaller the average particle size of MoS₂ is, it seems to be more beneficial to improve the flame retardancy of POM composites. Only a small amount of MoS₂ (0.8 wt%) is needed to synergize with IFR, the flame retardant POM composite (FR-POM) can achieve UL-94 (3.2 mm) V-0 rating, LOI of 62.5%, and heat release rate reduction of 25.3%, total smoke release decreased by 29.5%. In addition, from the mechanical properties analysis, it is found that the microscale MoS₂(M2) can better improve the bending and tensile properties of the FR-POM composites, while the nanoscale MoS₂(N80) is more helpful to improve the lubricating properties.     

季戊四醇磷酸蜜胺盐膨胀型阻燃剂的合成和应用

本文采用磷酸、季戊四醇和三聚氰胺为原料,乙二醇为介质在一定条件下合成无卤膨胀型阻燃剂季戊四醇磷酸蜜胺盐,并对产物进行了差热、热失重及红外分析;根据该阻燃剂的膨胀度、剩炭率的测定结果,确定最佳合成条件为：n（磷酸）：n（季戊四醇）：n（三聚氰胺）=3：1：1．5～2;中间产物磷酸季戊四醇酯的合成温度120℃,合成时间2h;最终产物磷酸蜜铵盐合成温度100℃,时间4h。将该阻燃剂和高密度聚乙烯以不同比例共混,测定复合材料的力学性能、加工性能和燃烧性能。结果表明：以m（阻燃剂）：m（聚乙烯）=15：85混合,可使复合材料有良好的机械加工性能和理想的阻燃效果。     

膨胀型阻燃剂在聚丙烯中的应用

对自制的膨胀型阻燃剂(IFR)进行了预处理并添加了协效阻燃剂等助剂,形成一种高效的膨胀型阻燃体系。通过氧指数、热重分析和扫描电子显微镜等检测手段,考察了该阻燃体系的阻燃性能和添加量。IFR、硼酸锌和其他助剂最佳质量比为25：2：2。改进后的膨胀型阻燃体系用于聚丙烯,不仅阻燃性能优良,同时还具有较好的力学性能。     

用反相悬浮聚合法制备膨胀型阻燃剂及其在丁苯橡胶中的应用

采用反相悬浮法聚合丙烯酸钠,同时将化学膨胀阻燃体系(IFR)三组分聚磷酸铵、季戊四醇和三聚氰胺加入到聚合体系中进行原位包裹,用傅里叶变换红外光谱对聚合产物的结构进行了表征,研究了三聚氰胺用量和聚磷酸铵与季戊四醇配比对丁苯橡胶硫化胶阻燃效果的影响,采用热重法分析了阻燃丁苯橡胶的热性能,并通过扫描电镜观察了添加IFR的丁苯橡胶在燃烧后表面的微观形态。结果表明,三聚氰胺的质量分数为IFR体系的3.0%、聚磷酸铵与季戊四醇的质量比为4.00～5.67时IFR体系的剩炭率最高,阻燃性能较好;添加IFR后丁苯橡胶的阻燃性能得到相应改善,当IFR质量分数为30%时丁苯橡胶硫化胶的极限氧指数可达27.5%;添加了IFR的丁苯橡胶硫化胶在燃烧时形成了较为致密的泡沫炭层,表明IFR对丁苯橡胶具有较好的膨胀阻燃效果。     

膨胀阻燃三元乙丙橡胶/聚丙烯热塑性硫化胶的性能

分析了膨胀型阻燃剂聚磷酸铵(APP)、季戊四醇(PER)的加入方式对三元乙丙橡胶(EPDM)/聚丙烯(PP)体系硫化特性的影响,研究了加入不同膨胀型阻燃剂及协效剂硼酸锌(ZB)、有机蒙脱土(OMMT)对动态硫化EPDM/PP热塑性硫化胶(EPDM/PPTPV)性能的影响。结果表明,在动态硫化前加入APP或PER时,EPDM/PP体系不能进行硫化;当APP的加入量为30份时,EPDM/PPTPV的综合力学性能较佳;在EPDM/PPTPV中同时加入APP、PER、三聚氰胺(MEL)时,随着三者加入量的增加,体系的阻燃性能增强,但拉伸强度明显降低,三者的最佳用量为30份APP、10份PER、10份MEL,此时体系的黏度与纯EPDM/PPTPV相当;加入ZB或OMMT时,EPDM/PPTPV的拉伸强度降低,且加入OMMT体系的阻燃效果优于加入ZB体系;加入OMMT时,在低剪切速率下,体系的黏度减小;在高剪切速率下,体系的黏度增大;加入ZB时,在低剪切速率下,体系的黏度与未加ZB体系相当;在高剪切速率下,体系的黏度增大。     

