一种基于氢氧化镁的环氧树脂固化剂的制备与表征
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摘要
通过己二酸(AA)和二乙烯三胺(DETA)改性制得了一种氨基功能化氢氧化镁(DETA-AA-MH),并将其用作环氧树脂固化剂。采用FTIR、XRD、固体核磁、纳米粒径分析仪、SEM和TGA对DETA-AA-MH的化学结构、形貌以及热稳定性进行了表征,并通过FTIR和DSC分析得到环氧树脂(DGEBA)和DETA-AA-MH发生固化反应的最佳质量分数分别为84.03%和15.97%,热固化实验分析得到最佳反应条件为:预固化温度及时间(80℃/0.5 h)和后固化温度及时间(110℃/3 h)。LOI测试分析结果表明,DGEBA/DETA-AA-MH较DGEBA/DETA的LOI提高了10.15%。采用SEM和EDS对环氧树脂燃烧后的炭残留物进行分析,结果表明,在燃烧过程中DETA-AA-MH促进保护碳层的形成。机械性能测试表明,DGEBA/DETA-AA-MH(固化剂质量分数15.97%)与DGEBA/DETA(固化剂质量分数7.38%)对比发现其弯曲强度、弯曲模量和冲击强度分别提高了663.64%、49.92%、235.77%。
A novel amine-functionalized curing agent for epoxy resin( EP) based on magnesium hydroxide( DETA-AA-MH) was obtained by successive treatment of magnesium hydrate( MH) with hexanedioic acid and diethylenetriamine( DETA). DETA-AA-MH was characterized by Fourier transform infrared spectroscopy( FTIR),X-ray power diffraction( XRD),solidstate nuclear magnetic resonance( SSNMR) technique,nano particle analyzer,scanning electron microscope( SEM) and thermogravimetric analysis( TGA). The curing reaction was investigated by FTIR and differential scanning calorimeter( DSC). The best mass ratio between epoxy resin( DGEBA) and DETA-AA-MH was 84. 03% and 15. 97%,and the optimum curing conditions were that the precured reaction was carried out at 80 ℃ for 0. 5 h and the post curing was performed at 110 ℃ for 3 h. Flame retardance of the EPs was evaluated by LOI tests,the LOI value of DGEBA/DETA-AA-MH was an improvement of10. 15% compared with that of DGEBA/DETA. In addition,the char residue of epoxy resin after combustion was characterized by SEM and EDS. The results showed that DETA-AA-MH could promotethe char formation served as a protective char layer during burning. The experiments for determining the mechanic properties of DETA-AA-MH cured EPs were also conducted,which indicated that compared to the properties of EP containing 7. 38% DETA( mass fraction),the flexural strength,flexural modulus and impact strength of EP containing 15. 97% DETA-AA-MH( mass fraction) efficiently increased by 663. 64%,49. 92% and 235. 77%,respectively.
A novel amine-functionalized curing agent for epoxy resin( EP) based on magnesium hydroxide( DETA-AA-MH) was obtained by successive treatment of magnesium hydrate( MH) with hexanedioic acid and diethylenetriamine( DETA). DETA-AA-MH was characterized by Fourier transform infrared spectroscopy( FTIR),X-ray power diffraction( XRD),solidstate nuclear magnetic resonance( SSNMR) technique,nano particle analyzer,scanning electron microscope( SEM) and thermogravimetric analysis( TGA). The curing reaction was investigated by FTIR and differential scanning calorimeter( DSC). The best mass ratio between epoxy resin( DGEBA) and DETA-AA-MH was 84. 03% and 15. 97%,and the optimum curing conditions were that the precured reaction was carried out at 80 ℃ for 0. 5 h and the post curing was performed at 110 ℃ for 3 h. Flame retardance of the EPs was evaluated by LOI tests,the LOI value of DGEBA/DETA-AA-MH was an improvement of10. 15% compared with that of DGEBA/DETA. In addition,the char residue of epoxy resin after combustion was characterized by SEM and EDS. The results showed that DETA-AA-MH could promotethe char formation served as a protective char layer during burning. The experiments for determining the mechanic properties of DETA-AA-MH cured EPs were also conducted,which indicated that compared to the properties of EP containing 7. 38% DETA( mass fraction),the flexural strength,flexural modulus and impact strength of EP containing 15. 97% DETA-AA-MH( mass fraction) efficiently increased by 663. 64%,49. 92% and 235. 77%,respectively.
