一种高效膨胀型阻燃涂层的制备及其在聚乙烯中的应用
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摘要
以甲基二氯膦和1,4-环己二醇为单体,经缩聚反应合成了一种新型阻燃剂-聚甲基亚膦酸环己二醇酯(PMPHE)。采用核磁氢谱(~1H NMR)、红外光谱(FTIR)等技术表征了目标产物,并与聚乙烯醇缩甲醛(PVF)和三聚氰胺氰尿酸盐(MCA)按特定比例在聚乙烯(PE)表面制备了不同厚度的阻燃涂层。当涂层厚度达到95μm时可使PE的极限氧指数(LOI)由17. 8%提高至29. 7%,垂直燃烧测试达到UL94 V-0级别。微形量热测试结果表明阻燃涂层对PE的热释放速率抑制作用明显。热重-红外联用(TG-FTIR)分析证实阻燃涂层能显著降低PE热分解过程中可燃性气体的释放。此外,通过扫描电镜(SEM)可以观察到阻燃复合材料燃烧后膨胀效果明显,表面形成了多孔的"蜂窝状"炭层。
A novel flame retardant poly( methylphosphite cyclohexanediol ester)( PMPHE) was synthesized by methylphosphonous dichloride and 1, 4-cyclohexanediol by condensation polymerization reaction. The target product was characterized by hydrogen nuclear magnetic resonance(~1H-NMR) and fourier transform infrared spectroscopy( FTIR). And the flame retardant coating with different thicknesses were prepared on the surface of polyethylene( PE) by PMPHE,polyvinyl formal( PVF) and melamine cyanurate( MCA) with specific ratio. When the thickness of coating achieved 95 μm,the limit oxygen index( LOI) of PE could increase from 17. 8%to 29. 7%,and the vertical burning test could achieve UL94 V-0 rating. Microscale combustion calorimeter results indicated that the flame retardant coating exhibited superior performance in the inhibition of heat release rate for PE. TG-FTIR combination analysis confirmed that the flame retardant coating could effectively reduce the release of flammable gases during the thermal decomposition process of PE. In addition,obviously intumescent effect could be observed after the combustion of flame retardant composite by scanning electronic microscopy( SEM). And the surface of the composites could be porous char layer which looks like "honeycomb".
A novel flame retardant poly( methylphosphite cyclohexanediol ester)( PMPHE) was synthesized by methylphosphonous dichloride and 1, 4-cyclohexanediol by condensation polymerization reaction. The target product was characterized by hydrogen nuclear magnetic resonance(~1H-NMR) and fourier transform infrared spectroscopy( FTIR). And the flame retardant coating with different thicknesses were prepared on the surface of polyethylene( PE) by PMPHE,polyvinyl formal( PVF) and melamine cyanurate( MCA) with specific ratio. When the thickness of coating achieved 95 μm,the limit oxygen index( LOI) of PE could increase from 17. 8%to 29. 7%,and the vertical burning test could achieve UL94 V-0 rating. Microscale combustion calorimeter results indicated that the flame retardant coating exhibited superior performance in the inhibition of heat release rate for PE. TG-FTIR combination analysis confirmed that the flame retardant coating could effectively reduce the release of flammable gases during the thermal decomposition process of PE. In addition,obviously intumescent effect could be observed after the combustion of flame retardant composite by scanning electronic microscopy( SEM). And the surface of the composites could be porous char layer which looks like "honeycomb".
引文
[1]刘莹,梁兵.新型含磷、氮阻燃剂的合成及其阻燃聚乙烯的性能研究[J].塑料工业,2017,45(2):33-36.
[2]欧育湘.阻燃剂制造、性能及应用[M].北京:化学工业出版社,2006.
[3]潘玉琴,刘媛,孔霞.相容剂种类对阻燃抗静电HDPE复合材料性能的影响[J].塑料工业,2017,45(4):111-115.
[4]GIJSMAN P,STEENBAKKERS R,FURST C,et al.Differences in flame retardant mechanism of melamine cyanurate in polyamide6 and polyamide66[J].Polym Degrad Stab,2002,78(2):219-224.
