罗子淇,陈江,杨小波,宋金星,王小君,包永忠

• 1:浙江大学化学工程与生物工程学院
• 2:化学工程联合国家重点实验室(浙江大学)
• 3:浙江传化功能新材料有限公司
• 4:传化智联股份有限公司

摘要(Abstract)：

研究含氟丙烯酸酯共聚物的结晶、氟元素分布和表面特性可为高疏水疏油涂层的开发提供基础。采用碘转移细乳液聚合制备了由聚（氟代丙烯酸酯-co-丙烯酸十八酯）和非氟代聚合物链段构成的嵌段共聚物，并研究嵌段共聚物组成和热处理条件对其结晶、表面氟元素富集和疏水疏油性的影响。结果表明，含以C8氟代烷基为主的氟代丙烯酸酯-丙烯酸十八酯无规共聚物或丙烯酸全氟己基乙基丙烯酸酯-丙烯酸十八酯无规共聚物链段的嵌段共聚物均具有结晶和表面氟元素富集特性，并在表面形成“峰谷状”粗糙结构。随着共聚物分子链运动能力和热处理温度的提升，氟元素表面富集程度增大。非氟代链段含量的增加会降低嵌段共聚物的结晶性，同时强化微相分离，因此，合成嵌段比适中的嵌段共聚物能够获得比聚（氟代丙烯酸酯-co-丙烯酸十八酯）无规共聚物更优的综合疏水疏油性。

关键词(KeyWords)： 聚(氟代丙烯酸酯-co-丙烯酸十八酯);嵌段共聚物;微相分离;结晶;疏水疏油

Abstract:

Keywords:

基金项目(Foundation): 浙江省“尖兵”研发攻关计划(2023C01111)

作者(Author): 罗子淇,陈江,杨小波,宋金星,王小君,包永忠

参考文献(References)：

• [1] TAIBI J, ROUIF S, AMEDURI B,et al. Radiation induced graft polymerization of fluorinated monomers onto flax fabrics for the control of hydrophobic and oleophobic properties[J].Polymer, 2023, 281:126132.
• [2]王红丹，李坚，陈豪杰，等．含氟丙烯酸酯嵌段共聚物的迁移行为及表面性能研究[J]．高校化学工程学报，2013, 27(2):283-289.WANG H D, LI J, CHEN H J,et al. Investigation on migration behaviors and surface performances of fluoro-containing acrylate block copolymers[J].Journal of Chemical Engineering of Chinese Universities, 2013, 27(2):283-289.
• [3]梁雷，王彦玲，张杉．超双疏含氟聚合物的研究进展[J]．化工进展，2020, 39(3):1070-1079.LIANG L, WANG Y L, ZHANG S. Research progress of super-amphiphobic fluoropolymers[J].Chemical Industry and Engineering Progress, 2020, 39(3):1070-1079.
• [4] CHEN Y T, LUO C, HU F Q,et al. Recent advances in fluorinated polymers:Synthesis and diverse applications[J].Science China Chemistry, 2023, 66(12):3347-3359.
• [5] HA J, CHUNG J, KIM S,et al. Transfer-printable micropatterned fluoropolymer-based triboelectric nanogenerator[J].Nano Energy,2017, 36:126-133.
• [6] WANG J G, MAO G P, OBER C K,et al. Liquid crystalline, semifluorinated side group block copolymers with stable low energy surfaces:Synthesis, liquid crystalline structure, and critical surface tension[J].Macromolecules, 1997, 30(7):1906-1914.
• [7]倪华钢，张伟，王新平，等．侧基含氟聚合物结构与表面性质研究进展[J]．高分子材料科学与工程，2007, 23(2):14-18.NI H G, ZHANG W, WANG X P,et al. Advances in polymer with fluorinated side group and its surface properties[J].Polymer Materials Science and Engineering, 2007, 23(2):14-18.
• [8] ZHANG Q H, WANG Q Y, ZHAN X L,et al. Synthesis and performance of novel fluorinated acrylate polymers:Preparation and reactivity of short perfluoroalkyl group containing monomers[J].Industrial&Engineering Chemistry Research, 2014, 53(19):8026-8034.
• [9] BRONIATOWSKI M, DYNAROWICZ-??TKA P. Semifluorinated alkanes—primitive surfactants of fascinating properties[J].Advances in Colloid and Interface Science, 2008, 138(2):63-83.
• [10] PARK I J, LEE S B, CHOI C K,et al. Surface properties and structure of poly(perfluoroalkylethyl methacrylate)[J].Journal of Colloid and Interface Science, 1996, 181(1):284-288.
• [11] KARAYIANNI M, PISPAS S. Block copolymer solution self-assembly:Recent advances, emerging trends, and applications[J].Journal of Polymer Science, 2021, 59(17):1874-1898.
• [12] KIM J K, YANG S Y, LEE Y,et al. Functional nanomaterials based on block copolymer self-assembly[J].Progress in Polymer Science, 2010, 35(11):1325-1349.
• [13] SAI H, TAN K W, HUR K,et al. Hierarchical porous polymer scaffolds from block copolymers[J].Science, 2013, 341(6145):530-534.
• [14] TIAN L L, SUN M M, LIU Y L,et al. Superhydrophobic and highly oleophobic coatings based on litchi-like FDA-SiO2-PS nanocomposite with excellent self-cleaning and anti-bioadhesion performances[J].Colloids and Surfaces A(Physicochemical and Engineering Aspects), 2023, 667:131395.
• [15] CHEN T L, HUANG C Y, XIE Y T,et al. Bioinspired durable superhydrophobic surface from a hierarchically wrinkled nanoporous polymer[J].ACS Applied Materials&Interfaces, 2019, 11(43):40875-40885.
• [16] FENG X J, JIANG L. Design and creation of superwetting/antiwetting surfaces[J].Advanced Materials, 2006, 18(23):3063-3078.
• [17] YONG J L, CHEN F, YANG Q,et al. Superoleophobic surfaces[J].Chemical Society Reviews, 2017, 46(14):4168-4217.
• [18] WEN X F, YE C, CAI Z Q,et al. Crosslinked superhydrophobic films fabricated by simply casting poly(methyl methacrylate-butyl acrylate-hydroxyethyl methacrylate)-b-poly(perfluorohexylethyl methacrylate)solution[J].Applied Surface Science, 2015, 339:109-115.
• [19] CHAKRABARTY A, SINGHA N K. Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion;improved hydrophobicity in the core-shell block copolymer[J].Journal of Colloid and Interface Science, 2013, 408:66-74.
• [20] LI Y W, ZHENG X W, XIA Z Y,et al. Synthesis of fluorinated block copolymer and superhydrophobic cotton fabrics preparation[J].Progress in Organic Coatings, 2016, 97:122-132.
• [21]陈江，宋金星，王胜鹏，等．碘转移细乳液聚合制备氟代丙烯酸酯-丙烯酸十八酯共聚物[J]．高校化学工程学报，2021,35(1):65-71.CHEN J, SONG J X, WANG S P,et al. Preparation of fluoroacrylate-stearyl acrylate copolymer by iodine transfer miniemulsion polymerization[J].Journal of Chemical Engineering of Chinese Universities, 2021, 35(1):65-71.