引文
[1]Shen Wei(沈威),Wang Xiaoping(王小萍),Jia Demin(贾德民).Research progress in toughening modification techniques of epoxy resin[J].Thermosetting Resin(热固性树脂),2010,25(3):49-54.
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[8]Liu W S,Wang Z G,Xiong L.Phosphorus-containing liquid cycloali-phatic epoxy resins for reworkable environment-friendly electronic packaging materials[J].Polymer,2010,51:4776-4783.
[9]Johnsen B B,Kinloch A J,Mohammed R D.Toughening mechanisms of nanoparticle-modified epoxy polymers[J].Polymer,2007,48:530-541.
[10]Chen Y,Zhou T,Fang H.A novel preparation of nanosized hexagonal Mg(OH)2as a flame retardant[J].Particuology,2016,24:177-182.
[11]An D,Wang L,Zheng Y.In situ preparation and surface modification of magnesium hydroxide nanoparticles[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,348:9-13.
[12]Zhu S,Zhang Y.Deformation and fracture of Mg(OH)2-filled polyolefin composites under tensile stress[J].Journal of Applied Polymer Science,2003,89:3248-3255.
[13]Zhang F,Zhang H,Su Z.Surface treatment of magnesium hydroxide to improve its dispersion in organic phase by the ultrasonic technique[J].Applied Surface Science,2007,253:7393-7397.
[14]Hui Xuemei(惠雪梅),Zhang Wei(张炜),Wang Xiaojie(王晓洁).Research progress of epoxy nano-composite materials[J].China Synthetic Resin and Plastics(合成树脂及塑料),2003,20(6):62-65.
[15]Yan H,Du X,Zhang Meng,et al.Synthesis and characterization of novel organic magnesium salt flame retardant[J].Materials Letters,2014,134:210-213.
[16]Xu Hongyin(许洪胤),Li Li(李莉),Tan Hui(谭慧).Preparation process of thiourea modified diethylenetriamine for epoxy curing agent[J].Thermosetting Resin(热固性树脂),2011,26(6):24-27.
[17]Cui Z F,Ren H J,Liu G X.Synthesis and characterization of terbium-trimesic acid luminescent complex in polyvinylpyrrolidone matrix[J].Journal of Rare Earths,2006,24:724-727.
[18]Liu Xiao(刘晓),Wang Ziming(王子明),Zhu Jie(朱洁),et al.Preparation and characterization of new type amide-structural polycarboxylate superplasticizer[J].Journal of the Chinese Ceramic Society(硅酸盐学报),2013,41(8):1079-1085.
[19]Li Cui(李翠),Xu Xin(徐昕),Bao Changli(鲍长利),et al.Adsorption of Au(Ⅲ)and Pd(Ⅱ)in solution of 2,2'-diaminodiethylamine modified multiwalled carbon nanotubes[J].Chemical Journal of Chinese Universities(高等学校化学学报),2012,33(3):856-590.
[20]Chen Y,Zhou T,Fang H.A novel preparation of nano-sized hexagonal Mg(OH)2[J].Procedia Engineering,2015,102:388-394.
[21]Shah F U,Akhtar F,Saif Ullah Khan M.Solid-state13C,15N and29Si NMR characterization of block copolymers with CO2capture properties[J].Magn Reson Chem,2016,DOI:10.1002/mrc.4440.
[22]De Angelis A A,Capitani D,Crescenzi V.Synthesis and13C CPMAS NMR characterization of a new chitosan-based polymeric network[J].Macromolecules,1998,31:1595-1601.
[23]Gao C,Wang L,Lei Z,et al.Property of intrinsic flame retardant epoxy resin cured by functional magnesium organic composite salt and diethylenetriamine[J].Fire and Materials,2017,41(2):180-192.
