CN103435830A - Modification method for functionalizing surface of material - Google Patents
Modification method for functionalizing surface of material Download PDFInfo
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- CN103435830A CN103435830A CN2013103923470A CN201310392347A CN103435830A CN 103435830 A CN103435830 A CN 103435830A CN 2013103923470 A CN2013103923470 A CN 2013103923470A CN 201310392347 A CN201310392347 A CN 201310392347A CN 103435830 A CN103435830 A CN 103435830A
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Abstract
The invention discloses a modification method for functionalizing the surface of a material. The modification method comprises the following steps of: (a) preparing a dopamine functional monomer; (b) in a reaction device, enabling the material to react with an alkaline solution containing the dopamine functional monomer; (c) obtaining a material of which the surface is connected with a carbon-carbon double-bond after the reaction in the step (b) is finished; (d) in the reaction device, performing free radical type graft copolymerization reaction on the material of which the surface is connected with the carbon-carbon double-bond, obtained in the step (c), and a monomer solution containing an initiating agent; and (e) obtaining a modified material of which the surface is functionalized after the graft copolymerization reaction in the step (d) is finished to finish the modification for functionalizing the surface of the material. The modification method disclosed by the invention is simple and convenient to operate and strong in universality.
Description
Technical field
The present invention relates to the material modification technology, be specifically related to a kind of method of modifying of functionalizing material surface.
Background technology
Macromolecular material, inorganic non-metallic and metallic substance are applied widely in mankind's activity, and the physicochemical property of accurately controlling these material surfaces have very important meaning at Materials science, chemistry and biological technical field.For example: the sensitivity of bio-sensing chip depends primarily on the chemical property of chip surface; Medicine equipment and drug conveying carrier surface properties have determined its biocompatibility and result for the treatment of; The kind of nano-material surface institute binding molecule and size have determined the size and dimension of nano material etc.And under normal conditions, material surface itself does not often possess required specific chemical property, therefore, material surface is carried out to the functional modification acquisition and there is the Important Action that specific chemical property material surface has become field application developments such as promoting material and apparatus.
Yet current existing most modification strategies often relate to polystep reaction and only for a certain material, and at first the material that lacks functional group for surface also needs through processing such as plasma body, ozone oxidation, gamma-radiation irradiation, electron beam or laser radiations, thereby introduce functional group and material surface is carried out to functional modification at material surface.These method of modifying not only need more expensive specific installation, and operation is comparatively complicated, processing parameter is wayward, does not have universality.
The prior art the most approaching with the present invention is the Chinese patent that publication number is CN101538373A, this patent discloses a kind of method of surface modification of polyurethane material by graft copolymerization, specifically on the polyurethane material surface, by chemical process, connect polymerisable carbon-carbon double bond, under the existence of initiator and vinyl monomer, through radical graft copolymerization and to the polyurethane material surface graft modification, but because this patent adopts acryloyl-oxy isothiocyanic acid ester solution and methacrylic acid acyl-oxygen isothiocyanic acid ester solution, the polyurethane material surface is acted on and realizes being connected to carbon-carbon double bond on the polyurethane material surface, although the method has solved the surface improvements problem of polyurethane material, but as described above, it is for polyurethane material, still can't be for the surface modification of other kind materials.
Because current disclosed all kinds of improvement technology all can only realize the process for modifying surface to specific single-material, this obviously makes applying of surface improvements technology be subject to very big restriction, therefore, for above-mentioned technical problem, be necessary to seek a kind of method of modifying of easy and simple to handle, functionalizing material surface with universality.
Summary of the invention
The object of the present invention is to provide a kind of method of modifying of functionalizing material surface, easy and simple to handle, universality is strong.
Before proposing technical scheme of the present invention, expertise and years of researches development Experience based on the applicant in the function modified technical field of material surface, discovery will obtain a kind of easy and simple to handle, method of modifying with functionalizing material surface of universality, at first to obtain a kind ofly thering is universality ground and can producing free radical at material surface, be beneficial to create the reaction primary condition of free radical type graft copolymerization, and find through theoretical investigation and in conjunction with experiment, the Dopamine monomer can be had an effect with material under aerobic conditions, make material surface be connected to polymerisable carbon-carbon double bond, therefore, can produce free radical at material surface becomes feasible program with having universality.
