DOPO-POSS掺杂没食子环氧纳米复合材料的制备及性能
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摘要
合成了没食子环氧树脂及2种不同分子结构的经9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)修饰的环氧基笼形倍半硅氧烷(DOPO-POSS),采用浇注工艺制备了新型没食子环氧纳米复合材料,考察了DOPO-POSS分子结构及用量对复合材料力学性能、阻燃性能及热稳定性的影响。结果表明:随着DOPO-POSS含量的增加,复合材料的阻燃性能提高,但力学性能有所下降;当DOPO-POSS末端基均为DOPO且体系磷质量分数为0.5%时,复合材料的冲击强度及极限氧指数较双酚A型环氧树脂分别提高了3.29 kJ/m~2,6.4%,初始降解温度达309℃;DOPO-POSS可以用作没食子环氧树脂的高效增韧剂及阻燃剂。
The bio-based fallic epoxy resin and two 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) modified polyhedral oligomeric silsesquioxane(POSS)(DOPO-POSS) in different molecular structures were synthesized,which were used to prepare a novel gallic epoxy nano-composites via pouring process. The influence of molecular structure and content of DOPO-POSS on mechanical properties,flame retardancy and thermal stability of the nanocomposites were investigated. The results show that with the increase of DOPO-POSS content,the flame retardancy of the composites is enhanced while its mechanical properties is decreased. The impact strength and limiting oxygen index of the nanocomposites are higher than those of pure Bisphenol A epoxy resin by 3.29 kJ/m~2 and6.4% respectively when all the terminal groups are DOPO in DOPO-POSS and the mass fraction of phosphorus in the nanocomposites is 0.5%. The initial thermal degradation temperature of the nanocomposites reaches 309 ℃. DOPOPOSS can be used as high-efficient toughening agent and flame retardant for gallic epoxy resin.
The bio-based fallic epoxy resin and two 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) modified polyhedral oligomeric silsesquioxane(POSS)(DOPO-POSS) in different molecular structures were synthesized,which were used to prepare a novel gallic epoxy nano-composites via pouring process. The influence of molecular structure and content of DOPO-POSS on mechanical properties,flame retardancy and thermal stability of the nanocomposites were investigated. The results show that with the increase of DOPO-POSS content,the flame retardancy of the composites is enhanced while its mechanical properties is decreased. The impact strength and limiting oxygen index of the nanocomposites are higher than those of pure Bisphenol A epoxy resin by 3.29 kJ/m~2 and6.4% respectively when all the terminal groups are DOPO in DOPO-POSS and the mass fraction of phosphorus in the nanocomposites is 0.5%. The initial thermal degradation temperature of the nanocomposites reaches 309 ℃. DOPOPOSS can be used as high-efficient toughening agent and flame retardant for gallic epoxy resin.
引文
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[16]Du Yonggang,Gao Jungang,Yang Jianbo,et al.Dynamic rheological behavior and mechanical properties of PVC/CPE/MAP-POSS nanocomposites[J].J Appl Polym Sci,2013,129(1):174-180.
[17]Xu Xiaopeng,Chen Si,Tang Wei,et al.Synthesis and application of uracil derivatives as novel thermal stabilizers for rigid poly(vinyl chloride)[J].Polym Degrad Stab,2013,98(2):659-665.
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[3]Marotta A,Ambrogi V,Cerruti P,et al.Green approaches in the synthesis of furan-based diepoxy monomers[J].RSC Adv,2018,8(29):16330-16335.
[4]Zhang Quanxuan,Molenda M,Reineke T M.Epoxy resin thermosets derived from trehalose andβ-cyclodextrin[J].Macromolecules,2016,49(22):8397-8406.
[5]Zhang Junhao,Kong Qinghong,Wang Deyi.Simultaneously improving the fire safety and mechanical properties of epoxy resin with Fe-CNTs via large-scale preparation[J].J Mater Chem A,2018,6(15):6376-6386.
[6]Faye I,Decostanzi M,Ecochard Y,et al.Eugenol bio-based epoxy thermosets:from cloves to applied materials[J].Green Chem,2017,19(21):5236-5242.
[7]Stemmelen M,Pessel F,Lapinte V,et al.A fully biobased epoxy resin from vegetable oils:from the synthesis of the precursors by thiol-ene reaction to the study of the final material[J].J Polym Sci Part A:Polym Chem,2011,49(11):2434-2444.
[8]Lligadas G,Ronda J C,Galia M,et al.Development of novel phosphorus-containing epoxy resins from renewable resources[J].J Polym Sci Part A:Polym Chem,2006,44(23):6717-6727.
[9]Pan Xiao,Sengupta P,Webster D C.High biobased content epoxy-anhydride thermosets from epoxidized sucrose esters of fatty acids[J].Biomacromolecules,2011,12(6):2416-2428.
[10]Aouf C,Nouailhas H,Fache M,et al.Multi-functionalization of gallic acid:synthesis of a novel bio-based epoxy resin[J].Eur Polym J,2013,49(6):1185-1195.
[11]Aouf C,Lecomte J,Villeneuve P,et al.Chemo-enzymatic functionalization of gallic and vanillic acids:synthesis of biobased epoxy resins prepolymers[J].Green Chem,2012,14(8):2328-2336.
[12]Ramirez S M,Diaz Y J,Campos R,et al.Incompletely condensed fluoroalkyl silsesquioxanes and derivatives:precursors for low surface energy materials[J].J Am Chem Soc,2011,133(50):20084-20087.
[13]杜永刚,王一鸣,于月茹,等.功能POSS掺杂新型生物基环氧树脂的制备[J].合成树脂及塑料,2018,35(5):45-49.
[14]Zhang Wenchao,Li Xiangmei,Yang Rongjie.Blowing-out effect in epoxy composites flame retarded by DOPO-POSS and its correlation with amide curing agents[J].Polym Degrad Stab,2012,97(8):1314-1324.
[15]Liu C,Chen T,Yuan C H,et al.Modification of epoxy resin through the self-assembly of a surfactant-like multi-element flame retardant[J].J Mater Chem A,2016,4(9):3462-3470.
[16]Du Yonggang,Gao Jungang,Yang Jianbo,et al.Dynamic rheological behavior and mechanical properties of PVC/CPE/MAP-POSS nanocomposites[J].J Appl Polym Sci,2013,129(1):174-180.
[17]Xu Xiaopeng,Chen Si,Tang Wei,et al.Synthesis and application of uracil derivatives as novel thermal stabilizers for rigid poly(vinyl chloride)[J].Polym Degrad Stab,2013,98(2):659-665.