一种基于立构复合及自组装方法构筑的耐受性疏水表面
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摘要
利用丙交酯开环聚合法制备了聚(D-乳酸)-聚二甲基硅氧烷-聚(D-乳酸)(PDLA-b-PDMS-b-PDLA)三嵌段聚合物,将其溶液涂覆至充斥着非溶剂蒸汽的聚(L-乳酸)(PLLA)表面,PDLA-b-PDMS-b-PDLA在缓慢沉积的过程中与PLLA发生立构复合及自组装,得到由立构复合的亚微米颗粒组装体形成的聚乳酸表面疏水层。研究了聚合物溶液的质量浓度、组装温度以及溶剂对聚乳酸表面的微观形貌和疏水性能产生的影响。结果表明,随着PDLA-b-PDMS-b-PDLA聚合物溶液质量浓度的增加,可以实现聚乳酸表面Wenzel-Cassie-Wenzel的疏水行为转变;在0℃下,可得到最大疏水角151°的疏水层;选择对聚合物溶解性、挥发速度不同的溶剂,得到的表面微观形貌和疏水性也不同。由于聚乳酸制品表面的PLLA链段与亚微米颗粒中的PDLA链段也能够立构复合,因此该表面疏水层对刀刮、胶带剥离和手指擦拭测试均表现出良好的耐受性。
Triblock copolymer,poly( D-lactide)-b-polydimethylsiloxane-b-poly( D-lactide)( PDLA-b-PDMSb-PDLA),was synthesized by ring-opening polymerization of D-lactide,and then its solution was coated onto the surface of poly( L-lactide)( PLLA) in a vail filled with non-solvent vapor. During the slow deposition process,PDMS with low surface energy was introduced to the PLLA surface. Meanwhile,PDLA segments stereocomplexed with the PLLA segments on the surface. A hydrophobic layer composed of stereocomposite submicron particles was formed on the surface of PLLA through the stereocomplexation between PLLA and PDLA-b-PDMS-b-PDLA and the self-assembly of PDLA-b-PDMS-b-PDLA. The influences of polymer solution concentration,assembly temperature and solvent on the surface morphology and the hydrophobicity of PLLA surface were further studied. With the increase of the concentration of PDLA-b-PDMS-b-PDLA, the hydrophobic behavior of the surface showed a transformation from Wenzel to Cassie status,and then returned to Wenzel status. When the assembly temperature was 0 ℃ and a 2 g/L PDLA-b-PDMS-b-PDLA/CH_2Cl_2 solution was deposited on the PLLA surface,the contact angle was 151°. When the assembly temperature raised to 30 ℃,the surface contact angle was 144° and the rolling angle was 5°. The obtained surface morphology and hydrophobicity were also varied with solvents with different solubility and volatilization rate. In addition,the hydrophobic surface of PLLA products can be achieved by means of stereocomplexation and self-assembly. By varying the concentration of PDLA-b-PDMS-b-PDLA solutions,the surface of PLLA products would eventually assembles into a "pearl necklace " shaped bicontinuous network structure. Because the surface of PLLA and the submicron particles were all connected with stereocomplexed PLLA/PDLA chains,the hydrophobic layer exhibited good durability against knife-scratch,tape-peel and finger-wipe tests. After the knife-scratch test and the tape peel test,the contact angle of the surface of the PLLA products was only slightly reduced,and the micro-spherical appearance of the PLLA surface existed after test.
Triblock copolymer,poly( D-lactide)-b-polydimethylsiloxane-b-poly( D-lactide)( PDLA-b-PDMSb-PDLA),was synthesized by ring-opening polymerization of D-lactide,and then its solution was coated onto the surface of poly( L-lactide)( PLLA) in a vail filled with non-solvent vapor. During the slow deposition process,PDMS with low surface energy was introduced to the PLLA surface. Meanwhile,PDLA segments stereocomplexed with the PLLA segments on the surface. A hydrophobic layer composed of stereocomposite submicron particles was formed on the surface of PLLA through the stereocomplexation between PLLA and PDLA-b-PDMS-b-PDLA and the self-assembly of PDLA-b-PDMS-b-PDLA. The influences of polymer solution concentration,assembly temperature and solvent on the surface morphology and the hydrophobicity of PLLA surface were further studied. With the increase of the concentration of PDLA-b-PDMS-b-PDLA, the hydrophobic behavior of the surface showed a transformation from Wenzel to Cassie status,and then returned to Wenzel status. When the assembly temperature was 0 ℃ and a 2 g/L PDLA-b-PDMS-b-PDLA/CH_2Cl_2 solution was deposited on the PLLA surface,the contact angle was 151°. When the assembly temperature raised to 30 ℃,the surface contact angle was 144° and the rolling angle was 5°. The obtained surface morphology and hydrophobicity were also varied with solvents with different solubility and volatilization rate. In addition,the hydrophobic surface of PLLA products can be achieved by means of stereocomplexation and self-assembly. By varying the concentration of PDLA-b-PDMS-b-PDLA solutions,the surface of PLLA products would eventually assembles into a "pearl necklace " shaped bicontinuous network structure. Because the surface of PLLA and the submicron particles were all connected with stereocomplexed PLLA/PDLA chains,the hydrophobic layer exhibited good durability against knife-scratch,tape-peel and finger-wipe tests. After the knife-scratch test and the tape peel test,the contact angle of the surface of the PLLA products was only slightly reduced,and the micro-spherical appearance of the PLLA surface existed after test.
