IFR/可膨胀石墨及协效剂氧化锌对PP阻燃性能影响的研究

制备了聚丙烯(PP)/有机膨胀型阻燃体系(IFR)、PP/IFR/可膨胀石墨(EG)和PP/IFR/可膨胀石墨(EG)/协效剂氧化锌(ZnO)三种体系,通过力学性能、氧指数(LOI)、垂直燃烧测试及热重分析(TG),探讨了复配膨胀型阻燃体系IFR/EG与协效阻燃剂ZnO之间的协同效应。结果表明,当IFR/EG/ZnO质量比为9.25/9.25/1.5时,阻燃PP的LOI值达到最高,同时阻燃PP的力学性能比不含ZnO的PP有所提高。TG结果表明,ZnO的加入使阻燃PP的热稳定性得到提高,形成了更稳定的保护层,从而提高了PP的阻燃效果。     

金属化合物在HDPE膨胀阻燃体系中的协同作用研究

研究了几种金属化合物对HDPE膨胀阻燃体系(IFR)的协同作用,通过极限氧指数（LOI）、DSC—TG、SEM对复合材料的阻燃、热稳定性和成炭情况进行研究,分析了金属化合物与膨胀阻燃剂协效作用机理。LOI测试显示：当ZEO、ZnO、Al2O3添加量分别为3%（质量百分比,下同）、1%、3%时,极限氧指数达到29.6%、29.0%、29.4%,比单独添加IFR分别高出4.6、4.0和4.4个百分点;DSC-TG和SEM结果表明：ZEO、ZnO、Al2O3主要通过促进PE-HD/IFR体系凝聚相快速成炭,稳定炭层强度来发挥其协效作用,而对最终成炭量贡献不大。     

氧化锌催化膨胀型阻燃剂对PP阻燃及力学性能的影响

研究了氧化锌催化膨胀型阻燃剂(APP/PER)对PP阻燃和力学性能的影响。研究表明,当APP/PER质量比为20/10,ZnO的质量分数为1．3%时,阻燃PP的LOI值达到最大；同时阻燃PP的拉伸强度和冲击强度比不含ZnO的PP有所提高。TG结果表明,ZnO的加入使阻燃PP燃烧时降解过程加快并生成更多的剩炭,形成稳定的保护层,从而提高了PP的阻燃效果。SEN的形貌观察表明,加入ZnO的试样燃烧炭膜孔径较小、孔膜较厚。     

ZnO对PP/MPP/PEPA膨胀阻燃体系的协同作用

以ZnO为阻燃协效剂,采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备了具有良好阻燃性能的无卤阻燃PP。研究了ZnO用量对PP阻燃性能和协效作用的影响。结果表明:添加少量的ZnO即可显著提高PP的阻燃性能。当MPP、PEPA和ZnO添加量分别为12%、8%和1%时,阻燃PP的氧指数高达29.5%。TGA、FTIR分析和体式显微镜观测结果表明:添加ZnO可以催化MPP/PEPA间的酯化反应,促进体系成炭,形成更致密的炭层,从而提高材料的阻燃性能。     

聚丙烯/氮磷共掺杂碳点/高岭土阻燃复合材料的非等温热降解动力学研究

为改善聚丙烯（PP）的阻燃性能，通常添加阻燃剂。以氮磷共掺杂碳点（N,P-CDs）和高岭土复配作为协效剂，与聚磷酸铵（APP）、双季戊四醇（DPER）以及PP，通过熔融挤出制备阻燃聚丙烯复合材料（PP/APP/DPER/高岭土/N,P-CDs）。通过Kissinger法和Flynn-Wall-Ozawa法研究阻燃复合材料的热降解动力学，探究阻燃剂机理。结果表明：2%N,P-CDs/高岭土（1.0∶1.0）的加入，明显提高APP/DPER膨胀阻燃剂的阻燃效果，阻燃复合材料的LOI高达29.8%,UL-94通过V-0级。N,P-CDs/高岭土协效剂的加入，不改变APP/DPER的阻燃机理，但其可促进复合材料成炭，减缓热降解速率，增大热降解活化能，提高阻燃材料的热稳定性。     