And current prior art all still is confined on concrete material form the composite bed with strong adhesive force for the use of Dopamine HCL, as the publication number Chinese patent that is CN102614783A, by composite bed, improve the antipollution of material or hydrophilic ability etc.This obviously still comparatively limits to for the use of Dopamine HCL, does not more possess universality, and the applicant has proposed technical scheme of the present invention after groping by great many of experiments, specifically please see below simultaneously.
The method of modifying of a kind of functionalizing material surface proposed according to purpose of the present invention, its operation steps comprises:
A), prepare the Dopamine monomer;
B), in reaction unit, material is reacted with the basic solution that contains the Dopamine monomer;
C), until above-mentioned steps b) after described reaction completes, obtain the material that surface is connected to carbon-carbon double bond;
D), in reaction unit, by above-mentioned steps c) surface that the obtains material that is connected to carbon-carbon double bond carries out the free radical type graft copolymerization with the monomer solution that contains initiator;
E), until above-mentioned steps d) after described graft copolymerization completes, obtain the material of surface-functionalized modification, complete the functionalizing material surface modification.
Preferably, described step a) comprising:
A10), in reaction unit, methacrylic chloride or acrylate chloride are slowly splashed into and contain in basic solution borax and dopamine hydrochloride and that the pH value is 9-10, under the condition that is 0-30 ℃ in temperature, reaction 10-24 hour, obtain reaction solution;
A20), by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that the pH value is 2-4, adopts this acid-reaction liquid of ethyl acetate extracting and separating, obtains organic phase;
A30), by above-mentioned steps a20) organic phase that obtains is rotated evaporation, recrystallization purifying, obtains the Dopamine monomer.
Preferably, in step b), the pH value of described basic solution is 8-9, and described temperature of reaction is 15-45 ℃, and the reaction times is 5-24 hour.
Preferably, in step b), the percentage concentration of the mass/volume of described Dopamine monomer in basic solution is 3-10%, and described basic solution is the San methylol An base Jia Wan – hydrochloride buffer aqueous solution.
Preferably, in step d), described monomer solution is vinyl monomer, and the quality mol ratio of described initiator and vinyl monomer is 1:100-1:400, and described temperature of reaction is 60-80 ℃, and the reaction times is 2-6 hour.
Preferably, at step a10) in, the quality mol ratio of described methacrylic chloride or acrylate chloride and dopamine hydrochloride is 1:1-1:1.2, and the quality mol ratio of described borax and dopamine hydrochloride is 1:1-1:1.2, and described basic solution is alkaline aqueous solution.
Preferably, at step a20) in, adopting hydrochloric acid by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2-4.
Preferably, described vinyl monomer is selected from one or more the mixing in methacrylic acid oligomeric ethylene glycol ester, vinylformic acid, methacrylic acid, Jia base Bing Xi Suan – (2 – hydroxyl) ethyl ester, N – vinyl pyrrolidone, glycidyl methacrylate, Jia base Bing Xi Suan – (N, N – dimethylamino) ethyl ester, N – N-isopropylacrylamide.
Preferably, described initiator is selected from one or more the mixing in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxy dicarbonate ethylhexyl, isopropyl benzene hydroperoxide, Guo Liu Suan Jia – sulphite system or Guo Yangization Qing – ferrite system.
Preferably, the solvent of described vinyl monomer is selected from acetonitrile, toluene, methyl alcohol, acetone, N, the mixing of one or more in N – dimethyl formamide, water.
Preferably, described material is solid-state material, and it is shaped as granular or membranaceous or tubulose or bar-shaped.
Preferably, described material is organic polymer material or ceramic or metallic substance.
Also it should be noted that; the pH value scope of the range of reaction temperature that the present invention relates in full, reaction time range and reaction solution or solution is preferred reaction parameter scope; milli far and away; in the parameter area that in employing and the present invention, preferred reaction parameter scope is interior or close; all should be considered as technique effect identical or that be equal to mutually, within all belonging to the scope of the present invention.
