CN103435830B - A kind of method of modifying of functionalizing material surface - Google Patents
A kind of method of modifying of functionalizing material surface Download PDFInfo
- Publication number
- CN103435830B CN103435830B CN201310392347.0A CN201310392347A CN103435830B CN 103435830 B CN103435830 B CN 103435830B CN 201310392347 A CN201310392347 A CN 201310392347A CN 103435830 B CN103435830 B CN 103435830B
- Authority
- CN
- China
- Prior art keywords
- reaction
- modifying
- material surface
- monomer
- mentioned steps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of method of modifying of functionalizing material surface, its operation steps comprises: a), prepare Dopamine monomer; B), in reaction unit, material and the basic solution containing Dopamine monomer are reacted; C), until above-mentioned steps b) described in reaction complete 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 free radical type graft copolymerization with the monomer solution containing initiator; E), until above-mentioned steps d) described in graft copolymerization complete after, obtain the material of surface-functionalized modification, complete functionalizing material surface modification, the present invention is easy and simple to handle, universality is strong.
Description
Technical field
The present invention relates to 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 accurately controlling these material surfaces have very important meaning at Materials science, chemistry and biological technical field.Such as: the sensitivity of bio-sensing chip depends primarily on the chemical property of chip surface; Medicine equipment and drug conveying carrier surface properties determine its biocompatibility and result for the treatment of; The kind of nano-material surface institute binding molecule and size determine the size and dimension etc. of nano material.And under normal conditions, material surface itself does not often possess required specified chemical character, therefore, functional modification acquisition is carried out to material surface and there is the Important Action that specified chemical character material surface has become the field such as material and apparatus of promotion application development.
But current existing most modification strategies often relates to polystep reaction and only for a certain material, and first the material of surface shortage functional group is also needed through process such as plasma body, ozone oxidation, gamma-radiation irradiation, electron beam or laser radiations, thus introduce functional group at material surface and functional modification is carried out to material surface.These method of modifying not only need specific installation costly, and operation is comparatively complicated, processing parameter is wayward, does not have universality.
The Chinese patent of the prior art the most close with the present invention to be publication number be CN101538373A, which disclose a kind of method of surface modification of polyurethane material by graft copolymerization, specifically connect polymerisable carbon-carbon double bond on polyurethane material surface by chemical process, under the existence of initiator and vinyl monomer, through radical graft copolymerization to polyurethane material surface graft modification, but realize being connected to carbon-carbon double bond on polyurethane material surface because this patent adopts acryloyl-oxy isothiocyanic acid ester solution and methacrylic acid acyl-oxygen isothiocyanic acid ester solution to carry out effect to polyurethane material surface, although the method solves the surface improvements problem of polyurethane material, but as described above, it is for polyurethane material, still the surface modification of other type materials cannot be used for.
Because disclosed all kinds of improvement opportunity all can only realize the process for modifying surface to specific single-material at present, 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, the 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 proposition technical scheme of the present invention, based on the applicant in the expertise of the function modified technical field of material surface and years of researches development Experience, discovery will obtain a kind of easy and simple to handle, there is the method for modifying of the functionalizing material surface of universality, first one to be obtained and free radical can be produced at material surface while there is universality, be beneficial to the reaction primary condition creating free radical type graft copolymerization, and through theoretical investigation and Binding experiment find, Dopamine monomer can be had an effect with material under aerobic conditions, material surface is made to 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 is all still confined to concrete material is formed the composite bed with strong adhesive force for the use of Dopamine HCL, if publication number is the Chinese patent of CN102614783A, improve the antipollution of material or hydrophilic ability etc. by composite bed.This obviously still comparatively limits to for the use of Dopamine HCL, does not possess universality simultaneously, after the applicant is groped by great many of experiments, proposes technical scheme of the present invention, specifically please see below.
The method of modifying of a kind of functionalizing material surface that object according to the present invention proposes, its operation steps comprises:
A) Dopamine monomer, is prepared;
B), in reaction unit, material and the basic solution containing Dopamine monomer are reacted;
C), until above-mentioned steps b) described in reaction complete 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 free radical type graft copolymerization with the monomer solution containing initiator;
E), until above-mentioned steps d) described in graft copolymerization complete after, obtain the material of surface-functionalized modification, complete functionalizing material surface modification.
