腰果酚型聚苯并噁嗪基超疏水涂层的制备及其性能
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摘要
首先合成了腰果酚型苯并噁嗪单体(C-a),然后采用旋涂和热固化的方法制备了腰果酚型聚苯并噁嗪/SiO_2(PC-a/SiO_2)超疏水涂层。通过傅里叶红外光谱(FT-IR)及核磁共振(NMR)等测试手段对单体结构进行了表征,并对PC-a/SiO_2涂层的超疏水性能进行了研究。结果表明,通过调控SiO_2纳米粒子的掺杂量,可制备水接触角为(166±4)°,滚动角为6°的"荷叶效应"型超疏水涂层和水接触角为(151±3)°的"玫瑰花效应"型超疏水涂层。该PC-a/SiO_2超疏水涂层具有良好的热稳定性和抗紫外性能。
Cardanol-based benzoxazine(C-a)was synthesized from cardanol,paraformaldehyde and aniline,and then superhydrophobic coating combined with cardanol-based polybenzoxazine.Silica nanoparticles(SiO_2 NPs)were produced through spinning coating technique and thermal curing method.The chemical structure of C-a benzoxazine monomer was characterized by Fourier transform infrared(FT-IR)spectroscopy and nuclear magnetic resonance(NMR).Then,the polybenzoxazine coating(PC-a)was fabricated through thermal curing method and exhibited surface free energy of 22.5mJ/m2 after thermal curing at 200 ℃ for 1h.The wettability properties of PC-a/SiO_2 coating were characterized by optical contact angle(OCA)meter.As a result,the water contact angle of pure PC-a coating was(104±2)°,showing a hydrophobic property.By incorporating different contents of SiO_2 NPs,a "lotus effect" superhydrophobic PC-a/SiO_2 coating with water contact angle of(166±4)°and water sliding angle of 6°,a"petal effect"superhydrophobic PC-a/SiO_2 coating with water contact angle of(151±3)°could be both developed.After thermal treatment at 200℃ for 1h,the water contact angle and sliding angle of PC-a/SiO_270 coating were(163±4)°and 7°,respectively.Therefore,the superhydrophobic PC-a/SiO_270 coating could keep its stable superhydrophobicity with a wide range temperature.Moreover,the as-prepared hydrophobic PC-a coating still had hydrophobicity with a water contact angle of(97±1)°.Superhydrophobic PC-a/SiO_270 coating could both keep stable after UV exposure for 8 h.So the hydrophobic PC-a coating and superhydrophobic PC-a/SiO_270 coating had UV resistant property.In conclusion,this superhydrophobic coating based on cardanol polybenzoxazine shows excellent thermal stability and UV resistant property,which show broad application in the fields of oil-water separation and anti-corrosion.
Cardanol-based benzoxazine(C-a)was synthesized from cardanol,paraformaldehyde and aniline,and then superhydrophobic coating combined with cardanol-based polybenzoxazine.Silica nanoparticles(SiO_2 NPs)were produced through spinning coating technique and thermal curing method.The chemical structure of C-a benzoxazine monomer was characterized by Fourier transform infrared(FT-IR)spectroscopy and nuclear magnetic resonance(NMR).Then,the polybenzoxazine coating(PC-a)was fabricated through thermal curing method and exhibited surface free energy of 22.5mJ/m2 after thermal curing at 200 ℃ for 1h.The wettability properties of PC-a/SiO_2 coating were characterized by optical contact angle(OCA)meter.As a result,the water contact angle of pure PC-a coating was(104±2)°,showing a hydrophobic property.By incorporating different contents of SiO_2 NPs,a "lotus effect" superhydrophobic PC-a/SiO_2 coating with water contact angle of(166±4)°and water sliding angle of 6°,a"petal effect"superhydrophobic PC-a/SiO_2 coating with water contact angle of(151±3)°could be both developed.After thermal treatment at 200℃ for 1h,the water contact angle and sliding angle of PC-a/SiO_270 coating were(163±4)°and 7°,respectively.Therefore,the superhydrophobic PC-a/SiO_270 coating could keep its stable superhydrophobicity with a wide range temperature.Moreover,the as-prepared hydrophobic PC-a coating still had hydrophobicity with a water contact angle of(97±1)°.Superhydrophobic PC-a/SiO_270 coating could both keep stable after UV exposure for 8 h.So the hydrophobic PC-a coating and superhydrophobic PC-a/SiO_270 coating had UV resistant property.In conclusion,this superhydrophobic coating based on cardanol polybenzoxazine shows excellent thermal stability and UV resistant property,which show broad application in the fields of oil-water separation and anti-corrosion.
