含氟丙烯酸酯聚合物修饰纳米二氧化钛粒子的制备
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摘要
经硅烷偶联剂KH550表面预处理后,采用原子转移自由基聚合(ATRP)法在纳米TiO_2粒子表面引入低表面能的含氟丙烯酸酯聚合物。运用傅里叶红外光谱(FT-IR)、光电子能谱(XPS)、热重分析(TGA)和扫描电子显微镜(SEM)等测试方法,对改性前后纳米TiO_2粒子的形貌和结构进行了系统研究。结果表明:KH550与纳米TiO_2粒子表面发生了缩合反应,纳米粒子表面接枝了氨基基团。硅烷偶联剂的用量增加,可显著提高最终产物的接枝率。含氟丙烯酸酯聚合物的接枝率最终可达38.5%。将接枝后的纳米TiO_2粒子负载在蓝湿革上,纳米粒子的团聚显著减少,分散性和疏水性能均得到提高。
Nano TiO_2 particles surface were pretreated by silane coupling agent KH550,and then fluorinated acrylate having low surface energy were polymerized on nano TiO_2 particles surface with atom transfer radical polymerization( ATRP) method. The morphology and structure of nano TiO_2 particles before and after modification was systematically investigated with testing methods of Fourier transform infrared spectroscopy( FT-IR),X-ray photoelectron spectroscopy( XPS),thermal gravimetric analyzer( TGA) and scanning electron microscope( SEM). Results indicate that there is condensation reaction between KH550 and nano TiO_2 particles surface. The amino group is grafted on the surface of nano particles. And the percent grafting of polymer is significantly improved with the increasing of silane coupling agent dosage. The percent grafting of fluorinated acrylate polymer on the surface of nano TiO_2 particles could reach 38. 5% eventually. When loading the modified nano TiO_2 particles on the surface of wet-blue leather,the reunite of the modified nano TiO_2 particles decreases significantly,and the dispersibility and hydrophobicity are improved.
Nano TiO_2 particles surface were pretreated by silane coupling agent KH550,and then fluorinated acrylate having low surface energy were polymerized on nano TiO_2 particles surface with atom transfer radical polymerization( ATRP) method. The morphology and structure of nano TiO_2 particles before and after modification was systematically investigated with testing methods of Fourier transform infrared spectroscopy( FT-IR),X-ray photoelectron spectroscopy( XPS),thermal gravimetric analyzer( TGA) and scanning electron microscope( SEM). Results indicate that there is condensation reaction between KH550 and nano TiO_2 particles surface. The amino group is grafted on the surface of nano particles. And the percent grafting of polymer is significantly improved with the increasing of silane coupling agent dosage. The percent grafting of fluorinated acrylate polymer on the surface of nano TiO_2 particles could reach 38. 5% eventually. When loading the modified nano TiO_2 particles on the surface of wet-blue leather,the reunite of the modified nano TiO_2 particles decreases significantly,and the dispersibility and hydrophobicity are improved.
引文
[1]Fujishima A,Honda K.Electrochemical photolysis of water at a semiconductor electrode[J].Nature,1972,238(5358):37-38.
[2]Macwan DP,Dave PN,Chaturvedi S.A review on nano-Ti O2sol–gel type syntheses and its applications[J].Journal of Materials Science,2011,46(11):3 669-3 686.
[3]王全杰,周庆芳,孙根行,等.纳米二氧化钛的制备及其在皮革涂饰剂中的应用展望[J].中国皮革,2004,33(23):11-15.
[4]李柯陈,王春华,彭健根,等.纳米二氧化钛的特性及其在制革工业中的应用[J].中国皮革,2015,44(7):21-25.
[5]Cheng B,Wang X,Wang L,et al.Surface modification of sub-micron spherical Si O2particles with butanedioic acid for electrophoresis in tetrachloroethylene[J].Materials Letters,2007,61(6):1 350-1 353.