基于胞苷酸阻燃剂的制备及其对PP阻燃性能的影响

为了提高膨胀阻燃剂(IFR)对于聚丙烯(PP)的阻燃效率,选择具有阻燃潜质的胞苷酸衍生物作为协效剂。胞苷酸与三缩水甘油基异氰尿酸酯反应形成阻燃微球,同时引入镍离子与磷酸基团反应成盐,以提高其热稳定性,得到基于胞苷酸镍的阻燃微球TC-Ni,通过红外光谱研究了其结构。将TC-Ni与膨胀阻燃剂(IFR)复合,通过熔融共混法制备阻燃PP复合材料。通过极限氧指数、垂直燃烧等研究了复合材料的阻燃性能,通过热失重分析测试其热稳定性,采用扫描电镜观察炭层结构。结果表明,添加17%IFR和1%TC-Ni可以使样品通过UL94 V–0级别,并且其LOI提高到29.2%。TC-Ni改善了PP/IFR形成的膨胀炭形态和完整性,使炭层表层炭致密,内层多孔,从而有效地提高了PP/IFR体系的阻燃效率。     

金属氧化物对聚丙烯膨胀阻燃体系阻燃性能的影响

采用聚磷酸铵（APP）和三聚氰胺（MEL）作为聚丙烯（PP）的膨胀型阻燃剂（IFR），添加微量金属氧化物（ZnO和Cr2O3）制备出阻燃效果较好的聚丙烯阻燃材料。研究了不同含量的金属氧化物（ZnO和Cr2O3）对材料阻燃性能的影响。利用氧指数（LOI）、垂直燃烧（UL-94）、热分析（TG）、扫描电镜（SEM）研究了金属氧化物（ZnO和Cr2O3）对聚丙烯阻燃材料阻燃性能的影响、材料热降解过程的影响、在阻燃体系中的分散情况以及燃烧产物的微观结构。结果表明：添加1％ZnO和1％Cr2O3的阻燃材料，LOI分别为28％和26％；ZnO和Cr2O3的加入，改变了材料的热降解过程；ZnO使材料在燃烧时形成了连续、致密、封闭的焦化炭层，相对于Cr2O3显示出更好的阻燃效果。     

ADP协效APP/PER阻燃PP的制备及性能

以二乙基次膦酸铝(ADP)为协效剂,与聚磷酸铵(APP)/季戊四醇(PER)传统膨胀型阻燃体系复配,通过熔融共混制备了膨胀阻燃聚丙烯(PP)。采用极限氧指数(LOI)、垂直燃烧测试、锥形量热仪、扫描电子显微镜和热重分析研究了阻燃PP的性能及相关作用机制。结果表明,ADP和APP/PER具有很好的协同阻燃作用,它不但可以同时提高阻燃体系的残炭量和炭层质量,有效抑制熔滴,还可以降低燃烧过程中的生烟量,是更加绿色的阻燃体系。当阻燃体系的总添加量为24%,APP/PER和ADP的质量比为6∶1时,阻燃PP的LOI可达到29.8%,垂直燃烧等级为V–0级,且生烟性比不添加ADP的体系下降了76.9%。阻燃机理研究表明,该体系是以凝聚相为主的凝聚相和气相协同阻燃机制。     

铁酸镍在膨胀阻燃聚乳酸复合材料中的作用

利用水热法制备了铁酸镍(NiFe_2O_4)纳米粒子,基于生物可降解材料聚乳酸(PLA)的易燃性,将NiFe_2O_4纳米粒子作为协效剂与膨胀型阻燃剂(IFR)复配,应用于PLA的阻燃改性。结果表明,所有的PLA复合材料均达到UL-94 V-0级别,LOI显著提高至39%以上;NiFe_2O_4纳米粒子有助于PLA膨胀阻燃体系形成更为膨胀和相对致密的炭层,明显提高炭渣中有序化炭的含量,有效提高PLA膨胀阻燃体系的初始降解温度,并显著提高其成炭量。因此,NiFe_2O_4纳米粒子在PLA膨胀阻燃体系中具有良好的协效作用,能够显著提高PLA膨胀阻燃体系的热稳定性和阻燃性能。     

