The Preparation Of Amphiphilic Fluorosilicone Copolymer Surfaces Based On The Applications Of Protein Resistance

Fluorinated silicones (PMTFPS) have excellent water and solvent repellent,fouling release properties, and polyethylene glycol (PEG) has excellent properties ofprotein resistance. The combination of two kinds of materials will obtain coatingmaterials of amphiphilic fluorosilicone copolymers, which are expected to be highlyanti-protein adsorption properties and therefore get potential applications ofbiomaterials, marine pollution prevention fields.In this paper, PEG-MA, PMTFPS-MA and MMA were chose for synthesizingamphiphilic fluorosilicone-containing graft copolymers. Then, the surface chemicalcomposition, surface morphology and surface wetting properties of copolymer filmswere studied. Finally, its anti-protein adsorption performance was investigated.Following conclusions were obtained:1. Amphiphilic fluorosilicone graft copolymers (PMMA-g-(PMTFPS, PEG))were prepared by conventional radical copolymerization. And their chemicalcomposition, surface morphology and surface wetting performance were studied.(1) AFM results showed that the surface of different compositions ofPMMA-g-(PMTFPS, PEG) graft copolymer films exhibited different surfacemorphology under dry conditions. Under wet conditions, the surface reconstructionoccurred, and the surface morphology changed.(2) XPS results showed that under wet or dry conditions, chemical compositionof the surface of PMMA-g-PEG graft copolymer films had little change, while thecomposition of the surface of PMMA-g-PMTFPS or PMMA-g-(PMTFPS, PEG)copolymer films had more change.(3) Contact angle measurements showed that the surface wettability of thecopolymers was influenced by chemical composition of surface, and the surfaceroughness also greatly influenced its surface wetting properties. With the incorporation of PMTFPS component, the surface energy of the copolymers could bereduced to20.7mN/m-22.1mN/m, the water contact angle reached95.1o, and thecontact angle of formamide and diiodomethane reached83.8oand71.8o, respectively.That is, the copolymers containing PMTFPS component showed good water repellentand solvent resistance.2. Reversible addition-fragmentation chain transfer (RAFT) radicalcopolymerization of PMTFPS-MA/PEG-MA and MMA was carried out in thiswork. Amphiphilic fluorosilicone graft copolymers were prepared by RAFTradical copolymerization of PMTFPS-MA, PEG-MA and MMA. And itschemical composition, surface morphology and surface wetting performancewere studied.(1) The kinetics of RAFT radical copolymerization was studied by RAFT radicalcopolymerization with PMTFPS-MA/PEG-MA and MMA. The results showed thatthe kinetics curve of RAFT radical copolymerization exhibited linear first-orderkinetic equation, and the copolymer had narrow molecular weight distribution (PDI<1.5). Therefore, the RAFT radical copolymerization of PMTFPS-MA/PEG-MA andMMA is controllable.(2) The surface morphology, chemical composition and wetting performance ofamphiphilic fluorosilicone graft copolymers (PMMA-g-(PMTFPS, PEG)) wereinvestigated.a. AFM results showed that the surface morphology of the copolymerPMMA-g-PEG was smooth, and the copolymers containing PMTFPS componentdisplayed porous microstructure. With the decrease of PMTFPS content, the porousmicrostructure is reduced, and the surface roughness of copolymer became small (Ra<2.0nm). Therefore, the surface roughness had little effect on the surface wettingperformance.b. XPS results showed that copolymer PMMA-g-PEG had more PEG segmentson surface. For the copolymers containing PMTFPS component, the content ofPMTFPS segment on surface reduced with the decrease of PMTFPS component incopolymers. C. The results of contact angle measurements showed that the PEG componentcontents in copolymer PMMA-g-PEG reached37.5wt%, and the surface energy was63.2mN/m, which displayed good hydrophilicity but poor solvent resistance. Forcopolymers containing PMTFPS component exhibited good water repellent andsolvent resistance, surface energy decreased from26.4mN/m down to21.1mN/mwith PMTFPS component content increased.3. Anti-protein adhesion performance of amphiphilic fluorosiliconecopolymer was investigated.(1) The results of fluorescence microscopy and XPS measurements showed thatthe copolymers could impedance protein adsorption with respect to PMMA film.When amphiphilic fluorosilicone graft copolymer had65.6wt%PEG and6.4wt%PMTFPS, the copolymer surface displayed excellent anti-protein adsorptionperformance.(2) For PMMA-g-PEG graft copolymers, the surface energy increased with theincrease of PEG content, and the anti-protein adsorption performance displayed thebetter thereafter. For the PMMA-g-PMTFPS, to a certain extent, the content ofPMTFPS segment on surface also displayed a certain anti-protein adsorptionproperties. For amphiphilic fluorinesilicone graft copolymer PMMA-g-(PMTFPS,PEG), however, the surface could reflect the role of both PEG and PMTFPS segmentsonly when PEG content reached a certain extent because of the strong surfaceenrichment tendency of fluorosilicone segment.