CN105153357A - Fluoro-terminated epoxy polymer, preparing method of fluoro-terminated epoxy polymer, and application of fluoro-terminated epoxy polymer in preparing hydrophobic surface - Google Patents
Fluoro-terminated epoxy polymer, preparing method of fluoro-terminated epoxy polymer, and application of fluoro-terminated epoxy polymer in preparing hydrophobic surface Download PDFInfo
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Abstract
The invention discloses a fluoro-terminated epoxy polymer and a preparing method thereof. The preparing method of the fluoro-terminated epoxy polymer comprises the steps that a fluoroacrylate monomer and hydrobromic acid react, and neutralization, separation, elution, rotary evaporation and drying are conducted, so that an active ATRP reactivity inimer is obtained; the prepared active ATRP reactivity inimer and glycidyl methacrylate are dissolved in a solvent, and a catalyst and a ligand are added for reaction, so that the fluoro-terminated epoxy polymer is obtained. The invention further discloses the application of the fluoro-terminated epoxy polymer in preparing a hydrophobic surface. According to the fluoro-terminated epoxy polymer, a fluoric group with low surface energy is introduced through simple and controllable chemical crosslinking, the durability of a hydrophobic material is improved, and the hydrophobic material is excellent in hydrophobic performance and high in durability. The hydrophobic surface of the prepared fluoro-terminated epoxy polymer is high in stability and durability.
Description
Technical field
The invention belongs to functional high polymer material field, be specifically related to a kind of epoxy polymer and preparation method of fluorine end-blocking and preparing the application of hydrophobic surface.
Background technology
Wettability is one of key property of material surface, and research shows, the chemical composition of material surface and microtexture play a decisive role to the wettability that it shows.In general, the wettability contact angle of material surface is weighed, and according to the size of contact angle, material surface can be divided into four classes: (1) contact angle be less than 10 ° for super hydrophilic (or super oleophylic) surface; (2) be less than 90 ° for hydrophilic (or oleophylic) surface; (3) be greater than 90 ° for hydrophobic (or oleophobic) surface; (4) be greater than 150 ° for super-hydrophobic (or super oleophobic) surface.
There is the material of hydrophobic function, the wettability special due to it and there is waterproof, antifouling, anticorrosive, the feature such as antibiont and organic solvent, at many special occasions, also there is self-cleaning feature, therefore, be widely used in the numerous areas of modern industry.Although the material of hydrophobic function achieves fast development, but still also there is a series of problem, as insecure in hydrophobic coating cohesiveness, stable poor with endurance quality, relate to a large amount of organic solvent and range of application narrow etc., complicated process of preparation, high, the very difficult industrialization of cost simultaneously.
Fluorinated compound has very low surface energy, carries out modification material can be made to obtain good hydrophobic performance with fluorinated compound to material.But fluorochemicals is expensive, therefore plating one deck fluorochemicals at material surface just becomes one of the most effective method preparing hydrophobic surface.But, with small molecules fluorochemicals to material surface modifying, although the material with hydrophobic performance can be obtained, but the hydrophobic performance of the modified material of small molecules fluorochemicals is also not satisfactory, this is mainly because the alkyl chain segment length of small molecules fluorochemicals is short, the adhesion layer of effective compact can not be formed and easily come off, causing poor durability.For the problems referred to above, contriver by synthesis fluorine end-blocking on the basis of previous work containing epoxide group polymkeric substance, solved the problem of hydrophobic material weather resistance by simply controlled chemically crosslinked mode.
Summary of the invention
For solving the shortcoming and defect part of prior art, the object of the present invention is to provide a kind of epoxy polymer of fluorine end-blocking.
Another object of the present invention is the preparation method of the epoxy polymer providing this fluorine end-blocking.
The application of hydrophobic surface prepared by the epoxy polymer that another object of the present invention there is provided fluorine end-blocking.
The object of the invention is to be achieved through the following technical solutions:
An epoxy polymer for fluorine end-blocking, has following structural formula:
Wherein 3x+2y+z=3,5,6,8,12; X=0,1; Y=0, Isosorbide-5-Nitrae, 6; Z=0,1; M is the integer of 10-50.