Preferably, described step a) comprising:
A10), in reaction unit, methacrylic chloride or acrylate chloride are slowly instilled containing borax and dopamine hydrochloride and pH value is in the basic solution of 9-10, be under the condition of 0-30 DEG C in temperature, reaction 10-24 hour, obtains reaction solution;
A20), by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2-4, and adopt extraction into ethyl acetate to be separated this acid-reaction liquid, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains carries out rotary evaporation, recrystallization purifying, obtains Dopamine monomer.
Preferably, in step b), the pH value of described basic solution is 8-9, and described temperature of reaction is 15-45 DEG C, and the reaction times is 5-24 hour.
Preferably, in step b), the percentage concentration of the described mass/volume of Dopamine monomer in basic solution is 3-10%, and described basic solution is the San methylol 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 DEG C, and the reaction times is 2-6 hour.
Preferably, in 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, in 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 one or more the mixing in acetonitrile, toluene, methyl alcohol, acetone, N, N – dimethyl formamide, water.
Preferably, described material is solid-state material, and its shape is 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 range of range of reaction temperature, reaction time range and reaction solution that the present invention relates in full or solution is preferred reaction parameter scope; milli far and away; adopt with preferred reaction parameter in the present invention within the scope of or in close parameter area; all should be considered as identical or equivalent mutually technique effect, all belong within the scope of the present invention.
The present invention carries out reaction by the basic solution containing Dopamine monomer and material and makes 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 material surface being connected to carbon-carbon double bond mixes with the mixing solutions of initiator-monomer, first initiator makes carbon-carbon double bond produce free radical, then under the initiation of free radical, make material surface and monomer carry out graft copolymerization to realize carrying out surface-functionalized modification to material, the present invention can change physics and/or the chemical property of material surface according to the performance of graftomer, as according to the present invention when poly-(N-sec.-propyl) acrylamide of material surface grafting, the material surface that temperature susceplibility is high can be obtained, when material surface grafted polyacrylic acid, can obtain the material surface that pH sensitive degree is high, universality is extremely strong, in addition, the method of modifying of functionalizing material surface provided by the invention is pure chemical solution reaction method, the material require lacking functional group for some surfaces as prior art is not needed to adopt gas ions, the specific installation costly such as ozonizer carries out process 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 can 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.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is unmodified polyvinyl chloride diaphragm and the surface hydrophilic performance comparison diagram through the polyvinyl chloride diaphragm of the embodiment of the present invention 4 modification.
Embodiment
The embodiment of the invention discloses a kind of method of modifying of functionalizing material surface, its operation steps comprises:
A) Dopamine monomer, is prepared;
B), in reaction unit, material and the basic solution containing Dopamine monomer are reacted;
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 free radical type graft copolymerization with the monomer solution containing initiator;
E), until above-mentioned steps d) after graft copolymerization completes, obtain the material of surface-functionalized modification, complete functionalizing material surface modification.
The embodiment of the present invention is carried out reaction by the basic solution containing Dopamine monomer and material and is made 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 material surface being connected to carbon-carbon double bond mixes with the mixing solutions of initiator-monomer, first initiator makes carbon-carbon double bond produce free radical, then under the initiation of free radical, make material surface and monomer carry out graft copolymerization to realize carrying out surface-functionalized modification to material, the embodiment of the present invention can change physics and/or the chemical property of material surface according to the performance of graftomer, as according to the embodiment of the present invention when poly-(N-sec.-propyl) acrylamide of material surface grafting, the material surface that temperature susceplibility is high can be obtained, when material surface grafted polyacrylic acid, can obtain the material surface that pH sensitive degree is high, 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, the material require lacking functional group for some surfaces as prior art is not needed to adopt gas ions, the specific installation costly such as ozonizer carries out process 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 can 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.
Technical scheme in the present invention is understood better in order to make those skilled in the art person, 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, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, should belong to the scope of protection of the invention.
