CN105669888A - Functional protective surface material with good adhesion performance and preparation method thereof - Google Patents
Functional protective surface material with good adhesion performance and preparation method thereof Download PDFInfo
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- CN105669888A CN105669888A CN201510961595.1A CN201510961595A CN105669888A CN 105669888 A CN105669888 A CN 105669888A CN 201510961595 A CN201510961595 A CN 201510961595A CN 105669888 A CN105669888 A CN 105669888A
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- ethyl
- methyl acrylamide
- dihydroxy phenyl
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001681 protective effect Effects 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- DGRQETMRLZZDLT-UHFFFAOYSA-N N-(3,4-dihydroxyphenyl)-N-propylprop-2-enamide Chemical compound C(C=C)(=O)N(C1=CC(=C(C=C1)O)O)CCC DGRQETMRLZZDLT-UHFFFAOYSA-N 0.000 claims description 33
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010129 solution processing Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000001338 self-assembly Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 claims 3
- -1 1,4-dihydroxy phenyl Chemical group 0.000 claims 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 37
- 239000011248 coating agent Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 19
- 229960003638 dopamine Drugs 0.000 abstract description 19
- 238000005260 corrosion Methods 0.000 abstract description 13
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 239000011253 protective coating Substances 0.000 abstract description 6
- 238000004873 anchoring Methods 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 3
- 239000011737 fluorine Substances 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 230000003075 superhydrophobic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 241000195493 Cryptophyta Species 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000001802 infusion Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical class Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000012531 culture fluid Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an N- (3, 4-dihydroxyphenyl) ethyl-methacrylamide copolymer and a preparation method thereof. The invention takes dopamine and fluorine-containing compounds as raw materials, adopts a copolymerization method to modify the dopamine by the fluorine-containing compounds, and prepares the copolymer containing the side chain of the fluorine compound and the side chain of the catechol anchoring group. On one hand, the copolymer has a catechol anchoring group of dopamine, and provides good adhesion performance; on the other hand, the coating has fluorine-containing functional groups, has weather resistance, corrosion resistance and hydrophobic and oleophobic properties, and greatly improves the protective performance of the functional protective coating. The invention also discloses a functional protective surface material with good adhesion performance, which is obtained by soaking the N- (3, 4-dihydroxyphenyl) ethyl-methacrylamide copolymer on the surface of the material. The material has good protective performance, super-hydrophobic performance, antifouling performance and adhesion performance; the substrate has wide application range; no toxicity and no pollution.
Description
Technical field
The invention belongs to Material Field, be specifically related to a kind of function protecting surfacing, particularly relate to a kind of function protecting surfacing with well attached performance and preparation method thereof.
Background technology
Along with the process developing, utilizing ocean space rapidly of marine economy is accelerated, ocean structure engineering such as breakwater, harbour, off-shore airport, seabed tunnel and bridge spanning the sea etc. are applied more and more extensive. Meanwhile, due to the impact of sea water long period of soaking, erosion, stormy waves and tide, the etching problem of ocean structure engineering is also increasingly prominent, and safety and the durability of ocean structure engineering in serious harm. Therefore, the corrosion protection problem of ocean structure more and more comes into one's own. At present, the safe service demand of a century ocean structure engineering proposed, it is necessary to ensureing the ocean structure durability in the whole service life phase, the guard technology of ocean structure engineering is proposed severe challenge by this.
Coating technology is that ocean structure protects important and effective method. Conventional ocean structure protective coating has continued to use metal protection material, is generally adopted the coating such as chlorinated rubber, polyurethane, chlorosulfonated polyethylene and epoxy. But, the combination property of these coating is not met by the requirement of harsh marine environment to a certain extent. At present, ocean structure protective coating still has many theory and technology problems being not solved by, and wherein the most key problem is the adhesive force how improving coating with the different substrate materials such as metal, concrete. It is exposed to the sun and under the complex environment influence factor such as salt fog, it is modal protection failure mode that coating interface comes off hot and humid, outdoor, the barrier propterty of coating is affected greatly. Therefore, research has well attached performance and the wide function protecting surfacing of the substrate suitability, to instructing engineering practice, delays base material corrosion rate, ensures engineering structure service life, improves engineering structure safety, reduces the coating protection caused because of adhesion problem and lost efficacy and have great importance.
