自旋交叉磁性聚合物微球的制备及性能表征
|
摘要
将丙烯酸和苯乙烯聚合得到羧基化改性的聚苯乙烯微球,以改性聚苯乙烯微球为核,表面接枝有机配体,通过自组装反应制备了一种具有自旋交叉性能的磁性聚合物微球。讨论了不同条件对改性聚苯乙烯微球粒径和分散性的影响,发现在苯乙烯用量为13mL、丙烯酸用量为1mL、引发剂用量为0.1g、水用量为125mL时,改性聚苯乙烯微球粒径最小,分散性最佳。通过场发射透射电镜(TEM)、红外光谱(FT-IR)、场发射扫描电镜(SEM)、拉曼光谱(Raman)、差示扫描量热法(DSC)、超导量子干涉(SQUID)等手段对磁性聚合物微球进行结构和磁学性能表征。结果表明,所制备的改性聚苯乙烯微球粒径在300nm左右,磁性聚合物微球粒径在350nm左右;自旋交叉配合物成功接枝到聚合物微球表面,表现出明显的自旋交叉现象,自旋转换温度为T_c↑=301K、T_c↓=293K,伴有一个8K的滞回宽度。
Modified polystyrene microspheres were prepared by copolymerization of styrene with acrylic acid and grafted with 4-amino-1,2,4-triazole.Then the spin crossover magnetic polymer microspheres were prepared by self-assembly reaction with Fe(Ⅱ).The effect of different reagent dosages on the size of microspheres was discussed,and the results showed that the optimal reagent dosages are as follows:styrene 13 mL,acrylic acid 1 mL,initiator 0.1 g,H_2O 125 mL.The composition and magnetic susceptibility of microspheres were characterized by TEM、FT-IR、SEM、Raman、DSC、SQUID.The results showed that the size of modified polystyrene microspheres was 300 nm,the size of polymer microspheres was 350 nm.The results also indicated that spin transition temperature(T_c↑=301 K,T_c↓=293 K)with a hysteresis loopΔ=8 K,it also meant that the polystyrene microspheres were grafted with spin crossover complex successfully.
Modified polystyrene microspheres were prepared by copolymerization of styrene with acrylic acid and grafted with 4-amino-1,2,4-triazole.Then the spin crossover magnetic polymer microspheres were prepared by self-assembly reaction with Fe(Ⅱ).The effect of different reagent dosages on the size of microspheres was discussed,and the results showed that the optimal reagent dosages are as follows:styrene 13 mL,acrylic acid 1 mL,initiator 0.1 g,H_2O 125 mL.The composition and magnetic susceptibility of microspheres were characterized by TEM、FT-IR、SEM、Raman、DSC、SQUID.The results showed that the size of modified polystyrene microspheres was 300 nm,the size of polymer microspheres was 350 nm.The results also indicated that spin transition temperature(T_c↑=301 K,T_c↓=293 K)with a hysteresis loopΔ=8 K,it also meant that the polystyrene microspheres were grafted with spin crossover complex successfully.
引文
[1] GUTLICH P,GARCIA Y.Spin crossover phenomena in Fe(Ⅱ)complexes[J].Chemical Society Reviews,2000,29(6):419-427.
[2] TITS-PADILLA S,HERRERA J M.Bifunctional hybrid SiO2 nanoparticles showing synergy between core spin crossover and shell luminescence properties[J].Angew Chem Int Ed Engl,2011,50(14):3290-3293.
[3] CORONADO E,GALAN-MASCAROS J R.Bistable spincrossover nanoparticles showing magnetic thermal hysteresis near room temperature[J].Advanced Materials,2007,19(10):1359.
[4] RUIZ E.Charge transport properties of spin crossover systems[J].Phys Chem Chem Phys,2014,16(1):14-22.
[5] JUNG J H,ONO Y.Creation of both right-handed and lefthanded silica structures by sol-gel transcription of organogel fibers compriced of chiral diaminoasclohexane derivalives[J].Journal of the American Chemical Society,2000,122(20):5008-5009.
[6] SATOSHI KOBAYASHI,NOBUHIRO HAMASAKI.Preparation of helical transition-metal oxide tubes using organogelators as structure-directing agents[J].Journal of the American Chemical Society,2002,124(23):6550.
[7] RODRIGUEZ-LLANSOLA F,ESCUDER B.Switchable performance of an L-proline-derived basic catalyst controlled by supramolecular gelation[J].Journal of the American Chemical Society,2009,131(32):11478-11484.
