为提高聚丙烯(PP)的阻燃性能,采用两步法制备阻燃剂(FR),经熔融共混制备无卤阻燃PP复合材料(FR-PP)。利用X-射线衍射仪(XRD)、傅里叶变换红外(FT-IR)光谱和热重(TG)分析方法对FR-PP进行理化性能表征;通过极限氧指数(LOI)、垂直燃烧测试考察FR-PP的阻燃性能和阻燃机理。结果表明,当FR的添加量为25%时,FR-PP的LOI由18.0%提高至26.1%,达到垂直燃测试UL-94的V-1等级;TG分析表明,600℃下FR-PP的残炭率由0.1%提高至15.2%,表明FR-PP具有良好的阻燃性和热稳定性;不同添加量的FR-PP的熔体质量流动速率均大于9.5g/min,具有良好的流动性;弯曲强度由27.8MPa提升至31.5MPa,断裂伸长率由55.8%下降至38.5%,弯曲模量由940.4MPa提升至1360.8MPa。研究结果对阻燃PP的制备具有一定的指导意义。
In order to improve the flame retardancy of polypropylene (PP),flame retardant (FR) was prepared by two-step method,and halogen-free flame retardant PP composite (FR-PP) was prepared by melt blending.The physical and chemical properties of FR-PP were characterized by X-ray diffraction (XRD),fourier transform infrared (FT-IR) spectroscopy and thermogravimetric (TG) analysis;The flame retardance and flame retardant mechanism of FR-PP were investigated by limiting oxygen index (LOI) and vertical combustion test.The results showed that when the addition of FR was 25%,the LOI of FR-PP increased from 18.0% to 26.1%,reaching the V-1 grade of UL-94 in vertical combustion test.TG analysis showed that the carbon residue rate of FR-PP increased from 0.1% to 15.2% at 600 ℃,indicating that FR-PP had good flame retardancy and thermal stability.The melt mass flow rate of FR-PP with different addition amounts was greater than 9.5g/min,which had good fluidity.The bending strength increased from 27.8MPa to 31.5MPa,the elongation at break decreased from 55.8% to 38.5%,and the bending modulus increased from 940.4MPa to 1360.8MPa.The research results had certain guiding significance for the preparation of flame retardant PP.
[1] Chen W,Qu B.Structural characteristics and thermal properties of PE-g-MA/MgAl-LDH exfoliation nanocomposites synthesized by solution intercalation[J].Chemistry of Materials,2003,15(16):3208-3213.
[2] Chhetri S,Chandra A N,Samanta P,et al.Rheological,mechanical,and thermal properties of silane grafted layered double hydroxide/epoxy composites[J].Industrial & Engineering Chemistry Research,2018,57(26):8729-8739.
[3] Du J Z,Jin L,Zeng H Y,et al.Facile preparation of an efficient flame retardant and its application in ethylene vinyl acetate[J].Applied Clay Science,2019,168:96-105.
[4] Evans D G,Duan X.Preparation of layered double hydroxides and their applications as additives in polymers,as precursors to magnetic materials and in biology and medicine[J].Chemical Communications,2006,(5):485-496.
[5] Francavilla M,Manara P,Kamaterou P,et al.Cascade approach of red macroalgae Gracilaria gracilis sustainable valorization by extraction of phycobiliproteins and pyrolysis of residue[J].Bioresource Technology,2015,184:305-313.
[6] Ran G,Liu X,Guo J,et al.Improving the flame retardancy and water resistance of polylactic acid by introducing polyborosiloxane microencapsulated ammonium polyphosphate[J].Composites Part B:Engineering,2019,173:106772.
[7] Shen H,Liu Y.One-step synthesis of hydrophobic magnesium hydroxide nanoparticles and their application in flame-retardant polypropylene composites[J].Chinese Journal of Chemical Engineering,2018,26(10):2199-2205.
[8] Liu X,Sun J,Zhang S,et al.Effects of carboxymethyl chitosan microencapsulated melamine polyphosphate on the flame retardancy and water resistance of thermoplastic polyurethane[J].Polymer Degradation and Stability,2019,160:168-176.
[9] Wang Y,Li Z,Li Y,et al.Spray-drying-assisted layer-by-layer assembly of alginate,3-aminopropyltriethoxysilane,and magnesium hydroxide flame retardant and its catalytic graphitization in ethylene-vinyl acetate resin[J].ACS Applied Materials & Interfaces,2018,10(12):10490-10500.
[10] Silvaf K,Santa R A A B,Fiori M A,et al.Synthesis of aluminum hydroxide nanoparticles from the residue of aluminum anodization for application in polymer materials as antiflame agents[J].Journal of Materials Research and Technology,2020,9(4):8937-8952.
[11] Zhao P P,Guo C G,Li L P.Exploring the effect of melamine pyrophosphate and aluminum hypophosphite on flame retardant wood flour/polypropylene composites[J].Construction and Building Materials,2018,170:193-199.
[12] Tawiah B,Yu B,Cheung W Y,et al.Synthesis and application of synergistic azo-boron-BPA/polydopamine as efficient flame retardant for poly(lactic acid)[J].Polymer Degradation and Stability,2018,152:64-74.
[13] Feng C M,Zhang Y,Liang D,et al.Influence of zinc borate on the flame retardancy and thermal stability of intumescent flame retardant polypropylene composites[J].Journal of Analytical and Applied Pyrolysis,2015,115:224-232.
[14] Yuan G W,Yang B,Chen Y H,et al.Synthesis of a novel multi-structure synergistic POSS-GO-DOPO ternary graft flame retardant and its application in polypropylene[J].Composites Part A:Applied Science and Manufacturing,2019,117:345-356.
[15] Nazir R,Gooneie A,Lehner S,et al.Alkyl sulfone bridged phosphorus flame-retardants for polypropylene[J].Materials & Design,2021,200:109459.
[16] Pan Y T,Zhang Z,Yang R.The rise of MOFs and their derivatives for flame retardant polymeric materials:a critical review[J].Composites Part B:Engineering,2020,199:108265.
[17] Tang W,Qian L,Chen Y,et al.Intumescent flame retardant behavior of charring agents with different aggregation of piperazine/triazine groups in polypropylene[J].Polymer Degradation and Stability,2019,169:108982.
[18] Zhao P,Zeng W,Yang Z,et al.Preparation of a novel functionalized magnesium-based curing agent as an intrinsic flame retardant for epoxy resin[J].Chemosphere,2021,273:129658.
[19] Wang X,Xu M,Zhang Z,et al.Synthesis of a novel N-alkoxyamine containing compound and its application as an effective flame retardant for polypropylene film by quenching free radical[J].Journal of analytical and applied pyrolysis,2018,134:243-253.
[20] Zhang Y,Lu Y,Guo F,et al.Preparation of microencapsulated ammonium polyphosphate with montmorillonite-melamine formaldehyde resin and its flame retardancy in EVM[J].Polymers for Advanced Technologies,2012,23(2):166-170.
基金资助
吉林省科技厅2013年科技基金项目(20130206070GX)
PDF