Preparation of a novel synergistic flame retardant and its application in silicone rubber composites

Dehydration condensation product (DHCP) was prepared by addition and dehydration condensation reactions of 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide (DOPO), vinyl trimethoxysilane, and (3-aminopropyl) triethoxysilane. DHCP-PA with high phosphorus content was prepared by reaction between DHCP and phytic acid (PA). It was then compounded with oxidized multi-walled carbon nanotubes (OMWCNTs) to prepare silicone rubber (SR) flame retardant composites. The results showed that the SR with a small amount of DHCP-PA owned good flame retardant effect. The heat release rate (HRR) was decreased from 436 kW/m² for pure SR to 288 kW/m² for the SR with 5 phr DHCP-PA, and the decreasing degree was 33.9%. After mixing 5 phr DHCP-PA with 1 phr OMWCNTs, the HRR of SR composite was decreased from 436 to 251 kW/m², the smoke production rate was decreased from 0.161 to 0.087 m²/s, the limited oxygen index value was increased from 20.4% to 28.4%, and the flame retardant grade can reach UL94 V-0. In addition, the synergistic flame retardant mechanism was researched and analyzed.     

基于废弃聚氨酯泡沫为碳源的膨胀型阻燃EVA的燃烧性能

以废弃聚氨酯泡沫(WPU)为碳源、聚磷酸铵(APP)为酸源和气源、乙烯-乙酸乙烯共聚物(EVA)为基体树脂制备EVA/WPU/APP复合材料,并采用极限氧指数仪、垂直燃烧仪、锥形量热仪、烟密度测试仪研究了WPU与APP的配比对EVA/WPU/APP复合材料燃烧性能和生烟量的影响。结果表明:EPA3[w(WPU),w(APP)分别为12%,18%]与EPA4[w(WPU),w(APP)分别为6%,24%]的极限氧指数分别为28.8%,29.8%,且UL94测试均达V-0级。与其他试样相比,EPA3的热释放速率、总释放热等均最低。点火条件下,EPA4的比光密度最高;而未点火条件下,WPU不能提高EVA/WPU/APP复合材料的比光密度。     

A novel intumescent flame‐retardant system for flame‐retarded LLDPE/EVA composites

A new intumescent flame retardant (IFR) system consisting of ammonium polyphosphate (APP) and charing‐foaming agent (CFA) and a little organic montmorillonite (OMMT) was used in low‐density polyethylene (LLDPE)/ethylene‐vinyl acetate (EVA) composite. According to limiting oxygen index (LOI) value and UL‐94 rating obtained from this work, the reasonable mass ratio of APP to CFA was 3 : 1, and OMMT could obviously enhance the flame retardancy of the composites. Cone calorimeter (CONE) and thermogravimetric analysis (TGA) were applied to evaluate the burning behavior and thermal stability of IFR‐LLDPE/EVA (LLDPE/EVA) composites. The results of cone calorimeter showed that heat release rate peak (HRR‐peak) and smoke production rate peak (SPR‐peak) and time to ignition (TTI) of IFR‐LLDPE/EVA composites decreased clearly compared with the pure blend. TGA data showed that IFR could enhance the thermal stability of the composites at high temperature and effectively increase the char residue. The morphological structures of the composites observed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) demonstrated that OMMT could well disperse in the composites without exfoliation, and obviously improve the compatibility of components of IFR in LLDPE/EVA blend. The morphological structures of char layer obtained from Cone indicated that OMMT make the char layer structure be more homogenous and more stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The mechanical properties and thermal performances of polypropylene with a novel intumescent flame retardant

A novel intumescent flame retardant: tetra‐spirophosphoryl‐benzoguanamine (TSPB) containing three constituents was used as a new flame retardant for polypropylene to prepare flame‐retardant materials, whose flammability and thermal behavior were studied by the limited oxygen index (LOI), thermogravimetric analysis (TGA), in addition whose mechanical properties were investigated in this work. It was found that when the addition of TSPB was 25 wt %, the LOI value of the PP could achieve to 29.5 and pass the UL‐94 V‐0 rating test. The TGA data showed that TSPB could enhance the thermal stability of PP and effectively increase the char residue formation. The mechanical performance test showed that the addition of TSPB improve the mechanical performances of PP to some extent. Thus, the trinity intumescent flame retardant TSPB is good to modify PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel intumescent flame retardants: synthesis and application in polycarbonate