A preparation method for the epoxy polymer of fluorine end-blocking, comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: by fluoro-acrylate monomer and Hydrogen bromide reaction, the neutralization of product saturated sodium bicarbonate solution is neutral, pillar layer separation, and elution, revolves steaming, dry, obtained active A TRP reactive behavior trigger monomer;
Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:1.5-4;
Described temperature of reaction is 20-25 DEG C; The described reaction times is 12-48h;
Described elutriant is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5;
2) preparation of the epoxy polymer (FPGm) of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and glycidyl methacrylate (GMA) are dissolved in solvent, and the solid content of the hierarchy of control is 40%, in massfraction; Then add catalyzer and part, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25-0.5h at 20-30 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer (FPGm) of fluorine end-blocking.
Described, fluoro-acrylate monomer is the one in vinylformic acid trifluoro ethyl ester, vinylformic acid five fluorine propyl ester, vinylformic acid hexafluoro butyl ester, vinylformic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, trifluoroethyl methacrylate, methacrylic acid five fluorine propyl ester, Hexafluorobutyl mathacrylate, methacrylic acid octafluoro pentyl ester and dodecafluoroheptyl methacrylate.
Described, catalyzer is cuprous bromide (CuBr).
Described, part is N, N, N', N, ' N''-five methyl diethylentriamine (PMDETA).
Described, solvent is methyl-phenoxide or phenyl ether.
Described, ATRP reactive behavior trigger monomer: glycidyl methacrylate: catalyzer: the mol ratio of part is 1:10-50:1:2.
The application of hydrophobic surface prepared by a kind of epoxy polymer of fluorine end-blocking, the epoxy polymer of fluorine end-blocking is dissolved in N, dinethylformamide, then adds catalyst of triethylamine and cotton, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
In the present invention, epoxide group a kind ofly has extensive and powerful active group, it is combined with the fluorochemicals of low surface energy, the synergy of the two can be given full play to, namely the activity of epoxide group and material surface is utilized to react, the chemistry of the fluoro-containing group and material that realize low surface energy is connected, thus obtained hydrophobic performance is excellent, the epoxy polymer of the fluorine end-blocking of good endurance.
Beneficial effect of the present invention:
(1) epoxy polymer of fluorine end-blocking prepared of the present invention, the fluoro-containing group of low surface energy is introduced by simply controlled chemically crosslinked mode, solve the problem of hydrophobic material weather resistance, be that a kind of hydrophobic performance is excellent, the preparation method of the hydrophobic material of good endurance, there is good industrial applications prospect.
(2) epoxy polymer of fluorine end-blocking prepared of the present invention, by changing the kind of end-blocking fluorine monomer and the ratio with GMA, regulating the ratio of fluorine unit and epoxide group, realizing the requirement of differing materials.
(3) the epoxy polymer hydrophobic surface of fluorine end-blocking prepared of the present invention, has satisfactory stability and weather resistance.The epoxy polymer of fluorine end-blocking also can obtain hydrophobic surface in paper product, plastics, concrete, glass, pottery or metallic surface, is widely used in the fields such as weaving, building materials, electric power, packaging, kitchen guarding, pipeline, boats and ships, military affairs.
Accompanying drawing explanation
Fig. 1 is the epoxy polymer (FPG of fluorine end-blocking of the present invention
m) structural formula;
Wherein 3x+2y+z=3,5,6,8,12; X=0,1; Y=0, Isosorbide-5-Nitrae, 6; Z=0,1; M is the integer of 10-50;
Fig. 2 is the nuclear magnetic spectrogram of active A TRP reactive behavior trigger monomer (a) of the present invention and the epoxy polymer (b) being caused the fluorine end-blocking of preparation by it;
Fig. 3 is the hydrophobic effect figure of the epoxy polymer of fluorine end-blocking of the present invention;
Fig. 4 is blank cotton (a, b, c) and the epoxy polymer of fluorine end-blocking of the present invention hydrophobic cotton surface (d, e, scanning electron microscope (SEM) photograph f) prepared.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
embodiment 1
An epoxy polymer for fluorine end-blocking, the following structural formula of its parameter as shown in Figure 1, wherein 3x+2y+z=3; X=1; Y=0; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: trifluoroethyl methacrylate and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 12h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow ATRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:1.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction; Then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25h at 20 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
The application of hydrophobic surface prepared by a kind of epoxy polymer of fluorine end-blocking, step is as follows: be dissolved in by the epoxy polymer of fluorine end-blocking in N, dinethylformamide, stir, respectively solution A 1, the solution A 2 of 5mg/ml, the solution A 3 of 10mg/ml of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface A1, A2, A3.