引文
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[32]Lafuma A,Quere D. Superhydrophobic States[J]. Nat Mater,2003,2(7):457-460.
[2]Song J,Gao M,Zhao C,et al. Large-Area Fabrication of Droplet Pancake Bouncing Surface and Control of Bouncing State[J]. ACS Nano,2017,11(9):9259-9267.
[3]Sang-Hyeon L,Minho S,Kyu K M,et al. Tunable Multimodal Drop Bouncing Dynamics and Anti-icing Performance of a Magnetically Responsive Hair Array[J]. ACS Nano,2018,12(11):10693-10702.
[4]Jeeva J K,Palanivelu K. Facile Fabrication of Core-Shell Pr6O11-Zn O Modified Silane Coatings for Anti-corrosion Applications[J]. Appl Surf Sci,2014,288:60-68.
[5]Han Z,Feng X,Guo Z,et al. Flourishing Bioinspired Antifogging Materials with Superwettability:Progresses and Challenges[J]. Adv Mater,2018,30(13):1704652(1-32).
[6]YE Wenbo,HUANG Shijun,GUAN Huanmin,et al. Preparation and Properties of Superhydrophobic Polysiloxane Coatings[J]. Chinese J Appl Chem,2012,29(10):1123-1129(in Chinese).叶文波,黄世俊,关怀民,等.超疏水聚硅氧烷涂层的制备及其性能[J].应用化学,2012,29(10):1123-1129.
[7]Jakobi V,Schwarze J,Finlay J A,et al. Amphiphilic Alginates for Marine Antifouling Applications[J]. Biomacromolecules,2018,19(2):402-408.
[8]Zhang P,Yang L,Li Q,et al. Ellipsoidal Colloids with a Controlled Surface Roughness via Bioinspired Surface Engineering:Building Blocks for Liquid Marbles and Superhydrophobic Surfaces[J]. ACS Appl Mater Interfaces,2017,9(8):7648-7657.
[9]Onda T,Shibuichi S,Satoh N,et al. Super-Water-Repellent Fractal Surfaces[J]. Langmuir,1996,12(9):2125-2127.
[10] Shiu J Y,Kuo C W,Chen P,et al. Fabrication of Tunable Superhydrophobic Surfaces by Nanosphere Lithography[J].Chem Mater,2004,16(4):561-564.
[11]Lau K K S,Bico J,Teo K B K,et al. Superhydrophobic Carbon Nanotube Forests[J]. Nano Lett,2003,3(12):1701-1705.
[12]Wang T,Chen K,Sun X,et al. Preparation of a Super-hydrophobic Zinc Coating with a Hierarchical Structure Inherited from the Indicalamus Leaf Through Electroplating[J]. Adv Mater Interfaces,2018,5(8):1-6.
[13]Montano-Figueroa A G,Alcantar-Pena J J,Tirado P,et al. Tailoring of Polycrystalline Diamond Surfaces from Hydrophilic to Superhydrophobic via Synergistic Chemical Plus Micro-structuring Processes[J]. Carbon,2018,139:361-368.
[14]Bai F,Wu J,Gong G,et al. Biomimetic“Water Strider Leg”with Highly Refined Nanogroove Structure and Remarkable Water-Repellent Performance[J]. ACS Appl Mater Interfaces,2014,6(18):16237-16242.
[15]Chen L,Hong Z,Li G,et al. Recent Progress in Polymer Solar Cells:Manipulation of Polymer:Fullerene Morphology and the Formation of Efficient Inverted Polymer Solar Cells[J]. Adv Mater,2010,21(14/15):1434-1449.