The protective action of organic coating shows the shielding action that coating has, the wet aspect such as tack and corrosion inhibition. Protection inefficacy has many reasons: the chemical erosion (degraded) of medium, the physical dissolution of medium and swelling, the local failure that medium diffusion in the coating and holiday cause; These all will cause the reduction of coating corrosion resistance energy. Wherein, coating aging degraded and corrosive medium are in the main cause that the diffusion of coat inside is coating failure. (1) being exposed to protective coating in harsh marine environment affects generation degradation with aging due to what be subject to the environmental factorss such as illumination, humidity and temperature, causes protective coating to lose efficacy; (2) Na+、Cl-、SO4 2-Plasma then carries out diffusion by coating, makes base material corrosion failure, causes coating failure. For these reasons, if coating has hydrophobicity, then can be greatly improved anti-Ionic diffusion and the permeability of coating.
The catechol group with strong adhesion is a side chain of dopamine, and it is widely present in the adhesion protein in mussel. Owing to it has great effect in distinct faces anchoring molecule, there is the polymer of this structure and show a series of different materials surfaces (including the surface moistened) are all had good interfacial adhesion intensity. Therefore, the method for dopamine film preparation anti-corrosion film on metal surface is adopted to have been reported. This dopamine film possesses the advantage that adhesion property is good, processing method is easy, and shows certain antiseptic property. Application for a patent for invention CN200910019178.X provides " preparation method of a kind of anti-corrosion film on metal surface "; Dopamine is dissolved in three (methylol) aminomethane hydrochlorides or phosphatic aqueous solution by the method, stirring, immerses metal, and contact 12～90h takes out, with deionized water rinsing; Nitrogen is put in the solution containing alkanethiol after drying, takes out, with the above-mentioned solvent washing containing alkanethiol solution at 20～30 DEG C after water-bath 24～48h; Nitrogen is dried, can form anti-corrosion film on the metal surface. The method can be readily formed stable anticorrosion film on the metallic substrate, and cohesive force is strong, it is not necessary to the longer response time, it is not necessary to metal is performed etching, and the Corrosion Protection of prepared anti-corrosion film on metal surface is good, and protective efficacy is up to 99%. But dopamine films of preparation only have good Corrosion Protection in these reports, not there is super-hydrophobicity, other barrier propterty performance such as antifouling. In complicated marine environment, metal and concrete surface also face multiple corrosion, and the multifunction of protective coating has been had further requirement.
Fluorochemical has good weatherability and chemical resistance, and its surface can be relatively low, has hydro-oleophobicity, is highly suitable for preparing protective material. At present, the preparation of fluorinated copolymer and the existing a large amount of reports of performance study. But due to the polarizability that fluorine atom is relatively low, strong electronegativity, the C-F bond energy that less van der Waals radius is very strong, so the dissolubility of fluorinated copolymer is relatively poor, the copolymer of fluorochemical and dopamine is very easily insoluble in any solvent so that it is can not be modified at material surface by copolymer solution infusion method. Therefore, for the preparation of this fluorochemical Yu dopamine copolymer, its deliquescent control is most important. At present, but without researcher, disclosed report is carried out with regard to this.
Summary of the invention
The present invention, with dopamine and fluorochemical for raw material, adopts the method fluorochemical of copolymerization that dopamine is modified, and preparation comprises fluorine compounds side chain and the copolymer of catechol anchoring group side chain.Described copolymer has the catechol anchoring group of dopamine on the one hand, it is possible to provide good adhesion property; Possess functional fluoropolymer group on the other hand, there is weatherability, antiseptic property and hydrophobic oleophobic performance, it is possible to be greatly enhanced the barrier propterty of function protecting coating.
Technical scheme: N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, the structural formula of described copolymer is:
Described N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, prepared by following method: 1. weigh appropriate 1-pi-allyl-4-(trifluoromethyl) benzene, N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, Cu-lyt., 2,2 '-bipyridyl and benzyl bromide a-bromotoluene; 2. step 1. ready material is added in toluene, stirring reaction 1-8h under atmosphere of inert gases protection, the temperature conditions of 50 DEG C-70 DEG C; 3. being evaporated step 2. reacted solution processing, washing is removed the solvent being attached to precipitation surface and is obtained product; Described step reaction equation 2. is such as shown in Eq.1.
Wherein, count by weight, described 1-pi-allyl-4-(trifluoromethyl) benzene is 3～6 parts, described N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide is 0.1～0.4 part, described Cu-lyt. is 0.01-0.06 part, described 2,2 '-bipyridyl is 0.1～0.4 part, and described benzyl bromide a-bromotoluene is 0.03～0.06 part.