引文
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[13]张程夕,凌鸿,顾宜.腰果酚型苯并噁嗪的固化特性[J].高分子材料科学与工程,2011,27(5):92-95.
[14]AMBROZIC R,SEBENIK U,KRAJNC M.Synthesis,curing kinetics,thermal and mechanical behavior of novel cardanol-based benzoxazines[J].Polymer,2015,76:203-212.
[15]FENG L,ZHANG Y,XI J,et al.Petal effect:A superhydrophobic state with high adhesive force[J].Langmuir,2008,24(8):4114-4119.
[16]邱宇辰,刘克松,江雷.花生叶表面的高粘附超疏水特性研究及其仿生制备[J].中国科学:化学,2011(2):403-408.
[17]WANG G,GUO Z,LIU W.Interfacial effects of superhydrophobic plant surfaces:A review[J].Journal of Bionic Engineering,2014,11(3):325-345.
[2]ZHANG W F,LU X,XIN Z,et al.A self-cleaning polybenzoxazine/TiO2 surface with superhydrophobicity and superoleophilicity for oil/water separation[J].Nanoscale,2015,7(46):19476-19483.
[3]张雪英,陆馨,张芮,等.二胺型聚苯并噁嗪涂层在低碳钢表面的防腐蚀性能[J].华东理工大学学报(自然科学版),2017,43(5):614-619.
[4]周长路,辛忠.聚苯并噁嗪功能表面的构筑、性能与应用[J].化学进展,2018(1):1-15.
[5]ISHIDA H,LOW H Y.A study on the volumetric expansion of benzoxazine-based phenolic resin[J].Macromolecules,1997,30(4):1099-1106.
[6]KIM H,BRUNOVSKA Z,ISHIDA H.Dynamic mechanical analysis on highly thermally stable polybenzoxazines with an acetylene functional group[J].Journal of Applied Polymer Science,1999,73(6):857-862.
[7]CALDONA E B,de LEON A C C,THOMA P G,et al.Superhydrophobic rubber-modified polybenzoxazine/SiO2nanocomposite coating with anticorrosion,anti-ice,and superoleophilicity properties[J].Industrial&Engineering Chemistry Research,2017,56(6):1485-1497.
[8]LIU J,LU X,XIN Z,et al.Preparation and surface properties of transparent UV-resistant“petal effect”superhydrophobic surface based on polybenzoxazine[J].Applied Surface Science,2015,353:1137-1142.
[9]CHIOU K,ISHIDA H.Incorporation of natural renewable components and waste byproducts to benzoxazine based high performance materials[J].Current Organic Chemistry,2013,17(9):913-925.
[10]SINI N K,BIJWE J,VARMA I K.Renewable benzoxazine monomer from vanillin:Synthesis,characterization,and studies on curing behavior[J].Journal of Polymer Science Part A:Polymer Chemistry,2014,52(1):7-11.
[11]THIRUKUMARAN P,SHAKILA A,MUTHUSAMY S.Synthesis and characterization of novel bio-based benzoxazines from eugenol[J].RSC Advances,2014,4(4):7959-7966.
[12]WANG C,SUN J,LIU X,et al.Synthesis and copolymerization of fully bio-based benzoxazines from guaiacol,furfurylamine and stearylamine[J].Green Chemistry,2012,14(10):2799-2806.
[13]张程夕,凌鸿,顾宜.腰果酚型苯并噁嗪的固化特性[J].高分子材料科学与工程,2011,27(5):92-95.
[14]AMBROZIC R,SEBENIK U,KRAJNC M.Synthesis,curing kinetics,thermal and mechanical behavior of novel cardanol-based benzoxazines[J].Polymer,2015,76:203-212.
[15]FENG L,ZHANG Y,XI J,et al.Petal effect:A superhydrophobic state with high adhesive force[J].Langmuir,2008,24(8):4114-4119.
[16]邱宇辰,刘克松,江雷.花生叶表面的高粘附超疏水特性研究及其仿生制备[J].中国科学:化学,2011(2):403-408.
[17]WANG G,GUO Z,LIU W.Interfacial effects of superhydrophobic plant surfaces:A review[J].Journal of Bionic Engineering,2014,11(3):325-345.