The present invention is reacted with material to make by the basic solution that contains the Dopamine monomer is comprising organic polymer material, the various types of materials surface of ceramic or metallic substance etc. all can connect polymerisable carbon-carbon double bond, then the material that surface is connected to carbon-carbon double bond mixes with the mixing solutions of initiator-monomer, at first initiator makes carbon-carbon double bond produce free radical, then under the initiation of free radical, making material surface and monomer carry out graft copolymerization realizes material is carried out to surface-functionalized modification, the present invention can change according to the performance of graftomer physics and/or the chemical property of material surface, as according to the present invention when poly-(N-sec.-propyl) acrylamide of material surface grafting, can obtain the material surface that temperature susceplibility is high, when the material surface grafted polyacrylic acid, can obtain the high material surface of pH value susceptibility, universality is extremely strong, in addition, the method of modifying of functionalizing material surface provided by the invention is pure chemical solution reaction method, do not need to adopt gas ions as the material require that prior art lacks functional group for some surfaces, the specific installation that ozonizer etc. are more expensive processes to obtain surface functional group, therefore the present invention is simple to operate, processing parameter is more easy to control and implementation cost is low, also make the present invention to carry out good modification to the solid material surface functionalization of different shape simultaneously, therefore the present invention is highly suitable for large-scale promotion application in the modification of various types of materials function of surface.
The accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, below will the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described, apparently, the accompanying drawing the following describes is only some embodiment that put down in writing in the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is unmodified polyvinyl chloride diaphragm and the surface hydrophilic performance comparison diagram of polyvinyl chloride diaphragm through the embodiment of the present invention 4 modifications.
Embodiment
The embodiment of the invention discloses a kind of method of modifying of functionalizing material surface, its operation steps comprises:
A), prepare the Dopamine monomer;
B), in reaction unit, material is reacted with the basic solution that contains the Dopamine monomer;
C), until above-mentioned steps b) reacted after, obtain the material that surface is connected to carbon-carbon double bond;
D), in reaction unit, by above-mentioned steps c) surface that the obtains material that is connected to carbon-carbon double bond carries out the free radical type graft copolymerization with the monomer solution that contains initiator;
E), until above-mentioned steps d) after graft copolymerization completes, obtain the material of surface-functionalized modification, complete the functionalizing material surface modification.
The embodiment of the present invention is reacted with material to make by the basic solution that contains the Dopamine monomer is comprising organic polymer material, the various types of materials surface of ceramic or metallic substance etc. all can connect polymerisable carbon-carbon double bond, then the material that surface is connected to carbon-carbon double bond mixes with the mixing solutions of initiator-monomer, at first initiator makes carbon-carbon double bond produce free radical, then under the initiation of free radical, making material surface and monomer carry out graft copolymerization realizes material is carried out to surface-functionalized modification, the embodiment of the present invention can change according to the performance of graftomer physics and/or the chemical property of material surface, as according to the embodiment of the present invention when poly-(N-sec.-propyl) acrylamide of material surface grafting, can obtain the material surface that temperature susceplibility is high, when the material surface grafted polyacrylic acid, can obtain the high material surface of pH value susceptibility, universality is extremely strong, in addition, the method of modifying of the functionalizing material surface that the embodiment of the present invention provides is pure chemical solution reaction method, do not need to adopt gas ions as the material require that prior art lacks functional group for some surfaces, the specific installation that ozonizer etc. are more expensive processes to obtain surface functional group, therefore the embodiment of the present invention is simple to operate, processing parameter is more easy to control and implementation cost is low, also make the embodiment of the present invention to carry out good modification to the solid material surface functionalization of different shape simultaneously, therefore the embodiment of the present invention is highly suitable for large-scale promotion application in the modification of various types of materials function of surface.
In order to make those skilled in the art person understand better the technical scheme in the present invention, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment obtained, should belong to the scope of protection of the invention.