Embodiment 1: surface of glass slide temperature susceplibility function modified
A) Dopamine monomer, is prepared:
A10), by 3.83g borax, 1.9g dopamine hydrochloride, 100mL water be placed in 250mL reaction unit, pH value is also adjusted to 9 ~ 10 with aqueous sodium carbonate by stirring and dissolving;
Slowly instilled in reaction unit by 1.05g methacrylic chloride, at room temperature, stirring reaction 24 hours, obtains reaction solution;
A20) concentrated hydrochloric acid, is adopted by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2, extraction into ethyl acetate is adopted to be separated this acid-reaction liquid, extraction times selects 3 times, more than 4 times or 4 times can certainly be adopted, merge extracting the organic phase obtained at every turn, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, obtain crude product after then carrying out rotary evaporation in vacuo removing ethyl acetate, then through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain Dopamine monomer;
B), in reaction unit, by the slide (thickness is 0.7mm) of 30 lengths of a film and the wide 0.5cm of being with containing Dopamine monomer and pH value be the San methylol Jia Wan – hydrochloride buffer aqueous solution of 8.5 at room temperature, stirring reaction 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) described in reaction complete after, slide is taken out, obtains through deionized water wash the slide that surface is connected to carbon-carbon double bond after drying;
D), by above-mentioned steps c) 20 surfaces obtaining mixing solutions of being connected to initiator-vinyl monomer that the slide of carbon-carbon double bond and 0.028g Diisopropyl azodicarboxylate, 2.26gN – N-isopropylacrylamide, 15mL methyl alcohol form together is placed in 50mL reaction unit, in nitrogen gas protective atmosphere, stirring, and be heated to 65 DEG C and carry out free radical type graft copolymerization under the condition of insulation, the reaction times is 6 hours;
E), until above-mentioned steps d) described in graft copolymerization complete after, slide is taken out, through methyl alcohol, water washing after drying, obtain poly-(N – sec.-propyl) Modified by Acrylamide Graft slide that 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) Dopamine monomer, is prepared:
A10), by 3.83g borax, 1.9g dopamine hydrochloride, 100mL water be placed in 250mL reaction unit, pH value is also adjusted to 9 ~ 10 with aqueous sodium carbonate by stirring and dissolving;
Slowly instilled in reaction unit by 1.05g methacrylic chloride, at room temperature, stirring reaction 24 hours, obtains reaction solution;
A20) concentrated hydrochloric acid, is adopted by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2, extraction into ethyl acetate is adopted to be separated this acid-reaction liquid, extraction times selects 3 times, more than 4 times or 4 times can certainly be adopted, merge extracting the organic phase obtained at every turn, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, obtain crude product after then carrying out rotary evaporation in vacuo removing ethyl acetate, then through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain Dopamine monomer;
B), in reaction unit, by the stainless steel substrates (thickness is 1.0mm) of 10 lengths of a film and the wide 1.0cm of being with containing Dopamine monomer and pH value be the San methylol Jia Wan – hydrochloride buffer aqueous solution of 8.5 at room temperature, stirring reaction 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) described in reaction complete after, stainless steel substrates is taken out, obtains through deionized water wash the stainless steel substrates that surface is connected to carbon-carbon double bond after drying;
D), by above-mentioned steps c) 5 surfaces obtaining are connected to stainless steel substrates and 0.028g Diisopropyl azodicarboxylate, the 3mL methacrylic acid (N of carbon-carbon double bond, N – dimethylamino) ethyl ester, 20mL methyl alcohol composition the mixing solutions of initiator-vinyl monomer be together placed in the reaction unit of 50mL, in nitrogen gas protective atmosphere, stirring, and be heated to 65 DEG C and carry out free radical type graft copolymerization under the condition of insulation, the reaction times is 6 hours;
E), until above-mentioned steps d) described in graft copolymerization complete after, stainless steel substrates is taken out, through methyl alcohol, water washing after drying, obtain polymethyl acrylic acid (N, N – dimethylamino) stainless steel substrates of ethyl ester graft modification, the stainless steel substrates that surface has good anti-microbial property can be obtained after quaternary ammoniated further, complete the function modified of stainless steel substrates antibacterial surface performance.