Novel phosphorus‐containing and nitrogen‐containing intumescent flame retardants, bis‐aminobenzyl spirocylic pentaerythritol bisphosphonate (BASPB) and arylene‐N,N′‐bis(2,2‐dimethyl‐1,3‐propanediol phosphoramidate) (ABDPP), were synthesized, and their structures were characterized with Fourier transform infrared spectroscopy and ¹H and ³¹P nuclear magnetic resonance. The phosphorus compounds were used to impart flame retardancy to polycarbonate (PC). Combustion behaviors and thermal degradation properties of the flame‐retarded‐PC composites were assayed by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test, and thermogravimetric analysis. PC/5 wt.% BASPB and PC/5 wt.% ABDPP composites passed UL‐94 V‐0 rating; their LOI values were 35.5% and 34.7%, respectively. Scanning electron microscopy revealed that the char properties had crucial effects on the flame retardancy. The mechanical properties and water resistance of the PC/BASPB and PC/ABDPP composites were also measured. After water resistance test, PC/5 wt.% BASPB and PC/5 wt.% ABDPP composites kept V‐0 rating, and the mass loss was only 1.0%. Copyright © 2012 John Wiley & Sons, Ltd.     

硅橡胶阻燃开发研究进展

简单介绍了硅橡胶的燃烧过程及其自身的燃烧特性,并确立了硅橡胶的阻燃研究方向。综述了铝-镁系、磷氮系、硼硅铂系、膨胀型等不同类型阻燃剂在硅橡胶中的实际应用,并对未来阻燃技术进行了展望。     

A novel lanthanum-based phosphorus-containing flame retardant agent and its application in polylactic acid

Currently, intumescent flame retardants (IFR) are often used in the flame retardant modification of polylactic acid (PLA). Due to the high loading, it will weaken the mechanical properties of PLA. In this study, lamellar lanthanum-based DOPO derivative (La@DDP) is prepared by solution method, and it acts as a flame retardant agent was added into PLA with IFR. The results show that PLA composite passes the UL94 V-0 rating with a limiting oxygen index (LOI) of 32.0, in the addition of 4.5 wt% IFR and 1.5 wt% La@DDP. Moreover, the peak heat release rate (PHRR) and total heat release (THR) of the PLA composite reduces by 31.0% and 23.2% compared to pure PLA, respectively. IFR/La@DDP agents assign the PLA composite with excellent thermal stability and carbon-forming ability. Through the analysis of residual char, the synergistic flame retardant mechanism between IFR and La@DDP in PLA composite is discussed. Notably, the tensile strength and elongation at break of the PLA composites are only reduced by 4.03% and 9.51% compared to pure PLA. This work provides a novel lanthanum-based flame retardant agent for designing PLA composites with good fire safety and mechanical properties, and it will broaden the application range of PLA.     

Synergistic effects of aluminium hypophosphite on the flame retardancy and thermal degradation behaviours of a novel intumescent flame retardant thermoplastic vulcanisate composite

ABSTRACT

The synergistic effects of aluminum hypophosphite (AHP) on the flame retardancy, thermal degradation behaviors of a novel intumescent flame retardant thermoplastic vulcanizate (TPV/IFR) composite were investigated. The results showed that the combination of AHP with IFR showed evident synergistic effects on the increase in the LOI value and reduction of the combustion parameters for the TPV/IFR/AHP composites at the optimum weight ratio of IFR/AHP (6/1) as evidenced by LOI, UL-94 and CCT. The TGA data revealed that AHP could change the degradation behavior of TPV/IFR composites and enhance the thermal stability of the TPV/IFR composites at high temperature. The results of FTIR, EDXS, LRS and SEM demonstrated that TPV/IFR/AHP composites could form more continuous, dense and stable char layer on the materials surface, and consequently improving the flame retardancy. Based on these results, the possible condensed flame retardant mechanism of TPV/IFR/AHP composites was concluded in detail.     

Thermal properties of polyethylene flame retarded with expandable graphite and intumescent fire retardant additives

Low‐density polyethylene was flame retarded by combinations of expandable graphite with either ethylenediamine phosphate or 3,5‐diaminobenzoic acid phosphate. Cone calorimeter, laser pyrolysis, and open flame exposure tests (supported by video and infrared camera data capture and analysis) were conducted to assess ignition and burn behavior. Cone calorimeter results indicated substantial reductions in the peak heat release rates for all flame‐retarded samples but with reduced ignition times and increased flame out times. Smoke generation was suppressed in the presence of expandable graphite. Infrared and video data from open flame fire tests indicated cohesive bonding of expanded strings and thermal shielding properties in all binary systems. All binary systems delivered fire retardation exceeding any of the single fire retardant compounds. They were also able to withstand higher temperatures before ignition, burn through, or sag occurred. All ethylenediamine phosphate‐containing binary systems prevented sample burn through, maintaining structural integrity of samples until eventual melting of the polymer media occurred. Thermogravimetric analysis laser pyrolysis results confirmed the good thermal shielding imparted by the intumescent additives. Copyright © 2016 John Wiley & Sons, Ltd.