Embodiment 1: surface of glass slide temperature susceplibility function modified
A), prepare the Dopamine monomer:
A10), 3.83g borax, 1.9g dopamine hydrochloride, 100mL water are placed in to the 250mL reaction unit, stirring and dissolving also is adjusted to 9～10 with aqueous sodium carbonate by the pH value;
The 1.05g methacrylic chloride is slowly splashed in reaction unit, and at room temperature, stirring reaction 24 hours, obtain reaction solution;
A20), adopting concentrated hydrochloric acid by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that the pH value is 2, adopt this acid-reaction liquid of ethyl acetate extracting and separating, extraction times is selected 3 times, can certainly adopt more than 4 times or 4 times, the organic phase that extraction obtains is at every turn merged, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, then carry out after rotary evaporation in vacuo is removed ethyl acetate obtaining crude product, then, through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain the Dopamine monomer;
B), in reaction unit, by the slide of 30 lengths of a film and the wide 0.5cm of being (thickness is 0.7mm) with contain the San methylol An base Jia Wan – hydrochloride buffer aqueous solution Dopamine monomer and that the pH value is 8.5 at room temperature, stirring reaction 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol An base Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) after described reaction completes, slide is taken out, obtain the slide that surface is connected to carbon-carbon double bond after deionized water wash drying;
D), by above-mentioned steps c) 20 surfaces obtaining are connected to the slide of carbon-carbon double bond and the mixing solutions of initiator-vinyl monomer that 0.028g Diisopropyl azodicarboxylate, 2.26g N – N-isopropylacrylamide, 15mL methyl alcohol form together is placed in the 50mL reaction unit, in nitrogen gas protective atmosphere, stirring, and be heated to carry out the free radical type graft copolymerization under 65 ℃ of conditions that also are incubated, the reaction times is 6 hours;
E), until above-mentioned steps d) after described graft copolymerization completes, slide is taken out, after methyl alcohol, water washing drying, obtain poly-(N – sec.-propyl) Modified by Acrylamide Graft slide that the surface temperature susceptibility is high, complete the function modified of surface of glass slide temperature susceplibility.
Embodiment 2: stainless steel substrates antibacterial surface performance function modified
A), prepare the Dopamine monomer:
A10), 3.83g borax, 1.9g dopamine hydrochloride, 100mL water are placed in to the 250mL reaction unit, stirring and dissolving also is adjusted to 9～10 with aqueous sodium carbonate by the pH value;
The 1.05g methacrylic chloride is slowly splashed in reaction unit, and at room temperature, stirring reaction 24 hours, obtain reaction solution;
A20), adopting concentrated hydrochloric acid by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that the pH value is 2, adopt this acid-reaction liquid of ethyl acetate extracting and separating, extraction times is selected 3 times, can certainly adopt more than 4 times or 4 times, the organic phase that extraction obtains is at every turn merged, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, then carry out after rotary evaporation in vacuo is removed ethyl acetate obtaining crude product, then, through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain the Dopamine monomer;
B), in reaction unit, by the stainless steel substrates of 10 lengths of a film and the wide 1.0cm of being (thickness is 1.0mm) with contain the San methylol An base Jia Wan – hydrochloride buffer aqueous solution Dopamine monomer and that the pH value is 8.5 at room temperature, stirring reaction 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol An base Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) after described reaction completes, stainless steel substrates is taken out, obtain the stainless steel substrates that surface is connected to carbon-carbon double bond after deionized water wash drying;
D), by above-mentioned steps c) 5 surfaces obtaining are connected to the stainless steel substrates of carbon-carbon double bond and 0.028g Diisopropyl azodicarboxylate, 3mL methacrylic acid (N, the mixing solutions of initiator-vinyl monomer that N – dimethylamino) ethyl ester, 20mL methyl alcohol form together is placed in the reaction unit of 50mL, in nitrogen gas protective atmosphere, stirring, and be heated to carry out the free radical type graft copolymerization under 65 ℃ of conditions that also are incubated, the reaction times is 6 hours;
E), until above-mentioned steps d) after described graft copolymerization completes, stainless steel substrates is taken out, after methyl alcohol, water washing drying, obtain polymethyl acrylic acid (N, N – dimethylamino) stainless steel substrates of ethyl ester graft modification, can obtain the stainless steel substrates that surface has good anti-microbial property after further quaternary ammoniated, complete the function modified of stainless steel substrates antibacterial surface performance.