Wherein, the method for step 3. described washing is for adopting methanol and acetone to be respectively washed 2-4 time.
The reaction mechanism preparing N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer in the present invention is: with Cu-lyt. and 2,2 '-bipyridyl is catalyst, the atom transition free radical polymerization reaction that benzyl bromide a-bromotoluene causes. The present invention has selected the fluorochemical monomer containing special construction (phenyl ring) and molecular weight, the method adopting free radical controllable polymerization accurately controls its molecular weight, the fluorinated copolymer making preparation has good dissolubility in toluene, it is possible to by infusion method by its self assembly at material surface. Using fluorochemical as monomer, after carrying out copolymerization with dopamine, it is possible to promote the barrier propterty of dopamine film further, make dopamine film on anti-corrosive properties basis, add hydro-oleophobicity and antifouling property.
There is the function protecting surfacing of well attached performance, by N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer by soaking the material that self assembly obtains at material surface.
The preparation method with the function protecting surfacing of well attached performance, comprises the following steps: 1. weighs appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, is configured to the toluene solution that concentration is 0.02～0.12g/mL; 2. pending material is put in the solution that 1. step is prepared, soak 10～30h, namely obtain the function protecting surfacing with well attached performance.
Wherein, described pending material is aluminum, ferrum, steel, pottery or concrete.
Beneficial effects of the present invention:
(1) copolymer synthesized by the present invention be suitable for substrate extensively, environmental protection, there is good barrier propterty; And with substrate surface, there is firmly chemical bonding, be therefore widely used prospect;
(2) present invention process is simple, only need to by can be obtained by the function protecting surfacing with well attached performance after simply soaking.
(3) the function protecting surfacing that prepared by the present invention has good barrier propterty, ultra-hydrophobicity, antifouling property and adhesion property;Substrate is applied widely; Nontoxic pollution-free, will not impact natural environment.
Figure of description
Fig. 1 is the microphotograph that microalgae cell attaches to material surface.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1:
N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, the structural formula of described copolymer is:
N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, prepared by following method: 1. count by weight, weigh 3 parts of 1-pi-allyl-4-(trifluoromethyl) benzene, 0.2 part of N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, 0.03 part of Cu-lyt., 0.4 part 2,2 '-bipyridyl, 0.03 part of benzyl bromide a-bromotoluene; 2. take the toluene of prior dried, it is passed into argon 15min; Step 1. ready material is added in described toluene, stirring reaction 6h under argon shield, under the temperature conditions of 50 DEG C; Reaction equation is such as shown in Eq.1. 3. it is evaporated step 2. reacted solution processing, then adopts methanol and acetone to be respectively washed 4 times, remove the solvent being attached to precipitation surface and obtain product. Every parts by weight are 10g.
The reaction mechanism preparing N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer in the present invention is: with Cu-lyt. and 2,2 '-bipyridyl is catalyst, the atom transition free radical polymerization reaction that benzyl bromide a-bromotoluene causes. The present invention has selected the fluorochemical monomer containing special construction (phenyl ring) and molecular weight, the method adopting free radical controllable polymerization accurately controls its molecular weight, the fluorinated copolymer making preparation has good dissolubility in toluene, it is possible to by infusion method by its self assembly at material surface. Using fluorochemical as monomer, after carrying out copolymerization with dopamine, it is possible to promote the barrier propterty of dopamine film further, make dopamine film on anti-corrosive properties basis, add hydro-oleophobicity and antifouling property.
There is the function protecting surfacing of well attached performance, by N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer by soaking the material that self assembly obtains at material surface. Its preparation method, comprises the following steps: 1. weighs appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, is configured to the toluene solution that concentration is 0.02g/mL; 2. pending concrete is put in the solution that 1. step is prepared, soak 30h, namely obtain the function protecting surfacing with well attached performance.
Embodiment 2:
As different from Example 1, N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, prepared by following method: 1. count by weight, weigh 4 parts of 1-pi-allyl-4-(trifluoromethyl) benzene, 0.3 part of N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, 0.06 part of Cu-lyt., 0.1 part 2,2 '-bipyridyl, 0.04 part of benzyl bromide a-bromotoluene; 2. take the toluene of prior dried, it is passed into argon 5min; Step 1. ready material is added in toluene, stirring reaction 8h under atmosphere of inert gases protection, the temperature conditions of 60 DEG C. 3. it is evaporated step 2. reacted solution processing, then adopts methanol and acetone to be respectively washed 2 times, remove the solvent being attached to precipitation surface and obtain product.
