甲基乙烯基硅橡胶/六苯氧基环三磷腈/三聚氰胺阻燃复合材料的制备与性能
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摘要
为了提高甲基乙烯基加成硫化型硅橡胶(VMQ)的阻燃性能,向基体中加入了六苯氧基环三磷腈(HPCP)和三聚氰胺(MEL)阻燃剂,研究了VMQ/HPCP/MEL阻燃复合材料的阻燃性能、燃烧行为、热稳定性能和力学性能。结果表明,HPCP和MEL对VMQ具有协同阻燃作用,当HPCP与MEL的质量比为1/2时,VMQ/HPCP/MEL阻燃复合材料的氧指数最高为30.8%,UL-94等级达到V-0级;燃烧时间从520 s缩短到415 s,总热释放量从53.53 MJ/m~2降低到45.80 MJ/m~2,燃烧后得到的残炭致密;材料的热稳定性比单独添加HPCP和MEL时更好,力学性能最好,拉伸强度为1.69 MPa,扯断伸长率为262%。
In order to improve the flame retardancy of methyl vinyl additive vulcanized silicone rubber(VMQ), hexophenoxy cyclophosphoronitrile(HPCP) and melamine(MEL) flame retardants were added to the matrix. The flame retardancy, combustion behavior, thermal stability and mechanical properties of VMQ/HPCP/MEL flame retardant composites were studied. The results showed that HPCP and MEL had a synergistic flame retarding effect on VMQ. When the mass ratio of HPCP and MEL was 1/2, the VMQ/HPCP/MEL flame retar-dant composites achieved the largest limiting oxygen index value of 30.8% and got UL-94 V-0 rating. Meanwhile, the combustion time was shortened from 520 s to 415 s, and the total heat release decreased from 53.53 MJ/m~2 to 45.80 MJ/m~2. The char residues after combustion was more compact and the thermal stability of the composites was better than those of composites added HPCP or MEL alone. The mechanical properties were the best. The tensile strength was 1.69 MPa, and the elongation at break was 262%.
In order to improve the flame retardancy of methyl vinyl additive vulcanized silicone rubber(VMQ), hexophenoxy cyclophosphoronitrile(HPCP) and melamine(MEL) flame retardants were added to the matrix. The flame retardancy, combustion behavior, thermal stability and mechanical properties of VMQ/HPCP/MEL flame retardant composites were studied. The results showed that HPCP and MEL had a synergistic flame retarding effect on VMQ. When the mass ratio of HPCP and MEL was 1/2, the VMQ/HPCP/MEL flame retar-dant composites achieved the largest limiting oxygen index value of 30.8% and got UL-94 V-0 rating. Meanwhile, the combustion time was shortened from 520 s to 415 s, and the total heat release decreased from 53.53 MJ/m~2 to 45.80 MJ/m~2. The char residues after combustion was more compact and the thermal stability of the composites was better than those of composites added HPCP or MEL alone. The mechanical properties were the best. The tensile strength was 1.69 MPa, and the elongation at break was 262%.
引文
[1] Chen Dongzhi,Yi Shengping,Wu Weibin,et al.Synthesis and characterization of novel room temperature vulcanized (RTV) silicone rubbers using vinyl-POSS derivatives as crosslinking agents[J].Polymers,2010,51(17):3867–3878.
[2] Chen Dongzhi,Nie Jiaorong,Yi Shengping,et al.Thermal behaviour and mechanical properties of novel RTV silicone rubbers using divinyl-hexa[(trimethoxysilyl)ethyl]-POSS as crosslinker[J].Polymer Degradation and Stability,2010,95(4):618–626.
[3] Fang Shoulin,Hu Yuan,Song Lei,et al.Mechanical properties,fire performance and thermal stability of magnesium hydroxide sulfate hydrate whiskers flame retardant silicone rubber[J].Journal of Materials Science,2008,43(3) :1057-1062.
[4] Hamdani S,Longuet C,Perrin D,et al.Flame retardancy of silicone-based materials[J].Polymer Degradation and Stability,2009,94(4):465-495.
[5] Yang Mi,Chen Li,Zhao Chengshou,et al.A novel phosphorus-containing thermotropic liquid crystalline poly(ester-imide) with high flame retardancy[J].Polymers for Advanced Technologies,2009,20(4):378-383.
[6] Covaci A,Harrad S,Abdallah M A E,et al.Novel brominated flame retardants:A review of their analysis,environmental fate and behavior[J].Environment International,2011,37(2):532–556.