[6]Bagwe R P,Hilliard L R,Tan W.Surface modification of silica nanoparticles to reduce aggregation and nonspecific binding[J].Langmuir,2006,22(9):4 357-4 362.
[7]Kim S,Kim E,Kim S,et al.Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate[J].Journal of Colloid and Interface Science,2005,292(1):93-98.
[8]Liu P.Polymer modified clay minerals:A review[J].Applied Clay Science,2007,38(S1-2):64-76.
[9]Wang H,Tang L,Wu X,et al.Fabrication and anti-frosting performance of super hydrophobic coating based on modified nano-sized calcium carbonate and ordinary polyacrylate[J].Applied Surface Science,2007,253(22):8 818-8 824.
[10]Chen X,Mao SS.Titanium dioxide nanomaterials:Synthesis,properties,modifications,and applications[J].Chemical Reviews,2007,107(7):2 891-2 959.
[11]许艳,刘阳思,张玉波,等.纳米Ti O2表面接枝聚甲基丙烯酸甲酯及其在白色油墨中的应用[J].化工新型材料,2009,37(1):75-76.
[12]Jariwala C P,Mathias L J.Syntheses,polymerization,and characterization of novel semifluorinated methacrylates,including novel liquid-crystalline materials[J].Macromolecules,1993,26(19):5 129-5 136.
[13]Boschet F,Kostov G,Ameduri B,et al.Kinetics of the radical copolymerization of 2,2,2-trifluoroethyl methacrylate with tertbutylα-trifluoromethacrylate[J].Journal of Polymer Science Part A:Polymer Chemistry,2010,48(5):1 029-1 037.
[2]Macwan DP,Dave PN,Chaturvedi S.A review on nano-Ti O2sol–gel type syntheses and its applications[J].Journal of Materials Science,2011,46(11):3 669-3 686.
[3]王全杰,周庆芳,孙根行,等.纳米二氧化钛的制备及其在皮革涂饰剂中的应用展望[J].中国皮革,2004,33(23):11-15.
[4]李柯陈,王春华,彭健根,等.纳米二氧化钛的特性及其在制革工业中的应用[J].中国皮革,2015,44(7):21-25.
[5]Cheng B,Wang X,Wang L,et al.Surface modification of sub-micron spherical Si O2particles with butanedioic acid for electrophoresis in tetrachloroethylene[J].Materials Letters,2007,61(6):1 350-1 353.
[6]Bagwe R P,Hilliard L R,Tan W.Surface modification of silica nanoparticles to reduce aggregation and nonspecific binding[J].Langmuir,2006,22(9):4 357-4 362.
[7]Kim S,Kim E,Kim S,et al.Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate[J].Journal of Colloid and Interface Science,2005,292(1):93-98.
[8]Liu P.Polymer modified clay minerals:A review[J].Applied Clay Science,2007,38(S1-2):64-76.
[9]Wang H,Tang L,Wu X,et al.Fabrication and anti-frosting performance of super hydrophobic coating based on modified nano-sized calcium carbonate and ordinary polyacrylate[J].Applied Surface Science,2007,253(22):8 818-8 824.
[10]Chen X,Mao SS.Titanium dioxide nanomaterials:Synthesis,properties,modifications,and applications[J].Chemical Reviews,2007,107(7):2 891-2 959.
[11]许艳,刘阳思,张玉波,等.纳米Ti O2表面接枝聚甲基丙烯酸甲酯及其在白色油墨中的应用[J].化工新型材料,2009,37(1):75-76.
[12]Jariwala C P,Mathias L J.Syntheses,polymerization,and characterization of novel semifluorinated methacrylates,including novel liquid-crystalline materials[J].Macromolecules,1993,26(19):5 129-5 136.
[13]Boschet F,Kostov G,Ameduri B,et al.Kinetics of the radical copolymerization of 2,2,2-trifluoroethyl methacrylate with tertbutylα-trifluoromethacrylate[J].Journal of Polymer Science Part A:Polymer Chemistry,2010,48(5):1 029-1 037.