Embodiment 3: polyurethane tube surface pH value susceptibility function modified
A), prepare the Dopamine monomer:
A10), 3.83g borax, 1.9g dopamine hydrochloride, 100mL water are placed in to the 250mL reaction unit, stirring and dissolving also is adjusted to 9～10 with aqueous sodium carbonate by the pH value;
The 1.05g methacrylic chloride is slowly splashed in reaction unit, and at room temperature, stirring reaction 24 hours, obtain reaction solution;
A20), adopting concentrated hydrochloric acid by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that the pH value is 2, adopt this acid-reaction liquid of ethyl acetate extracting and separating, extraction times is selected 3 times, can certainly adopt more than 4 times or 4 times, the organic phase that extraction obtains is at every turn merged, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, then carry out after rotary evaporation in vacuo is removed ethyl acetate obtaining crude product, then, through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain the Dopamine monomer;
B), in reaction unit, by 10 long be 1cm, the polyurethane tube that internal diameter is 5mm with contain the San methylol An base Jia Wan – hydrochloride buffer aqueous solution Dopamine monomer and that the pH value is 8.5 at room temperature, react 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol An base Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) after described reaction completes, polyurethane tube is taken out, obtain the polyurethane tube that surface is connected to carbon-carbon double bond after deionized water wash drying;
D), by above-mentioned steps c) 8 surfaces obtaining mixing solutions of being connected to the polyurethane tube of carbon-carbon double bond and initiator-vinyl monomer that 0.040g dibenzoyl peroxide, 1.4mL vinylformic acid, 15mL acetone form together is placed in the reaction unit of 25mL, in nitrogen gas protective atmosphere, stirring, and be heated to carry out the free radical type graft copolymerization under 70 ℃ of conditions that also are incubated, the reaction times is 3 hours;
E), until above-mentioned steps d) after described graft copolymerization completes, polyurethane tube is taken out, after water washing drying, obtain the polyurethane tube of the polyacrylic acid grafted modification that the surface pH value susceptibility is high, complete the function modified of polyurethane tube surface pH value susceptibility.
Embodiment 4: polyvinyl chloride diaphragm surface hydrophilicity can function modified
A), prepare the Dopamine monomer:
A10), 3.83g borax, 1.9g dopamine hydrochloride, 100mL water are placed in to the 250mL reaction unit, stirring and dissolving also is adjusted to 9～10 with aqueous sodium carbonate by the pH value;
The 1.05g methacrylic chloride is slowly splashed in reaction unit, and at room temperature, stirring reaction 24 hours, obtain reaction solution;
A20), adopting concentrated hydrochloric acid by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that the pH value is 2, adopt this acid-reaction liquid of ethyl acetate extracting and separating, extraction times is selected 3 times, can certainly adopt more than 4 times or 4 times, the organic phase that extraction obtains is at every turn merged, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, then carry out after rotary evaporation in vacuo is removed ethyl acetate obtaining crude product, then, through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain the Dopamine monomer;
B), in reaction unit, 30 diameters are about to the polyvinyl chloride diaphragm (thickness is 0.5mm) of 5mm and contain the three methylol ammonia base first alkane – hydrochloride buffer aqueous solution Dopamine monomer and that the pH value is 8.5 at room temperature, stirring reaction 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol An base Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) after described reaction completes, the polyvinyl chloride diaphragm is taken out, obtain the polyvinyl chloride diaphragm that surface is connected to carbon-carbon double bond after deionized water wash drying;
D), by above-mentioned steps c) 20 surfaces obtaining mixing solutions of being connected to the polyvinyl chloride diaphragm of carbon-carbon double bond and initiator-vinyl monomer that 0.028g Diisopropyl azodicarboxylate, 2.22g N – vinyl pyrrolidone, 15mL methyl alcohol form together is placed in the reaction unit of 50mL, in nitrogen gas protective atmosphere, stirring, and be heated to carry out the free radical type graft copolymerization under 65 ℃ of conditions that also are incubated, the reaction times is 5 hours;
E), until above-mentioned steps d) after described graft copolymerization completes, the polyvinyl chloride diaphragm is taken out, after methyl alcohol, water washing drying, obtain the polyvinyl chloride diaphragm that surface has the polyvinylpyrrolidone graft modification of good hydrophilic performance, complete the function modified of polyvinyl chloride diaphragm surface hydrophilicity energy.