[7] Liu Yufeng,Shi Yunhui,Zhang Dian,et al.Preparation and thermal degradation behavior of room temperature vulcanized silicone rubber-g-polyhedral oligomeric silsesquioxanes[J].Polymers,2013,54(22) :6140–6149.
[8] Zhu Chen,Deng Cong,Cao Jingyu,et al.An efficient flame retardant for silicone rubber:Preparation and application[J].Polymer Degradation and Stability,2015,121(1):42–50.
[9] Ma Haiyun,Tong Lifang,Xu Zhongbin,et al.Functionalizing carbon nanotubes by grafting on intumescent flame retardant:Nanocomposite synthesis,morphology,rheology,and flammability[J].Advanced Functional Materials,2008,18(3):414-421.
[10] Hamdani S,Longuet C,Lopez-Cuesta J M,et al.Calcium and aluminium-based fillers as flame-retardant additives in silicone matrices:Blend preparation and thermal properties[J].Polymer Degradation and Stability,2010,95(9):1911–1919.
[11] Yang Yunyun,Kong Weibo,Wang Youchuan,et al.Synthesis of tris(phenoxy)trifluorocyclotriphosphazenes and study of its effects on the flammable,thermal,optical,and mechanical properties of bisphenol-A polycarbonate[J].Journal of Thermal Analysis Calorimetry,2015,122(2):805-816.
[12] Matusinovic Z,Wilkie C A.Fire retardancy and morphology of layered double hydroxide nanocomposites:A review[J].Journal of Materials Chemistry,2012,22(36):18701-18704.
[13] Hoang D,Kim J.Synthesis and applications of biscyclic phosphorus flame retardants[J].Polymer Degradation and Stability,2008,93(1):36-42.
[2] Chen Dongzhi,Nie Jiaorong,Yi Shengping,et al.Thermal behaviour and mechanical properties of novel RTV silicone rubbers using divinyl-hexa[(trimethoxysilyl)ethyl]-POSS as crosslinker[J].Polymer Degradation and Stability,2010,95(4):618–626.
[3] Fang Shoulin,Hu Yuan,Song Lei,et al.Mechanical properties,fire performance and thermal stability of magnesium hydroxide sulfate hydrate whiskers flame retardant silicone rubber[J].Journal of Materials Science,2008,43(3) :1057-1062.
[4] Hamdani S,Longuet C,Perrin D,et al.Flame retardancy of silicone-based materials[J].Polymer Degradation and Stability,2009,94(4):465-495.
[5] Yang Mi,Chen Li,Zhao Chengshou,et al.A novel phosphorus-containing thermotropic liquid crystalline poly(ester-imide) with high flame retardancy[J].Polymers for Advanced Technologies,2009,20(4):378-383.
[6] Covaci A,Harrad S,Abdallah M A E,et al.Novel brominated flame retardants:A review of their analysis,environmental fate and behavior[J].Environment International,2011,37(2):532–556.
[7] Liu Yufeng,Shi Yunhui,Zhang Dian,et al.Preparation and thermal degradation behavior of room temperature vulcanized silicone rubber-g-polyhedral oligomeric silsesquioxanes[J].Polymers,2013,54(22) :6140–6149.
[8] Zhu Chen,Deng Cong,Cao Jingyu,et al.An efficient flame retardant for silicone rubber:Preparation and application[J].Polymer Degradation and Stability,2015,121(1):42–50.
[9] Ma Haiyun,Tong Lifang,Xu Zhongbin,et al.Functionalizing carbon nanotubes by grafting on intumescent flame retardant:Nanocomposite synthesis,morphology,rheology,and flammability[J].Advanced Functional Materials,2008,18(3):414-421.
[10] Hamdani S,Longuet C,Lopez-Cuesta J M,et al.Calcium and aluminium-based fillers as flame-retardant additives in silicone matrices:Blend preparation and thermal properties[J].Polymer Degradation and Stability,2010,95(9):1911–1919.
[11] Yang Yunyun,Kong Weibo,Wang Youchuan,et al.Synthesis of tris(phenoxy)trifluorocyclotriphosphazenes and study of its effects on the flammable,thermal,optical,and mechanical properties of bisphenol-A polycarbonate[J].Journal of Thermal Analysis Calorimetry,2015,122(2):805-816.
[12] Matusinovic Z,Wilkie C A.Fire retardancy and morphology of layered double hydroxide nanocomposites:A review[J].Journal of Materials Chemistry,2012,22(36):18701-18704.
[13] Hoang D,Kim J.Synthesis and applications of biscyclic phosphorus flame retardants[J].Polymer Degradation and Stability,2008,93(1):36-42.