Embodiment 3: polyurethane tube surface pH value susceptibility function modified
A) Dopamine monomer, is prepared:
A10), by 3.83g borax, 1.9g dopamine hydrochloride, 100mL water be placed in 250mL reaction unit, pH value is also adjusted to 9 ~ 10 with aqueous sodium carbonate by stirring and dissolving;
Slowly instilled in reaction unit by 1.05g methacrylic chloride, at room temperature, stirring reaction 24 hours, obtains reaction solution;
A20) concentrated hydrochloric acid, is adopted by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2, extraction into ethyl acetate is adopted to be separated this acid-reaction liquid, extraction times selects 3 times, more than 4 times or 4 times can certainly be adopted, merge extracting the organic phase obtained at every turn, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, obtain crude product after then carrying out rotary evaporation in vacuo removing ethyl acetate, then through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain Dopamine monomer;
B), in reaction unit, by 10 long be 1cm, internal diameter be 5mm polyurethane tube with containing Dopamine monomer and pH value be the San methylol Jia Wan – hydrochloride buffer aqueous solution of 8.5 at room temperature, react 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) described in reaction complete after, polyurethane tube is taken out, obtains through deionized water wash the polyurethane tube that surface is connected to carbon-carbon double bond after drying;
D), by above-mentioned steps c) the 8 root table faces that the obtain mixing solutions that is connected to initiator-vinyl monomer that the polyurethane tube of carbon-carbon double bond and 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 70 DEG C and carry out free radical type graft copolymerization under the condition of insulation, the reaction times is 3 hours;
E), until above-mentioned steps d) described in graft copolymerization complete after, polyurethane tube is taken out, after drying, obtain the polyurethane tube of the high polyacrylic acid grafted modification of surface pH value susceptibility through water washing, complete the function modified of polyurethane tube surface pH value susceptibility.
Embodiment 4: polyvinyl chloride diaphragm surface hydrophilicity can function modified
A) Dopamine monomer, is prepared:
A10), by 3.83g borax, 1.9g dopamine hydrochloride, 100mL water be placed in 250mL reaction unit, pH value is also adjusted to 9 ~ 10 with aqueous sodium carbonate by stirring and dissolving;
Slowly instilled in reaction unit by 1.05g methacrylic chloride, at room temperature, stirring reaction 24 hours, obtains reaction solution;
A20) concentrated hydrochloric acid, is adopted by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2, extraction into ethyl acetate is adopted to be separated this acid-reaction liquid, extraction times selects 3 times, more than 4 times or 4 times can certainly be adopted, merge extracting the organic phase obtained at every turn, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains after anhydrous magnesium sulfate drying, obtain crude product after then carrying out rotary evaporation in vacuo removing ethyl acetate, then through ethyl acetate/methanol mixed solvent recrystallization purifying, obtain Dopamine monomer;
B), in reaction unit, the polyvinyl chloride diaphragm (thickness is 0.5mm) 30 diameters being about 5mm with containing Dopamine monomer and pH value be the three methylol first alkane – hydrochloride buffer aqueous solution of 8.5 at room temperature, stirring reaction 20 hours, wherein, the percentage concentration of the mass/volume of Dopamine monomer in the San methylol Jia Wan – hydrochloride buffer aqueous solution is 5%;
C), until above-mentioned steps b) described in reaction complete after, polyvinyl chloride diaphragm is taken out, obtains through deionized water wash the polyvinyl chloride diaphragm that surface is connected to carbon-carbon double bond after drying;
D), by above-mentioned steps c) 20 surfaces obtaining mixing solutions of being connected to initiator-vinyl monomer that the polyvinyl chloride diaphragm of carbon-carbon double bond and 0.028g Diisopropyl azodicarboxylate, 2.22gN – 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 65 DEG C and carry out free radical type graft copolymerization under the condition of insulation, the reaction times is 5 hours;
E), until above-mentioned steps d) described in graft copolymerization complete after, polyvinyl chloride diaphragm is taken out, through methyl alcohol, water washing after 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 illustrates the polyvinyl chloride diaphragm surface obtained through the embodiment of the present invention 4 modification and possess very good hydrophilicity.
In sum, functional modification method of the present invention adopts the basic solution containing Dopamine monomer to act on material surface under aerobic conditions, material surface is made to form polymerisable carbon-carbon double bond, then material surface being connected to carbon-carbon double bond carries out free radical type graft copolymerization with the monomer solution containing initiator, select different monomer solutions and initiator to obtain different graftomer according to differing materials simultaneously, and then realization carries out modification to the physics on differing materials surface and chemical property, simultaneously because the method for modifying of functionalizing material surface provided by the invention is pure chemical solution reaction method, therefore the present invention is not only applicable to various organic polymer material, the modification of ceramic or metal material surface functionalization, and be applicable to the modification of the solid material surface functionalization to different shape, universality is extremely strong.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.Any Reference numeral in claim should be considered as the claim involved by limiting.
