Self-assembled colloid and solvent-responsive property of amphiphilic fluoropolymer for protein-resistance coatings
Self-assembled colloid and solvent-responsive property of amphiphilic fluoropolymer for protein-resistance coatings
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DOI：
10.1007/s00396-017-4065-1
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发表时间：
2017-03
影响因子：
2.4
通讯作者：
H. Guo;Ling He
中科院分区：
文献类型：
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作者：
H. Guo;Ling He
通过原子转移自由基聚合(ATRP)合成了疏水性十二氟甲基丙烯酸氢丁酯(DFHM)和亲水性聚乙二醇甲基醚甲基丙烯酸酯(PEGMA)两亲氟聚合物P(PEGMA)-co-P(DFHM)。根据溶剂介电常数(ε=38.3-4.8)，讨论了P(PEGMA)-P(DFHM)在乙醇、二甲基甲酰胺、四氢呋喃和氯仿溶液中的自组装胶体。根据胶体的表面形貌和化学成分，对胶体形成的薄膜的亲水/疏水性能、耐蛋白质性能和粘接强度进行了评价。P(PEGMA)-co-P(DFHM)在DMF中能自组装成500-600 nm的核壳胶束，在乙醇中自组装为300-400 nm，在THF和CHCl3溶液中自组装为200-250 nm。这些胶体为薄膜表面提供了高氟含量(39.4041.70wt%)，表明在成膜过程中含氟基团迁移到薄膜表面，从而具有明显的亲水/疏水性能(94.3°-102.4°水接触角和58.5°-60.2°十六烷接触角)。相比之下，由于胶体尺寸较大，DMF浇铸膜的表面粗糙度最高(Ra0.98 nm)，氟含量最低(39.40wt%)，表面自由能最高(20.41mN/m−1)，而CHCl3浇铸膜的表面自由能最低(17.82mN/m−1)。DMF和乙醇浇铸膜的粘结强度(210和168nN)高于四氢呋喃和三氯甲烷浇铸膜(105nN和63nN)，而DMF浇铸膜表现出更好的抗蛋白质性能(Δf=−15.0 HZ)，远高于其他三种膜(Δf=−17-20 HZ)。研究结果表明，P(P-EGMA)-co-P(DFHM)可作为溶剂型耐蛋白质涂料具有广阔的应用前景。
Amphiphilic fluorocopolymer P (PEGMA)-co-P (DFHM) is prepared by hydrophobic dodecafluorohrptyl methacrylate (DFHM) and hydrophilic poly (ethylene glycol) methyl ether methacrylate (PEGMA) monomers via atom transfer radical polymerization (ATRP). The self-assembled colloids of P (PEGMA)-co-P (DFHM) in ethanol, dimethylformamide (DMF), tetrahydrofuran (THF), and chloroform (CHCl3) solutions are discussed according to solvent dielectric constants (ε= 38.3–4.8). The hydrophilic/hydrophobic property, protein resistance, and adhesive strength of films formed by these colloids are evaluated based on the surface morphologies and chemical compositions. P (PEGMA)-co-P (DFHM) can self-assembly into core-shell micelles composed of P (PEGMA) shell and P (DFHM) core (~130 nm) as 500–600 nm in DMF, 300–400 nm in ethanol, and 200–250 nm in THF and CHCl3solutions. These colloids provide the film surfaces with high fluorine content (39.40–41.70 wt%) to indicate the migration of fluorine-containing groups onto the film surface during the film formation and therefore the obvious hydrophilic/hydrophobic properties (94.3°–102.4° water contact angles and 58.5°–60.2° cetane contact angles). Comparatively, DMF-casted film gains the highest surface roughness (Ra = 0.98 nm), the lowest fluorine content (39.40 wt%), and the highest surface free energy (20.41 mN m−1) due to its large size of colloids, but CHCl3-casted film gives the lowest surface free energy (17.82 mN m−1). The adhesive strength for DMF- and ethanol-casted films (210 and 168 N) proves higher than THF- and CHCl3-casted films (105 and 63 N), while DMF-casted film shows much better protein resistance (Δf= −15.0 Hz) than other three films (Δf= −17–20 Hz). It is believed that the obtained P (P EGMA)-co-P(DFHM) could have a promising application as solvent-dependent and protein-resistance coatings.