改性海泡石与金属氧化物对膨胀阻燃PP燃烧性能的影响

采用极限氧指数、垂直燃烧、TGA、FTIR和SEM等方法研究了改性海泡石(SP)及金属氧化物(ZnO、Ni2O3)对聚丙烯(PP)/马来酸酐接枝三元乙丙橡胶(EPDM-g-MAH)/膨胀阻燃剂(IFR)体系燃烧性能的影响。极限氧指数和垂直燃烧结果表明:SP及金属氧化物均对IFR有一定的协效作用,能提高体系的极限氧指数和阻燃性能。TGA结果表明:SP可以提高燃烧残余炭层的稳定性和残炭率。SEM观察表明:SP与ZnO复配体系的燃烧残余炭层更致密和连续。FTIR测试发现SP、金属氧化物促进了IFR在PP体系中的交联成炭作用,较快生成连续的保护性炭层。     

Synergistic effects of hydroxy silicone oil on intumescent flame retardant polypropylene system

The effects of hydroxy silicone oil as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (IFR-PP) were studied, and the IFR system mainly consisted of the ammonium polyphosphate (APP), melamine (MEL) and pentaerythritol (PER). The UL 94 rating, thermogravimetric analysis (TGA), cone calorimeter (CONE) and digital photograph were used to evaluate the synergistic effects of hydroxy silicone oil (HSO). It has been found that the PP composite containing only APP, MEL and PER does not show good flame retardancy at 30% additive level. The cone calorimeter results show that the heat release rate, mass loss rate, mass, total heat release, carbon monoxide and carbon dioxide of PP/APP/MEL/PER/HSO composites decrease in comparison with the PP/APP/MEL/PER composite. The digital photographs demonstrated that HSO could promote to form the homogenous and compact intumescent char layer. Thus, a suitable amount of HSO plays a synergistic effect in the flame retardancy.     

Synthesis of amino trimethylene phosphonic acid melamine salt and its application in flame‐retarded polypropylene

Amino trimethylene phosphonic acid melamine salt (MATMP) was synthesized and used as acid source and blowing agent in intumescent flame‐retarded polypropylene (PP); its compositions were characterized by Fourier transform infrared spectroscopy and X‐ray powder diffraction. An intumescent flame retardant (IFR) system composed of MATMP, pentaerythritol (PER), and PP was tested by limiting oxygen index (LOI), UL‐94, cone calorimeter tests, and thermogravimetric analysis and compared with an ammonium polyphosphate (APP)/PER system. The results showed that MATMP had better water resistance than APP, the LOI value of PP/MATMP/PER composite can reach 30.3%, and a UL‐94 V‐0 rating can be reached at 25 wt % IFR loading. The amount of residual char of IFR MATMP/PER was 20.3 and 9.5 wt % at 400 and 600 °C, respectively. A thermooxidative degradation route and a possible flame‐retardant mechanism of IFR were proposed according to the analysis of evolved gases and residual chars. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46274.     

硼酸锌在膨胀型阻燃聚丙烯中的协同阻燃机理研究

通过氧指数，热重分析（TGA）和扫描电子显微镜（SEM）研究了硼酸锌在膨胀型阻燃丙烯中的协同阻燃作用，硼酸锌的加入在用量低时可显著增加膨胀型阻燃聚丙烯（PP）的氧指数,而当用量超过一定值后，氧指数则急剧降低，TGA显示硼酸锌用量为2．5份时，500℃的剩焦量出现最大值。这与氧指数的数值非常吻合。扫描电子显微镜观察到硼酸锌用量为2．5份时，燃烧剩炭出现大泡孔结构，这种大泡孔具有非常薄的壁，为此，我们认为该体系的阻燃机理是聚磷酸铵分解后形成的玻璃状物与硼酸锌分解物形成一种乳液体系覆盖在燃烧物表面，该体系使聚磷酸铵分解产生的气泡稳定，形成有效的隔离层使阻燃性能得到提高。     