The preparation method with the function protecting surfacing of well attached performance, comprises the following steps: 1. weighs appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, is configured to the toluene solution that concentration is 0.05g/mL;2. pending ceramic material is put in the solution that 1. step is prepared, soak 20h, namely obtain the function protecting surfacing with well attached performance.
Embodiment 3:
As different from Example 1, N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, prepared by following method: 1. count by weight, weigh 5 parts of 1-pi-allyl-4-(trifluoromethyl) benzene, 0.4 part of N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, 0.01 part of Cu-lyt., 0.2 part 2,2 '-bipyridyl, 0.05 part of benzyl bromide a-bromotoluene; 2. take the toluene of prior dried, it is passed into argon 10min; Step 1. ready material is added in toluene, stirring reaction 1h under atmosphere of inert gases protection, the temperature conditions of 70 DEG C. 3. it is evaporated step 2. reacted solution processing, then adopts methanol and acetone to be respectively washed 3 times, remove the solvent being attached to precipitation surface and obtain product.
The preparation method with the function protecting surfacing of well attached performance, comprises the following steps: 1. weighs appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, is configured to the toluene solution that concentration is 0.08g/mL; 2. pending Steel material is put in the solution that 1. step is prepared, soak 15h, namely obtain the function protecting surfacing with well attached performance.
Embodiment 4:
As different from Example 1, N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, prepared by following method: 1. count by weight, weigh 6 parts of 1-pi-allyl-4-(trifluoromethyl) benzene, 0.1 part of N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, 0.02 part of Cu-lyt., 0.3 part 2,2 '-bipyridyl, 0.06 part of benzyl bromide a-bromotoluene; 2. take the toluene of prior dried, it is passed into argon 12min; Step 1. ready material is added in toluene, stirring reaction 5h under atmosphere of inert gases protection, the temperature conditions of 55 DEG C. 3. it is evaporated step 2. reacted solution processing, then adopts methanol and acetone to be respectively washed 4 times, remove the solvent being attached to precipitation surface and obtain product.
The preparation method with the function protecting surfacing of well attached performance, comprises the following steps: 1. weighs appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, is configured to the toluene solution that concentration is 0.010g/mL; 2. pending iron material is put in the solution that 1. step is prepared, soak 12h, namely obtain the function protecting surfacing with well attached performance.
Embodiment 5:
As different from Example 1, N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, prepared by following method: 1. count by weight, weigh 3.5 parts of 1-pi-allyl-4-(trifluoromethyl) benzene, 0.2 part of N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, 0.04 part of Cu-lyt., 0.3 part 2,2 '-bipyridyl, 0.05 part of benzyl bromide a-bromotoluene; 2. take the toluene of prior dried, it is passed into argon 8min; Step 1. ready material is added in toluene, stirring reaction 4h under atmosphere of inert gases protection, the temperature conditions of 65 DEG C. 3. it is evaporated step 2. reacted solution processing, then adopts methanol and acetone to be respectively washed 2 times, remove the solvent being attached to precipitation surface and obtain product.
The preparation method with the function protecting surfacing of well attached performance, comprises the following steps: 1. weighs appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, is configured to the toluene solution that concentration is 0.12g/mL;2. pending aluminum is put in the solution that 1. step is prepared, soak 10h, namely obtain the function protecting surfacing with well attached performance.
Embodiment 6:
As different from Example 1, N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, prepared by following method: 1. count by weight, weigh 4.5 parts of 1-pi-allyl-4-(trifluoromethyl) benzene, 0.2 part of N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, 0.05 part of Cu-lyt., 0.4 part 2,2 '-bipyridyl, 0.03 part of benzyl bromide a-bromotoluene; 2. take the toluene of prior dried, it is passed into argon 15min; Step 1. ready material is added in toluene, stirring reaction 3h under atmosphere of inert gases protection, the temperature conditions of 60 DEG C. 3. it is evaporated step 2. reacted solution processing, then adopts methanol and acetone to be respectively washed 3 times, remove the solvent being attached to precipitation surface and obtain product.
The preparation method with the function protecting surfacing of well attached performance, comprises the following steps: 1. weighs appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, is configured to the toluene solution that concentration is 0.05g/mL; 2. pending concrete is put in the solution that 1. step is prepared, soak 25h, namely obtain the function protecting surfacing with well attached performance.