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 by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (11)
1. a method of modifying for functionalizing material surface, is characterized in that, its operation steps comprises:
A), Dopamine monomer is prepared,
Described step a) comprising:
A10), in reaction unit, methacrylic chloride or acrylate chloride are slowly instilled containing borax and dopamine hydrochloride and pH value is in the basic solution of 9-10, be under the condition of 0-30 DEG C in temperature, reaction 10-24 hour, obtains reaction solution;
A20), by above-mentioned steps a10) reaction solution that obtains is adjusted to the acid-reaction liquid that pH value is 2-4, and adopt extraction into ethyl acetate to be separated this acid-reaction liquid, obtain organic phase;
A30), by above-mentioned steps a20) organic phase that obtains carries out rotary evaporation, recrystallization purifying, obtains Dopamine monomer;
B), in reaction unit, material and the basic solution containing Dopamine monomer are reacted;
C), until above-mentioned steps b) described in reaction complete 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 free radical type graft copolymerization with the monomer solution containing initiator;
E), until above-mentioned steps d) described in graft copolymerization complete after, obtain the material of surface-functionalized modification, complete functionalizing material surface modification.
2. the method for modifying of functionalizing material surface as claimed in claim 1, is characterized in that, in step b) in, the pH value of described basic solution is 8-9, and described temperature of reaction is 15-45 DEG C, and the reaction times is 5-24 hour.
3. the method for modifying of functionalizing material surface as claimed in claim 1, it is characterized in that, in step b) in, the percentage concentration of the described mass/volume of Dopamine monomer in basic solution is 3-10%, and described basic solution is the San methylol Jia Wan – hydrochloride buffer aqueous solution.
4. the method for modifying of functionalizing material surface as claimed in claim 1, it is characterized in that, in steps d) in, 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 DEG C, and the reaction times is 2-6 hour.
5. the method for modifying of functionalizing material surface as claimed in claim 1, it is characterized in that, in 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.
6. the method for modifying of functionalizing material surface as claimed in claim 1, is characterized in that, in 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.
7. the method for modifying of functionalizing material surface as claimed in claim 4, 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.
8. the method for modifying of functionalizing material surface as claimed in claim 4, 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.
9. the method for modifying of functionalizing material surface as claimed in claim 4, it is characterized in that, the solvent of described vinyl monomer is selected from one or more the mixing in acetonitrile, toluene, methyl alcohol, acetone, N, N – dimethyl formamide, water.
10. the method for modifying of the functionalizing material surface as described in one of claim 1-9, is characterized in that, described material is solid-state material, and its shape is granular or membranaceous or tubulose or bar-shaped.
The method of modifying of 11. functionalizing material surfaces as described in one of claim 1-9, is characterized in that, described material is organic polymer material or ceramic or metallic substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310392347.0A CN103435830B (en) | 2013-09-02 | 2013-09-02 | A kind of method of modifying of functionalizing material surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310392347.0A CN103435830B (en) | 2013-09-02 | 2013-09-02 | A kind of method of modifying of functionalizing material surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103435830A CN103435830A (en) | 2013-12-11 |
| CN103435830B true CN103435830B (en) | 2016-03-02 |
Family
ID=49689557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310392347.0A Active CN103435830B (en) | 2013-09-02 | 2013-09-02 | A kind of method of modifying of functionalizing material surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435830B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617718A (en) * | 2014-11-03 | 2016-06-01 | 中国科学院兰州化学物理研究所 | Preparation method of hydrophobic lipophilic oil-water separation material |
| CN104744635B (en) * | 2015-04-17 | 2017-08-25 | 西安科技大学 | A kind of preparation method of pair of Biomimetic Polymers |
| 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 |