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     

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

A novel mono-component intumescent flame retardant(m-IFR), called poly-(spirocyclic pentaerythritol bisphosphonate-1,3,5-triazine-O-bicyclic pentaerythritol phosphate) (PSTBP) was synthesized and characterized. PSTBP was used in polypropylene (PP) to obtain PP/PSTBP mixture whose flame retardancy, thermostability, and water resistance were studied by limiting oxygen index (LOI), vertical burning test (UL-94 V) and thermogravimetric analysis (TGA). In addition, flame-retardant mechanism of the PSTBP was investigated. The results showed that the residue of PSTBP reached 34.58% at 800°C and the volume of the PSTBP increased by dozens of times. When the content of PSTBP was 30.0 wt%, the PP/PSTBP mixture could achieve an LOI value of 32.5% and an UL-94 V-0 rating. Compared with PP/APP/PER system, PP/PSTBP mixture showed better water resistance. The TGA and Fourier transform infrared spectroscopy (FTIR) results showed that PSTBP could generate free radicals and capture the free radicals of the thermal decomposition of PP, and form a dense, strong, and thick intumescent char on the substrate, thus effectively retard the degradation and combustion of PP.     

Synthesis of a novel oligomeric intumescent flame retardant and its application in polypropylene

A novel oligomeric phosphorous‐nitrogen containing intumescent flame retardant, poly (4,4‐diamino diphenyl methane‐O‐bicycli pentaerythritol phosphate‐phosphate) (PDBPP), was synthesized and characterized. Thermal stability and flammability properties of polypropylene (PP)/PDBPP composites with various PDBPP loading were investigated by thermogravimetric analysis (TGA), limited oxygen index (LOI), and cone calorimeter, respectively. The results showed that the incorporation of PDBPP could improve both the thermal stability and flame retardancy of PP considerably. PP/30%PDBPP system had a LOI value of 28 and its peak heat release rate was reduced by 60% relative to pure PP. Infrared spectrum and field emission scanning electron microscope measurements revealed that PDBPP and PP/PDBPP composites would form a continuous multicellular char layer containing phosphoric acid when exposed to elevated temperature. It was suggested that the very char layer was responsible for the enhanced thermal stability and improved flame retardancy. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Flame retardation and thermal degradation of intumescent flame‐retarded polypropylene composites containing spirophosphoryldicyandiamide and ammonium polyphosphate

A novel halogen‐free intumescent flame retardant, spirophosphoryldicyandiamide (SPDC), was synthesized and combined with ammonium polyphosphate (APP) to produce a compound intumescent flame retardant (IFR). This material was used in polypropylene (PP) to obtain IFR‐PP systems whose flammability and thermal behavior were studied by the limiting oxygen index (LOI) test, UL‐94, thermogravimetric analysis, and cone calorimetry. In addition, the mechanical properties of the systems were investigated. The results indicated that the compound intumescent flame retardant showed both excellent flame retardancy and antidripping ability for PP when the two main components of the IFR coexisted in appropriate proportions. The optimum flame retardant formulation was SPDC:APP = 3:1, which gave an LOI value of 38.5 and a UL‐94 V‐0 rating. Moreover, the heat release rate, production of CO, smoke production rate, and mass loss rate of the IFR‐PP with the optimum formulation decreased significantly relative to those of pure PP, according to the cone calorimeter analysis. The char residues from the cone calorimetry experiments were observed by scanning electron microscopy, which showed that a homogeneous and compact intumescent char layer was formed. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Vinyl polysiloxane microencapsulated ammonium polyphosphate and its application in flame retardant polypropylene

Vinyl polysiloxane microencapsulated ammonium polyphosphate (MAPP) was prepared by a sol-gel method using vinyltrimethoxysilane as a precursor to improve its thermal stability and hydrophobicity. The MAPP was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and thermogravimetric analyzer (TGA). The results showed that ammonium polyphosphate (APP) was successfully coated with vinyl polysiloxane. MAPP and pentaerythritol (PER) were used together to improve the flame retardancy of polypropylene (PP). The flame retardant properties of PP composites were investigated by limiting oxygen index (LOI), UL-94 test, TGA and SEM. When the MAPP was added as a flame retardant, with PER as a char forming agent, the LOI of PP/MAPP/PER composites was 33.1%, and it reached the UL-94 V-0 level. The results also demonstrated that the flame retardant properties of PP/MAPP/PER composites were better than those of PP/APP/PER composites at the same loading. Moreover, the addition of flame retardant and carbon forming agent could promote the crystallization behavior of PP.     

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。