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.
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.