embodiment 2
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=5; X=1; Y=1; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: methacrylic acid five fluorine propyl ester and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 20h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:2.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction; Then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25h at 20 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
The application of hydrophobic surface prepared by a kind of epoxy polymer of fluorine end-blocking, step is as follows: be dissolved in by the epoxy polymer of fluorine end-blocking in N, dinethylformamide, stir, respectively solution A 1, the solution A 2 of 5mg/ml, the solution A 3 of 10mg/ml of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface A1, A2, A3.
embodiment 3
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=6; X=1; Y=1; Z=1; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: Hexafluorobutyl mathacrylate and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 30h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:2.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction, then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25h at 25 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
The application of hydrophobic surface prepared by a kind of epoxy polymer of fluorine end-blocking, step is as follows: be dissolved in by the epoxy polymer of fluorine end-blocking in N, dinethylformamide, stir, respectively solution A 1, the solution A 2 of 5mg/ml, the solution A 3 of 10mg/ml of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface A1, A2, A3.
embodiment 4
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=8; X=0; Y=4; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: methacrylic acid octafluoro pentyl ester and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 40h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:3.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction; Then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.3h at 25 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 5
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=12; X=0; Y=6; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: dodecafluoroheptyl methacrylate and Hydrogen bromide are mixed, at 25 DEG C, the reaction times is 48h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:4.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction, then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.5h at 30 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking.Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 6
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=3; X=1; Y=0; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: vinylformic acid trifluoro ethyl ester and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 12h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:1.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction; Then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25h at 20 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 7
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=5; X=1; Y=1; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: vinylformic acid five fluorine propyl ester and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 20h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:2.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction, then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25h at 20 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 8
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=6; X=1; Y=1; Z=1; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: vinylformic acid hexafluoro butyl ester and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 30h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:2.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction; Then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25h at 25 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 9
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=8; X=0; Y=4; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: vinylformic acid octafluoro pentyl ester and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 40h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:3.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction; Then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.5h at 25 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 10
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=12; X=0; Y=6; Z=0; M=10.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: dodecafluorhe-ptylacrylate and Hydrogen bromide are mixed, at 25 DEG C, the reaction times is 48h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:4.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in phenyl ether, the solid content of the hierarchy of control is 40%, in massfraction, then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.5h at 30 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:10:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 11
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=6; X=1; Y=1; Z=1; M=20.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: Hexafluorobutyl mathacrylate and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 30h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:2.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction, then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25h at 25 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:20:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 12
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=6; X=1; Y=1; Z=1; M=30.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: Hexafluorobutyl mathacrylate and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 30h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:2.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction, then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.5h at 25 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:30:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 13
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=6; X=1; Y=1; Z=1; M=50.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: Hexafluorobutyl mathacrylate and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 30h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:2.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction, then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.5h at 25 DEG C, cross neutral alumina pillar copper removal salt, then by the normal hexane precipitation of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:50:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
embodiment 14
An epoxy polymer for fluorine end-blocking, structural formula as shown in Figure 1, wherein 3x+2y+z=8; X=0; Y=4; Z=0; M=20.
Preparation method comprises the steps:
1) preparation of active A TRP reactive behavior trigger monomer: vinylformic acid octafluoro pentyl ester and Hydrogen bromide are mixed, at 20 DEG C, the reaction times is 40h, it is neutral that reaction terminates the neutralization of rear saturated sodium bicarbonate solution, pillar layer separation, elutriant used is that ethyl acetate and sherwood oil are mixed to get according to the volume ratio of 1:5, then steaming, drying is revolved, i.e. obtained light yellow active A TRP reactive behavior trigger monomer; Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:3.5.
