丙烯腈-衣康酸共聚物接枝聚乙二醇固-固相变材料的制备及表征
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摘要
将衣康酸与丙烯腈共聚,构建具有双端羧基活性点的聚合物骨架,以二苯甲烷二异氰酸酯(MDI)为桥基,将聚乙二醇(PEG)接枝到聚合物骨架上,制备了丙烯腈-衣康酸共聚物接枝聚乙二醇(AIPCMs).采用红外光谱、差示扫描量热、X射线衍射、偏光显微镜、热失重及水静态接触角等方法研究了其结构、相变潜热性能、结晶性能、结晶形态、热稳定性及亲水性.结果表明,合成的AIPCMs具有固-固相变特性及优异的热储能性能,相变潜热达到70.5 J/g.化学接枝改变了AIPCMs中PEG的结晶结构及结晶形态.AIPCMs的热稳定性优异,初始分解温度达289℃,并且其亲水性较好,接触角最小可达33.71°.
The core of this study firstly synthesizes an "active"matrix materials with the itaconic acid containing double-carboxyl end group and acrylonitrile copolymer through molecular design. Then,the poly( ethylene glycol)( PEG) was grafted to the poly( acrylonitrile-co-itaconate) [P( AN-co-IA) ]using methylenediphenyl diisocyanate( MDI) as a bridge-base and cross-linking agent. The poly( acrylonitrile-co-itaconate)-graftpoly( ethylene glycol) [P( AN-co-IA)-g-PEG] solid-solid phase change materials( SSPCMs) were obtained in this paper. Furthermore,the chemical structure,crystallization properties,thermal energy storage properties,crystallization process,thermal stabilities,and hydrophilic property of the SSPCMs were investigated using Fourier transform infrared,differential scanning calorimetry,wide-angle X-ray diffraction,polarized optical microscopy,thermogravimetric analysis and water contact angle,respectively. The results showed that these SSPCMs had the characteristics of solid-solid phase change,excellent energy storage properties and latent heat of 70 J/g or more. The crystalline morphology and crystal structures of the synthesized SSPCMs are difference from PEG and P( AN-co-IA). Moreover,The SSPCMs have a good thermal stability and the initial decomposition temperature( T_d) is 289 ℃,and the hydrophilic property of the blend membrane were improved,the water contact angle minimum can be achieved at 33.71°.
The core of this study firstly synthesizes an "active"matrix materials with the itaconic acid containing double-carboxyl end group and acrylonitrile copolymer through molecular design. Then,the poly( ethylene glycol)( PEG) was grafted to the poly( acrylonitrile-co-itaconate) [P( AN-co-IA) ]using methylenediphenyl diisocyanate( MDI) as a bridge-base and cross-linking agent. The poly( acrylonitrile-co-itaconate)-graftpoly( ethylene glycol) [P( AN-co-IA)-g-PEG] solid-solid phase change materials( SSPCMs) were obtained in this paper. Furthermore,the chemical structure,crystallization properties,thermal energy storage properties,crystallization process,thermal stabilities,and hydrophilic property of the SSPCMs were investigated using Fourier transform infrared,differential scanning calorimetry,wide-angle X-ray diffraction,polarized optical microscopy,thermogravimetric analysis and water contact angle,respectively. The results showed that these SSPCMs had the characteristics of solid-solid phase change,excellent energy storage properties and latent heat of 70 J/g or more. The crystalline morphology and crystal structures of the synthesized SSPCMs are difference from PEG and P( AN-co-IA). Moreover,The SSPCMs have a good thermal stability and the initial decomposition temperature( T_d) is 289 ℃,and the hydrophilic property of the blend membrane were improved,the water contact angle minimum can be achieved at 33.71°.
引文
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[3]Chen C.Z.,Wang L.,Huang Y.,Sol.Energy Mater.Sol.Cells,2008,92(11),1382—1387
[4]Zhang Z.L.,Tang X.F.,Meng J.Y.,Zhang X.X.,Shi H.F.,Chem.J.Chinese Universities,2014,35(1),175—179(张智力,唐孝芬,孟洁云,张兴祥,石海峰.高等学校化学学报,2014,35(1),175—179)
[5]Li M.,Wu Z.S.,Tan J.M.,Appl.Energy,2013,103,393—399
[6]Zhang J.S.,Zhang X.,Wan Y.Z.,Mei D.D.,Zhang B.,Sol.Energy,2012,86(5),1142—1148
[7]Cai Y.B.,Xu X.L.,Gao C.T.,Bian T.Y.,Qiao H.,Wei Q.F.,Materials Letters,2012,89,43—46
[8]Kuznik F.,David D.,Johannes K.,Renew Sustain Energy Rev.,2011,15,379—391
[9]SarA.,Allcan C.,Bier A.,Mater.Chem.Phys.,2012,133,87—94
[10]SarA.,Alkcan C.,Bicer A.,Karaipe Kli A.,Sol.Energy Mater.Sol.Cells,2011,95,3195—201
[11]Zhou X.M.,J.Appl.Polym.Sci.,2009,113,2041—2045
[12]Zhang M.,Na Y.,Jiang Z.H.,Chem.J.Chinese Universities,2005,26(1),170—174(张梅,那莹,姜振华.高等学校化学学报,2005,26(1),170—174)
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[15]Chen C.Z.,Liu W.M.,Wang Z.Q.,Peng K.L.,Pan W.L.,Xie Q.,Sol.Energy Mater.Sol.Cells,2015,134,80—88
[16]Li Y.X.,Liu R.G.,Huang Y.,J.Appl.Polym.Sci.,2008,1100,1797—1803
[17]Guo J.,Xie P.,Zhang X.,Yu C.F.,Guan F.C.,Liu Y.F.,J.Appl.Polym.Sci.,2014,131
[18]Guo J.,Xiang H.X.,Gong X.Y.,Zhang Y.P.,Energy Source Part A,2011,33,1067—1175
[19]Luo N.,Wang D.N.,Ying S.K.,Macromolecules,1997,30,4405—4409
[20]Hu J.,Yu H.,Chen Y.,Zhu M.,J.Macromol.Sci.B,2006,45,615—621
[21]Wang D.,Han N.,Zhang X.X.,Wang L.J.,Wang N.,Li W.,Yu W.Y.,Li Z.N.,Chem.J.Chinese Universities,2015,36(6),1221—1227(王栋,韩娜,张兴祥,王乐军,王宁,李伟,于万永,李志南.高等学校化学学报,2015,36(6),1221—1227)
[22]Zhang X.W.,Qin F.Z.,Tong Y.J.,Xu L.H.,China Synthetic Fiber Industry,2007,30(4),63—65(张晓威,覃福作,童元建,徐樑华.合成纤维工业,2007,30(4),63—65)