As shown in Figure 1, the surface static water contact angle α 1 of unmodified polyvinyl chloride diaphragm 1 is about 78 °, and the surface static water contact angle α 2 of the polyvinyl chloride diaphragm 2 of Polyvinylpyrolidone (PVP) modification is about 30 °, therefore can further illustrate the polyvinyl chloride diaphragm surface obtained through the embodiment of the present invention 4 modifications has possessed very good hydrophilicity.
In sum, functional modification method of the present invention adopt contain the Dopamine monomer basic solution under aerobic conditions to the material surface effect, make material surface form polymerisable carbon-carbon double bond, then the material that surface is connected to carbon-carbon double bond carries out the free radical type graft copolymerization with the monomer solution that contains initiator, according to differing materials, select different monomer solutions and initiator to obtain different graftomer simultaneously, and then realize physics and the chemical property on differing materials surface are carried out to modification, method of modifying due to functionalizing material surface provided by the invention is pure chemical solution reaction method simultaneously, therefore the present invention is not only applicable to various organic polymer materials, the modification of ceramic or metal material surface functionalization, and be applicable to the modification to the solid material surface functionalization of different shape, universality is extremely strong.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that do not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.Any Reference numeral in claim should be considered as limit related claim.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through appropriate combination, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (12)
1. the method for modifying of a functionalizing material surface, is characterized in that, its operation steps comprises:
A), prepare the Dopamine monomer;
B), in reaction unit, material is reacted with the basic solution that contains the Dopamine monomer;
C), until above-mentioned steps b) after described reaction completes, obtain the material that surface is connected to carbon-carbon double bond;
D), in reaction unit, by above-mentioned steps c) surface that the obtains material that is connected to carbon-carbon double bond carries out the free radical type graft copolymerization with the monomer solution that contains initiator;
E), until above-mentioned steps d) after described graft copolymerization completes, obtain the material of surface-functionalized modification, complete the functionalizing material surface modification.
2. the method for modifying of functionalizing material surface as claimed in claim 1, is characterized in that, described step a) comprising:
A10), in reaction unit, methacrylic chloride or acrylate chloride are slowly splashed into and contain in basic solution borax and dopamine hydrochloride and that the pH value is 9-10, under the condition that is 0-30 ℃ in temperature, reaction 10-24 hour, obtain reaction solution;
A20), by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that the pH value is 2-4, adopts this acid-reaction liquid of ethyl acetate extracting and separating, obtains organic phase;
A30), by above-mentioned steps a20) organic phase that obtains is rotated evaporation, recrystallization purifying, obtains the Dopamine monomer.
3. the method for modifying of functionalizing material surface as claimed in claim 1, is characterized in that, in step b), the pH value of described basic solution is 8-9, and described temperature of reaction is 15-45 ℃, and the reaction times is 5-24 hour.
4. the method for modifying of functionalizing material surface as claimed in claim 1, it is characterized in that, in step b), the percentage concentration of the mass/volume of described Dopamine monomer in basic solution is 3-10%, and described basic solution is the San methylol An base Jia Wan – hydrochloride buffer aqueous solution.
5. the method for modifying of functionalizing material surface as claimed in claim 1, it is characterized in that, in step d), described monomer solution is vinyl monomer, the quality mol ratio of described initiator and vinyl monomer is 1:100-1:400, described temperature of reaction is 60-80 ℃, and the reaction times is 2-6 hour.