[5]FANG Y,WANG Q,GUO C,et al.Effect of zinc borate and woodflour on thermal degradation and fire retardancy of polyvinyl chloride(PVC)composites[J].J Anal Appl Pyrolysis,2013,100(17):230-236.
[6]RAMOS R,BOSCHI-FILHO H.The size of compact extra dimensions from black-body radiation laws[J].Physica A,2014,39(1):261-267.
[7]KING J A,TUCKER K W,VOGT B D,et al.Electrically and thermally conductive nylon 6,6[J].Polym Compos,1999,20(5):643-654.
[8]董秀洁.抗静电阻燃材料ABS、PP、PE的研究与开发[J].印染助剂,2002,19(1):48-51.
[9]李德龙,李振宇,刘焱.加工工艺对聚乙烯热收缩膜性能的影响[J].塑料科技,2012,40(2):64-66.
[10]SHAO Z B,DENG C,TAN Y,et al.An efficient monocomponent polymeric intumescent flame retardant for polypropylene:Preparation and application[J].ACS Appl Mater Int,2014,6(1):7363-7370.
[11]LI X S,ZHAO Z L,WANG Y H,et al.Highly efficient flame retardant,flexible,and strong adhesive intumescent coating on polypropylene using hyperbranched polyamide[J].Chem Eng J,2017,324(9):237-250.
[12]廖阳飞,张旭东.塑料涂料研究进展[J].上海涂料,2008,46(8):14-18.
[13]HU X,GUO Y,CHEN L,et al.A novel polymeric intumescent flame retardant:Synthesis,thermal degradation mechanism and application in ABS co-polymer[J].Polym Degrad Stab,2012,97(9):1772-1778.
[2]欧育湘.阻燃剂制造、性能及应用[M].北京:化学工业出版社,2006.
[3]潘玉琴,刘媛,孔霞.相容剂种类对阻燃抗静电HDPE复合材料性能的影响[J].塑料工业,2017,45(4):111-115.
[4]GIJSMAN P,STEENBAKKERS R,FURST C,et al.Differences in flame retardant mechanism of melamine cyanurate in polyamide6 and polyamide66[J].Polym Degrad Stab,2002,78(2):219-224.
[5]FANG Y,WANG Q,GUO C,et al.Effect of zinc borate and woodflour on thermal degradation and fire retardancy of polyvinyl chloride(PVC)composites[J].J Anal Appl Pyrolysis,2013,100(17):230-236.
[6]RAMOS R,BOSCHI-FILHO H.The size of compact extra dimensions from black-body radiation laws[J].Physica A,2014,39(1):261-267.
[7]KING J A,TUCKER K W,VOGT B D,et al.Electrically and thermally conductive nylon 6,6[J].Polym Compos,1999,20(5):643-654.
[8]董秀洁.抗静电阻燃材料ABS、PP、PE的研究与开发[J].印染助剂,2002,19(1):48-51.
[9]李德龙,李振宇,刘焱.加工工艺对聚乙烯热收缩膜性能的影响[J].塑料科技,2012,40(2):64-66.
[10]SHAO Z B,DENG C,TAN Y,et al.An efficient monocomponent polymeric intumescent flame retardant for polypropylene:Preparation and application[J].ACS Appl Mater Int,2014,6(1):7363-7370.
[11]LI X S,ZHAO Z L,WANG Y H,et al.Highly efficient flame retardant,flexible,and strong adhesive intumescent coating on polypropylene using hyperbranched polyamide[J].Chem Eng J,2017,324(9):237-250.
[12]廖阳飞,张旭东.塑料涂料研究进展[J].上海涂料,2008,46(8):14-18.
[13]HU X,GUO Y,CHEN L,et al.A novel polymeric intumescent flame retardant:Synthesis,thermal degradation mechanism and application in ABS co-polymer[J].Polym Degrad Stab,2012,97(9):1772-1778.