[16]Zhang X,Chen R,Hu J,et al. Superhydrophobic Surface Constructed on Electrodeposited Silica Films by Two-Step Method for Corrosion Protection of Mild Steel[J]. Corros Sci,2016,104:336-343.
[17]Joung Y S,Buie C R. Antiwetting Fabric Produced by a Combination of Layer-by-Layer Assembly and Electrophoretic Deposition of Hydrophobic Nanoparticles[J]. ACS Appl Mater Interfaces,2015,7(36):20100-20110.
[18]HUANG Chunmei,ZHANG Meng,WANG Donghui,et al. Fabrication of Polymeric Micropheres by Breath Figures in Different Nonsolvent Atmospheres[J]. Acta Polym Sin,2014,(12):1606-1612(in Chinese).黄春梅,张萌,王冬晖,等.不良溶剂氛围中用breath figures法制备聚合物微球[J].高分子学报,2014,(12):1606-1612.
[19]Xiong X,Zou W,Yu Z,et al. Microsphere Pattern Prepared by a“Reverse”Breath Figure Method[J]. Macromolecules,2009,42:9351-9356.
[20]De León A S,Mu?oz-Bonilla A. Breath Figures Method to Control the Topography and the Functionality of Polymeric Surfaces in Porous Films and Microspheres[J]. J Polym Sci Polym Chem,2012,50(5):851-859.
[21]Xiao X,Bai W,Lin J. Strategy for Self-assembly of the Poly(9,9-Dihexylfluorene)to Microspheres:Optimizing the Self-assembling Conditions[J]. Polym Bull,2014,71(8):2103-2112.
[22]Wan L,Lv J,Ke B,et al. Facilitated and Site-Specific Assembly of Functional Polystyrene Microspheres on Patterned Porous Films[J]. ACS Appl Mater Interfaces,2010,2(12):3759-3765.
[23]Ke Q,Liao Y,Lin M,et al. A Superhydrophobic Film with High Water Vapor Transmission Prepared from Block Copolymer Micelle Solution via VIPS Method[J]. J Polym Res,2015,22(11):1-9.
[24]Xiao X,Bai W,Cai L,et al. Solvent-Induced Controllable Self-Assembly of Poly(9,9-Dihexylfluorene)[J]. Chem Lett,2014,43(3):331-333.
[25]Brockway L,Berryman L,Taylor H. Nonsolvent-Induced Phase Separation Synthesis of Superhydrophobic Coatings Composed of Polyvinylidene Difluoride Microspheres with Tunable Size and Roughness[J]. Prog Org Coat,2018,119:230-238.
[26]Khoddami A,Avinc O,Mallakpour S. A Novel Durable Hydrophobic Surface Coating of Poly(Lactic Acid)Fabric by Pulsed Plasma Polymerization[J]. Prog Org Coat,2010,67(3):311-316.
[27]Yu H,Zhang H,Song M,et al. From Celluloses Nanospheres,Nanorod to Nanofibers:Various Aspect Ratios Induced Different Nucleation/Reinforcing Effect on Polylactic Acid for Robust-Barrier Food Packaging[J]. ACS Appl Mater Interfaces,2017,9:43920-43938.
[28]SUN Bin,LIU Yanlong,BIAN Xinchao,et al. Preparation of High Heat Resistance Polylactide by Stereocomplexation[J].Chinese J Appl Chem,2016,33(9):1033-1039(in Chinese).孙彬,刘延龙,边新超,等.高耐热聚乳酸立体复合材料的制备[J].应用化学,2016,33(9):1033-1039.
[29]Nikos P,David W,Andrew P,et al. Crystallization-Driven Sphere-to-Rod Transition of Poly(Lactide)-b-Poly(acrylicacid)Diblock Copolymers:Mechanism and Kinetics[J]. Soft Matter,2012,8(28):7408-7414.
[30]Lodge T P. Block Copolymers:Past Successes and Future Challenges[J]. Macromol Chem Phys,2003,204(2):265-273.
[31]Mei L,Ren Y,Gu Y,et al. Strengthened and Thermally Resistant Poly(lactic acid)Based Composite Nanofibers Prepared via Easy Stereocomplexation with Antibacterial Effects[J]. ACS Appl Mater Interfaces,2018,10(49):42992-43002.
[32]Lafuma A,Quere D. Superhydrophobic States[J]. Nat Mater,2003,2(7):457-460.