Copolymer prepared by table 1. embodiment 1-6 and the contact angle of function protecting material and adhesive force
Embodiment 7:
Adopt microscope to observe microalgae cell and attach to the situation of material surface. (A) after: glass, immersing algae solution 1h; (B): copolymer modifies microscope slide, after immersing algae solution 1h; (C): copolymer modifies load glass, after immersing algae solution 5h; (D): copolymer modifies glass, after immersing algae solution 10h. Wherein, the cell concentration of algae solution is about 1.2 × 106Individual/mm2. Then, being respectively put into by the sample through above-mentioned process in the glass weighing botle loading 10mL culture fluid, microphotograph is in detail as shown in Figure 1.
According to Fig. 1 it can be seen that not modified glass is immersing algae solution, after microalgae is deposited in glass surface, in 1h, microalgae cell just mushrooms out division, forms group's (as shown in Figure 1A). And the sheet glass that copolymer is modified immerses algae solution, after microalgae cell is deposited in glass surface, until after 10h, microalgae there is no significantly growth and division, does not form group (as shown in Figure 1B, 1C, 1D). Thus proving, the copolymer of glass surface can suppress the growth of microalgae cell effectively, has good antifouling property.
Claims (7)
1.N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, it is characterised in that: the structural formula of described copolymer is:
2. N-(3 according to claim 1,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, it is characterized in that: prepared by following method: 1. weigh appropriate 1-pi-allyl-4-(trifluoromethyl) benzene, N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide, Cu-lyt., 22,2 '-bipyridyl and benzyl bromide a-bromotoluene; 2. step 1. ready material is added in toluene solution, stirring reaction 1-8h under atmosphere of inert gases protection, the temperature conditions of 50 DEG C-70 DEG C; 3. it is evaporated step 2. reacted solution processing, after washing, obtains product; Described step reaction equation 2. is:
3. N-(3 according to claim 2,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, it is characterized in that: count by weight, described 1-pi-allyl-4-(trifluoromethyl) benzene is 3～6 parts, and described N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide is 0.1～0.4 part, described Cu-lyt. is 0.01-0.06 part, described 2,2 '-bipyridyl is 0.1～0.4 part, and described benzyl bromide a-bromotoluene is 0.03～0.06 part.
4. N-according to claim 2 (3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, it is characterised in that: the method for described washing is respectively washed 2-4 time for adopting methanol and acetone.
5. there is the function protecting surfacing of well attached performance, it is characterised in that: by N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer by soaking the material that self assembly obtains at material surface.
6. the preparation method of the function protecting surfacing with well attached performance according to claim 5, it is characterized in that: comprise the following steps: 1. weigh appropriate N-(3,4-dihydroxy phenyl) Ethyl-Methyl acrylamide copolymer, it is configured to the toluene solution that concentration is 0.02～0.12g/mL; 2. pending material is put in the solution that 1. step is prepared, soak 10～30h, namely obtain the function protecting surfacing with well attached performance.
7. the preparation method of the function protecting surfacing with well attached performance according to claim 6, it is characterised in that: described pending material is aluminum, ferrum, steel, pottery or concrete.
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| CN107446401A (en) * | 2017-04-01 | 2017-12-08 | 华南理工大学 | Using dopamine as high hydrophobicity anti-bacterial attachment surface of anchor molecule and preparation method thereof |
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| CN101781161B (en) * | 2009-01-20 | 2013-11-27 | 上海开拓者化学研究管理有限公司 | Method for preparing trifluoromethyl styrene compound |
| JP6111052B2 (en) * | 2012-11-22 | 2017-04-05 | 国立大学法人 東京大学 | Water-soluble surface treatment agent for imparting stain resistance, and surface treatment method |
| CN104073114B (en) * | 2013-03-29 | 2016-04-13 | 中国科学院兰州化学物理研究所 | A kind of preparation method with anti-marine biological polution function surface material |
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| CN107446401A (en) * | 2017-04-01 | 2017-12-08 | 华南理工大学 | Using dopamine as high hydrophobicity anti-bacterial attachment surface of anchor molecule and preparation method thereof |
| CN107446401B (en) * | 2017-04-01 | 2019-08-20 | 华南理工大学 | Using dopamine as high hydrophobicity anti-bacterial attachment surface of anchor molecule and preparation method thereof |
| CN108395497A (en) * | 2018-01-22 | 2018-08-14 | 中国科学院兰州化学物理研究所 | Ultraluminescence type space lubricating oil is creeped barrier material |
| CN108485389A (en) * | 2018-03-19 | 2018-09-04 | 浙江巨化技术中心有限公司 | A kind of fluoropolymer powder coatings and its preparation method and application |
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