[24]Huang K,Zhang Y,Li M.Preparation of a light color cardanolbased curing agent and epoxy resin composite:Cure-induced phase separation and its effect on properties[J].Progress in Organic Coatings,2012,74:240-247.
[25]Jiang Qibin(姜其斌),Wu Biyao(吴壁耀).Synthesis and characterization of epoxy diacrylates resin[J].Thermosetting Resin(热固性树脂),2001,16(4):6-8.
[26]Denq B L,Hu Y S,Chen L W.The curing reaction and physical properties of DGEBA/DETA epoxy resin blended with propyl ester phosphazene[J].Journal of Applied Polymer Science,1999,74:229-237.
[27]Pukanszky B,Voros G.Mechanism of interfacial interactions in particulatefilled composites[J].Journal of Composite Interfaces,1993,1:411-427.
[28]Yin J,Zhang Y,Zhang Y X.Fracture behavior and deformation mechanism of polypropylene/ethylene octene copolymer/magnesium hydroxide ternary phase composites[J].Journal of Applied Polymer Science,2005,98:957-967.
[29]Elbasuney S,Mostafa S F.Continuous flow formulation and functionalization of magnesium di-hydroxide nanorods as a clean nano-fire extinguisher[J].Powder Technology,2015,278:72-83.
[30]Reimschuessel H K,Dege G J.Polyamides:Decarboxylation and desamination in nylon 6 equilibrium polymer[J].Journal of Polymer Science:Part A-1,1970,8:3265-3283.
[31]Wang Z,Han E,Ke W.Influence of nano-LDHs on char formation and fire-resistant properties of flame-retardant coating[J].Progress in Organic Coatings,2005,53:29-37.
[2]Wan J,Gan B,Li C.A sustainable,eugenol-derived epoxy resin with high biobased content,modulus,hardness and low flammability:Synthesis,curing kinetics and structure-property relationship[J].Chemical Engineering Journal,2016,284:1080-1093.
[3]Yang S,Wang J,Huo S.The synergistic effect of maleimide and phosphaphenanthrene groups on a reactive flame-retarded epoxy resin system[J].Polymer Degradation and Stability,2015,115:63-69.
[4]Ren R,Xiong X,Ma X.Isothermal curing kinetics and mechanism of DGEBA epoxy resin with phthalide-containing aromatic diamine[J].Thermochim Acta,2016,623:15-21.
[5]Chekanov Y,Arrington D,Brust G.Frontal curing of epoxy resins:Comparison of mechanical and thermal properties to batch-cured materials[J].Journal of Applied Polymer Science,1997,66:1209-1216.
[6]Dean K,Cook W D,Zipper M D.Curing behaviour of IPNs formed from model VERs and epoxy systems I amine cured epoxy[J].Polymer,2001,42:1345-1359.
[7]Wang C S,Shieh J Y.Phosphorus-containing epoxy resin for an electronic application[J].Journal of Applied Polymer Science,1999,73:353-361.
[8]Liu W S,Wang Z G,Xiong L.Phosphorus-containing liquid cycloali-phatic epoxy resins for reworkable environment-friendly electronic packaging materials[J].Polymer,2010,51:4776-4783.
[9]Johnsen B B,Kinloch A J,Mohammed R D.Toughening mechanisms of nanoparticle-modified epoxy polymers[J].Polymer,2007,48:530-541.
[10]Chen Y,Zhou T,Fang H.A novel preparation of nanosized hexagonal Mg(OH)2as a flame retardant[J].Particuology,2016,24:177-182.
[11]An D,Wang L,Zheng Y.In situ preparation and surface modification of magnesium hydroxide nanoparticles[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,348:9-13.
[12]Zhu S,Zhang Y.Deformation and fracture of Mg(OH)2-filled polyolefin composites under tensile stress[J].Journal of Applied Polymer Science,2003,89:3248-3255.
[13]Zhang F,Zhang H,Su Z.Surface treatment of magnesium hydroxide to improve its dispersion in organic phase by the ultrasonic technique[J].Applied Surface Science,2007,253:7393-7397.