[8] TOKAREV A,SALMON L,GUARI Y.Synthesis of spin crossover nano-objects with different morphologies and properties[J].New Journal of Chemistry,2011,35(10):2081.
[9] BARTUAL-MURGUI C,SALMON L.High quality nanopatterned thin films of the coordination compound{Fe(pyrazine)[Pt(CN)(4)]}deposited layer-by-layer[J].New Journal of Chemistry,2011,35(10):2089-2094.
[10]PAQUIRISSAMY A,RUYACK A R.Versatile nano-platforms for hybrid systems:expressing spin-transition behavior on nanoparticles[J].J Mater Chem C,2015,3(14):3350-3355.
[11]王晔晨,全微雷,张金敏,等.磁性聚合物微球的制备及其应用研究进展[J].化工进展,2017,36(8):2971-2977.
[12]WANG X,MCHALE R.Metal-containing polymers:building blocks for functional(nano)materials[J].Macromol Rapid Commun,2010,31(4):331-350.
[13]PHONSRI W,HARDING D J,HARDING P.Stepped spin crossover in Fe(Ⅲ)halogen substituted quinolylsalicylaldimine complexes[J].Dalton Trans,2014,43(46):17509-17518.
[14]STOCK N,BISWAS S.Synthesis of metal-organic frameworks(MOFs):routes to various MOF topologies,morphologies,and composites[J].Chem Rev,2012,112(2):933-969.
[15]SEREDYUK M,GASPAR A B.One-dimensional iron(Ⅱ)compounds exhibiting spin crossover and liquid crystalline properties in the room temperature region[J].Inorganic Chemistry,2008,47(22):10232-10245.
[2] TITS-PADILLA S,HERRERA J M.Bifunctional hybrid SiO2 nanoparticles showing synergy between core spin crossover and shell luminescence properties[J].Angew Chem Int Ed Engl,2011,50(14):3290-3293.
[3] CORONADO E,GALAN-MASCAROS J R.Bistable spincrossover nanoparticles showing magnetic thermal hysteresis near room temperature[J].Advanced Materials,2007,19(10):1359.
[4] RUIZ E.Charge transport properties of spin crossover systems[J].Phys Chem Chem Phys,2014,16(1):14-22.
[5] JUNG J H,ONO Y.Creation of both right-handed and lefthanded silica structures by sol-gel transcription of organogel fibers compriced of chiral diaminoasclohexane derivalives[J].Journal of the American Chemical Society,2000,122(20):5008-5009.
[6] SATOSHI KOBAYASHI,NOBUHIRO HAMASAKI.Preparation of helical transition-metal oxide tubes using organogelators as structure-directing agents[J].Journal of the American Chemical Society,2002,124(23):6550.
[7] RODRIGUEZ-LLANSOLA F,ESCUDER B.Switchable performance of an L-proline-derived basic catalyst controlled by supramolecular gelation[J].Journal of the American Chemical Society,2009,131(32):11478-11484.
[8] TOKAREV A,SALMON L,GUARI Y.Synthesis of spin crossover nano-objects with different morphologies and properties[J].New Journal of Chemistry,2011,35(10):2081.
[9] BARTUAL-MURGUI C,SALMON L.High quality nanopatterned thin films of the coordination compound{Fe(pyrazine)[Pt(CN)(4)]}deposited layer-by-layer[J].New Journal of Chemistry,2011,35(10):2089-2094.
[10]PAQUIRISSAMY A,RUYACK A R.Versatile nano-platforms for hybrid systems:expressing spin-transition behavior on nanoparticles[J].J Mater Chem C,2015,3(14):3350-3355.
[11]王晔晨,全微雷,张金敏,等.磁性聚合物微球的制备及其应用研究进展[J].化工进展,2017,36(8):2971-2977.
[12]WANG X,MCHALE R.Metal-containing polymers:building blocks for functional(nano)materials[J].Macromol Rapid Commun,2010,31(4):331-350.
[13]PHONSRI W,HARDING D J,HARDING P.Stepped spin crossover in Fe(Ⅲ)halogen substituted quinolylsalicylaldimine complexes[J].Dalton Trans,2014,43(46):17509-17518.
[14]STOCK N,BISWAS S.Synthesis of metal-organic frameworks(MOFs):routes to various MOF topologies,morphologies,and composites[J].Chem Rev,2012,112(2):933-969.
[15]SEREDYUK M,GASPAR A B.One-dimensional iron(Ⅱ)compounds exhibiting spin crossover and liquid crystalline properties in the room temperature region[J].Inorganic Chemistry,2008,47(22):10232-10245.