6. the method for modifying of functionalizing material surface as claimed in claim 2, it is characterized in that, at step a10) in, the quality mol ratio of described methacrylic chloride or acrylate chloride and dopamine hydrochloride is 1:1-1:1.2, the quality mol ratio of described borax and dopamine hydrochloride is 1:1-1:1.2, and described basic solution is alkaline aqueous solution.
7. the method for modifying of functionalizing material surface as claimed in claim 2, is characterized in that, at step a20) in, adopting hydrochloric acid by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2-4.
8. the method for modifying of functionalizing material surface as claimed in claim 5, it is characterized in that, described vinyl monomer is selected from one or more the mixing in methacrylic acid oligomeric ethylene glycol ester, vinylformic acid, methacrylic acid, Jia base Bing Xi Suan – (2 – hydroxyl) ethyl ester, N – vinyl pyrrolidone, glycidyl methacrylate, Jia base Bing Xi Suan – (N, N – dimethylamino) ethyl ester, N – N-isopropylacrylamide.
9. the method for modifying of functionalizing material surface as claimed in claim 5, it is characterized in that, described initiator is selected from one or more the mixing in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxy dicarbonate ethylhexyl, isopropyl benzene hydroperoxide, Guo Liu Suan Jia – sulphite system or Guo Yangization Qing – ferrite system.
10. the method for modifying of functionalizing material surface as claimed in claim 5, is characterized in that, the solvent of described vinyl monomer is selected from acetonitrile, toluene, methyl alcohol, acetone, N, the mixing of one or more in N – dimethyl formamide, water.
11. the method for functionalizing material surface modification as described as one of claim 1-10, is characterized in that, described material is solid-state material, and it is shaped as granular or membranaceous or tubulose or bar-shaped.
12. the method for functionalizing material surface modification as described as one of claim 1-10, is characterized in that, described material is organic polymer material or ceramic or metallic substance.
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| CN106317442A (en) * | 2016-08-17 | 2017-01-11 | 大连理工大学 | Dopamine and dopamine derivative polymerization and high-molecular material surface modification technology |
| CN106943971A (en) * | 2016-01-07 | 2017-07-14 | 天津科技大学 | Strengthen the method for high molecular microcapsule intensity under a kind of temperate condition |
| CN106967228A (en) * | 2017-04-26 | 2017-07-21 | 西北大学 | A kind of pervasive, efficient material surface modifying method |
| CN110100045A (en) * | 2016-12-22 | 2019-08-06 | 汉高股份有限及两合公司 | For the catechin compounds of metal pretreatment application and the reaction product of functionalization coreaction compound |
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| US11407921B2 (en) | 2016-12-22 | 2022-08-09 | Henkel Ag & Co. Kgaa | Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications |
| CN110100045A (en) * | 2016-12-22 | 2019-08-06 | 汉高股份有限及两合公司 | For the catechin compounds of metal pretreatment application and the reaction product of functionalization coreaction compound |
| US11891534B2 (en) | 2016-12-22 | 2024-02-06 | Henkel Ag & Co. Kgaa | Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds |
| CN110100045B (en) * | 2016-12-22 | 2022-09-06 | 汉高股份有限及两合公司 | Reaction products of catechol compounds with functionalized co-reactive compounds for metal pretreatment applications |
| CN106967228A (en) * | 2017-04-26 | 2017-07-21 | 西北大学 | A kind of pervasive, efficient material surface modifying method |
| CN110642980A (en) * | 2018-06-27 | 2020-01-03 | 华东理工大学 | Ultrahigh-strength mineralized hydrogel, and synthesis method and application thereof |
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| CN113082300A (en) * | 2021-04-06 | 2021-07-09 | 西南交通大学 | Antibacterial and anticoagulant coating, preparation method and application thereof |
| CN114106443A (en) * | 2021-12-03 | 2022-03-01 | 上海长园电子材料有限公司 | Antibacterial heat-shrinkable tube and preparation method and application thereof |
| CN114933414A (en) * | 2022-07-25 | 2022-08-23 | 西安宏星电子浆料科技股份有限公司 | Temperature sensitivity resistant LTCC insulating medium slurry |
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