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and GMA are dissolved in methyl-phenoxide, the solid content of the hierarchy of control is 40%, in massfraction; Then add CuBr and PMDETA, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.5h at 25 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking; Described ATRP reactive behavior trigger monomer: GMA:CuBr:PMDETA mol ratio is 1:20:1:2.
An application for hydrophobic surface prepared by the epoxy polymer of fluorine end-blocking, and step is as follows: be dissolved in N, dinethylformamide by the epoxy polymer of fluorine end-blocking, stir, the solution of obtained 1mg/ml; Then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
performance test
Measure water contact angle and the coating property of the hydrophobic surface that embodiment 1-14 is prepared with cotton, the contact angle of water measures with deionized water, and droplet size is 2 μ L.
The testing method of wear resistance is as follows: the hydrophobic surface (5cm × 5cm) prepared with cotton by embodiment 1-14 is placed on above 1000 object sand paper (50cm × 50cm), this hydrophobic surface is placed a counterweight (weight is 1000g), traction hydrophobic surface moves ahead 30cm, and then hairpinning, so repeat 10 times.First observe hydrophobic surface change, meanwhile, then carry out the water contact angle measurement experiment of hydrophobic surface.Result is as shown in table 1.
Table 1 performance test results
As can be seen from Table 1: the hydrophobic surface that embodiment 1-14 prepares and base material bonding firm, there is good hydrophobic performance; Simultaneously the hydrophobic surface crocking resistance for preparing of embodiment 1-14 is good, therefore excellent durability.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. an epoxy polymer for fluorine end-blocking, is characterized in that, has following structural formula:
Wherein 3x+2y+z=3,5,6,8,12; X=0,1; Y=0, Isosorbide-5-Nitrae, 6; Z=0,1; M is the integer of 10-50.
2. a preparation method for the epoxy polymer of fluorine end-blocking according to claim 1, is characterized in that, comprise the steps:
1) preparation of active A TRP reactive behavior trigger monomer: by fluoro-acrylate monomer and Hydrogen bromide reaction, the neutralization of product saturated sodium bicarbonate solution is neutral, pillar layer separation, and elution, revolves steaming, dry, obtained active A TRP reactive behavior trigger monomer;
Described fluoro-acrylate monomer and hydrobromic mol ratio are 1:1.5-4;
Described temperature of reaction is 20-25 DEG C; The described reaction times is 12-48h;
2) preparation of the epoxy polymer of fluorine end-blocking: the active A TRP reactive behavior trigger monomer the first step prepared and glycidyl methacrylate are dissolved in solvent, the solid content of the hierarchy of control is 40%, in massfraction; Then add catalyzer and part, through three times freezing-vacuumize-melt-rouse argon cycles after, react 0.25-0.5h at 20-30 DEG C, cross neutral alumina pillar copper removal salt, then precipitate with the normal hexane of 5 DEG C, lyophilize, obtains the epoxy polymer of fluorine end-blocking.
3. preparation method according to claim 2, it is characterized in that, described fluoro-acrylate monomer is the one in vinylformic acid trifluoro ethyl ester, vinylformic acid five fluorine propyl ester, vinylformic acid hexafluoro butyl ester, vinylformic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, trifluoroethyl methacrylate, methacrylic acid five fluorine propyl ester, Hexafluorobutyl mathacrylate, methacrylic acid octafluoro pentyl ester and dodecafluoroheptyl methacrylate.
4. preparation method according to claim 2, is characterized in that, described catalyzer is cuprous bromide.
5. preparation method according to claim 2, is characterized in that, described part is N, N, N', N, ' N''-five methyl diethylentriamine.
6. preparation method according to claim 2, is characterized in that, described solvent is methyl-phenoxide or phenyl ether.
7. preparation method according to claim 2, is characterized in that, described ATRP reactive behavior trigger monomer: glycidyl methacrylate: catalyzer: the mol ratio of part is 1:10-50:1:2.
8. the application of hydrophobic surface prepared by the epoxy polymer of a fluorine end-blocking according to claim 1, it is characterized in that, the epoxy polymer of fluorine end-blocking is dissolved in N, dinethylformamide, then catalyst of triethylamine and cotton is added, 80 DEG C of stirring reaction 30min, then dry 1h at taking-up 120 DEG C, cotton, i.e. obtained hydrophobic surface.
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