| Fluorinated acrylic resins,as a kind of typical low surface energy resins,are widely used in the fields of stone protection,fabric finishing and marine antifouling coatings.Traditional fluorinated acrylic resins usually contain long perfluoroalkyl chains(CnF2n+1-,n?8),and their final oxidative degradation products are mostly Perfluorooctanoic acid compounds(PFOA).PFOA has biological accumulation and can enter the human body through the food chain and interact with blood proteins,suspected to cause a variety of pathological reactions.The accumulation of PFOA in soil or water environment has aroused widespread concern.The European Union has banned or restricted the use of PFOA-related substances with perfluoroheptyl(C7F15-),perfluorooctyl(C8F17-)or other length perfluoroalkyl structure as one of the structural elements in Article 68 of Annex XVII of REACH regulation.Perfluorohexyl(C6F13-)can be used as the replacement structure of long perfluoroalkyl chains(CnF2n+1-,n?8),but the surface energy of acrylic resin with Perfluorohexyl(C6F13-)as the functional structure is higher,which cannot provide enough hydrophobic and oil-repellent performance.To solve above problems,a scheme to enhance the hydrophobic and oil-repellent performance of perfluorohexyl(C6F13-)structure by the copolymerization of fluorinated monomer and organosilicon monomer is proposed in the second chapter,a series of fluorine-silicone copolymer acrylic resin were prepared,the surface energy and stone protection properties of fluorine-silicone copolymer acrylic resin with different monomers were studied in detail,the experimental results show that the copolymerization of fluorinated monomer and organosilicon monomer can effectively reduce the surface energy of resin,and the vinyl-terminated silicone monomer is better than the acrylate terminated silicone monomer in reducing degree;The surface energy of the resin decreased with the increase of the length of the side group of the polydimethylsiloxane chain,the increase of the amount of organosilicon monomer and the increase of the amount of SMA monomer.The stone protection ability of resin is not strictly related to the surface energy of resin.In the research process,two patents were applied,which provided a reasonable route for the preparation of fluroresin or silicone resin,and also provides reference for the development of high performance environmentally-friendly fluorinated acrylic resins and its application in stone protection.In the third chapter,we try to enhance the adhesion ability of acrylic resin containing fluorine and silicon to polymer substrate by hydrogen stripping coupling reaction of benzophenone group.Three benzophenone-methacrylate monomers(CH2=CH(CH3)-Cx-BP)were successfully synthesized by Williamson reaction,the structure of the product was characterized by 1H-NMR and IR spectra,and subsequently,benzophenone-fluorinated acrylic resin was successfully prepared by referring to the polymerization process in Chapter 2.The thermal stability of the resin was determined by thermogravimetric analysis,and the actual content of benzophenone monomer in the resin was calculated by UV-Vis absorption spectrum standard curve.Then,through scanning electron microscopy and contact Angle test,it is proved that the stable adhesion of benzophenone-fluorinated acrylic resin film can be formed on PET sheet after ultraviolet radiation.On the basis of the second chapter,we successfully prepared four kinds of benzophenone fluorine-silicone copolymer acrylic resins with CH2=CH(CH3)-Cx-BP,studied the influence of the content and structure of CH2=CH(CH3)-Cx-BP monomer on the adhesion ability,studied the influence of benzophenone group on the side group of the resin molecule and benzophenone group on the small molecule on the adhesion ability of the resin,the experimental results show that:The higher the amount of CH2=CH(CH3)-Cx-BP monomer,the larger number of carbon atoms x,the stronger the adhesion ability is;The benzophenone group on the side group of the resin molecule can improve the adhesion ability of the resin more effectively.The work in this chapter provides a new way to solve the problem of adhesion of low surface energy resin to polymer substrate and provides a reference for the development of special acrylic resin with high performance. |
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