[14]Hui Xuemei(惠雪梅),Zhang Wei(张炜),Wang Xiaojie(王晓洁).Research progress of epoxy nano-composite materials[J].China Synthetic Resin and Plastics(合成树脂及塑料),2003,20(6):62-65.
[15]Yan H,Du X,Zhang Meng,et al.Synthesis and characterization of novel organic magnesium salt flame retardant[J].Materials Letters,2014,134:210-213.
[16]Xu Hongyin(许洪胤),Li Li(李莉),Tan Hui(谭慧).Preparation process of thiourea modified diethylenetriamine for epoxy curing agent[J].Thermosetting Resin(热固性树脂),2011,26(6):24-27.
[17]Cui Z F,Ren H J,Liu G X.Synthesis and characterization of terbium-trimesic acid luminescent complex in polyvinylpyrrolidone matrix[J].Journal of Rare Earths,2006,24:724-727.
[18]Liu Xiao(刘晓),Wang Ziming(王子明),Zhu Jie(朱洁),et al.Preparation and characterization of new type amide-structural polycarboxylate superplasticizer[J].Journal of the Chinese Ceramic Society(硅酸盐学报),2013,41(8):1079-1085.
[19]Li Cui(李翠),Xu Xin(徐昕),Bao Changli(鲍长利),et al.Adsorption of Au(Ⅲ)and Pd(Ⅱ)in solution of 2,2'-diaminodiethylamine modified multiwalled carbon nanotubes[J].Chemical Journal of Chinese Universities(高等学校化学学报),2012,33(3):856-590.
[20]Chen Y,Zhou T,Fang H.A novel preparation of nano-sized hexagonal Mg(OH)2[J].Procedia Engineering,2015,102:388-394.
[21]Shah F U,Akhtar F,Saif Ullah Khan M.Solid-state13C,15N and29Si NMR characterization of block copolymers with CO2capture properties[J].Magn Reson Chem,2016,DOI:10.1002/mrc.4440.
[22]De Angelis A A,Capitani D,Crescenzi V.Synthesis and13C CPMAS NMR characterization of a new chitosan-based polymeric network[J].Macromolecules,1998,31:1595-1601.
[23]Gao C,Wang L,Lei Z,et al.Property of intrinsic flame retardant epoxy resin cured by functional magnesium organic composite salt and diethylenetriamine[J].Fire and Materials,2017,41(2):180-192.
[24]Huang K,Zhang Y,Li M.Preparation of a light color cardanolbased curing agent and epoxy resin composite:Cure-induced phase separation and its effect on properties[J].Progress in Organic Coatings,2012,74:240-247.
[25]Jiang Qibin(姜其斌),Wu Biyao(吴壁耀).Synthesis and characterization of epoxy diacrylates resin[J].Thermosetting Resin(热固性树脂),2001,16(4):6-8.
[26]Denq B L,Hu Y S,Chen L W.The curing reaction and physical properties of DGEBA/DETA epoxy resin blended with propyl ester phosphazene[J].Journal of Applied Polymer Science,1999,74:229-237.
[27]Pukanszky B,Voros G.Mechanism of interfacial interactions in particulatefilled composites[J].Journal of Composite Interfaces,1993,1:411-427.
[28]Yin J,Zhang Y,Zhang Y X.Fracture behavior and deformation mechanism of polypropylene/ethylene octene copolymer/magnesium hydroxide ternary phase composites[J].Journal of Applied Polymer Science,2005,98:957-967.
[29]Elbasuney S,Mostafa S F.Continuous flow formulation and functionalization of magnesium di-hydroxide nanorods as a clean nano-fire extinguisher[J].Powder Technology,2015,278:72-83.
[30]Reimschuessel H K,Dege G J.Polyamides:Decarboxylation and desamination in nylon 6 equilibrium polymer[J].Journal of Polymer Science:Part A-1,1970,8:3265-3283.
[31]Wang Z,Han E,Ke W.Influence of nano-LDHs on char formation and fire-resistant properties of flame-retardant coating[J].Progress in Organic Coatings,2005,53:29-37.