| 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 |
| KR102673133B1 (en) * | 2016-12-22 | 2024-06-10 | 헨켈 아게 운트 코. 카게아아 | Reaction products of catechol compounds and functionalized co-reactive compounds for metal pretreatment applications |
| EP3558667B1 (en) | 2016-12-22 | 2024-03-20 | Henkel AG & Co. KGaA | Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds |
| 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 |
| CN112159496B (en) * | 2020-10-13 | 2022-02-25 | 乐陵泰山人造草坪产业有限公司 | Synthetic method of artificial grass fiber surface modification functional gel |
| CN113082300B (en) * | 2021-04-06 | 2022-05-31 | 西南交通大学 | Antibacterial and anticoagulant coating, preparation method and application thereof |
| CN114106443B (en) * | 2021-12-03 | 2023-07-18 | 上海长园电子材料有限公司 | Antibacterial heat-shrinkable tube and preparation method and application thereof |
| CN114933414B (en) * | 2022-07-25 | 2022-11-08 | 西安宏星电子浆料科技股份有限公司 | Temperature sensitivity resistant LTCC insulating medium slurry |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538373B (en) * | 2009-04-08 | 2011-06-08 | 武汉理工大学 | Method for surface modification of polyurethane material by graft copolymerization |
| CN101844993B (en) * | 2010-05-21 | 2013-08-14 | 北京化工大学 | Photo-curing monomer with ortho-phenolic hydroxyl structure, preparation method and bond thereof |
| CN102504082A (en) * | 2011-10-26 | 2012-06-20 | 杭州师范大学 | Poly(propenoyl dopamine), and preparation method and application thereof |
| CN102976307A (en) * | 2012-12-04 | 2013-03-20 | 北京化工大学 | Carbon nano tube surface functionalization method |
-
2013
- 2013-09-02 CN CN201310392347.0A patent/CN103435830B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103435830A (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435830B (en) | A kind of method of modifying of functionalizing material surface | |
| CN104194026A (en) | Visible light triggered material surface graft polymerization based functional modifying method | |
| CN102229683B (en) | Preparation method of graphene based nano composite hydrogel | |
| US20100280184A1 (en) | Surface functionalisation of plastic optical fibre | |
| JP2011526577A5 (en) | ||
| CN102711978A (en) | Porous polymer monoliths, processes for preparation and use thereof | |
| TW200732445A (en) | Removable water-dispersible acrylic adhesive composition and adhesive sheet | |
| KR101831613B1 (en) | Substrate-independently surface-coated polymer using aromatic-amine compound and coating method thereof | |
| CN101735416A (en) | Method for preparing water-soluble cross-linked polymer grafted carbon nano tube | |
| CN101899132B (en) | Preparation method of polyacrylonitrile adsorbing materials | |
| CN101538373B (en) | Method for surface modification of polyurethane material by graft copolymerization | |
| CN101948823A (en) | Microorganism-embedded carrier with composite nanostructure and preparation method thereof | |
| Gallastegui et al. | Catechol-containing acrylic poly (ionic liquid) hydrogels as bioinspired filters for water decontamination | |
| Köse | Nucleotide incorporated magnetic microparticles for isolation of DNA | |
| CN105037664A (en) | Superparamagnetic advanced functional polymer monodisperse microspheres prepared by adopting swelling copolymerization method | |
| CN104262880B (en) | Antibacterial nano combined positively charged ion double-network hydrogel of a kind of high strength and preparation method thereof | |
| JP5040176B2 (en) | Microchannel device | |
| Tarannum et al. | Advances in synthesis and applications of sulfo and carbo analogues of polybetaines: a review | |
| Bal et al. | Study on adsorption, regeneration, and reuse of crosslinked chitosan graft copolymers for Cu (II) ion removal from aqueous solutions | |
| Wang et al. | Synergy of noncovalent interlink and covalent toughener for tough hydrogel adhesion | |
| CN112538131B (en) | Hydrogel bonding method, hydrogel bonded body and debonding method thereof | |
| CN107286341A (en) | A kind of method on the auto polymerization reaction preparation temperature response type surface based on dopamine | |
| TW201113380A (en) | Indium adsorbent, indium adsorbent producing method, and indium adsorption method | |
| CN109232833A (en) | A kind of preparation method of low bacterial adhesion, bacterium release and reproducible high-strength nano composite hydrogel | |
| JP2020019842A (en) | Hydrogel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170908 Address after: Suzhou City, Jiangsu province 215123 Xiangcheng District Ji Road No. 8 Patentee after: Soochow University Address before: Zhangjiagang mayor Jingyang Road Suzhou City, Jiangsu province 215600 No. 10 Patentee before: Zhangjiagang Institute of Industrial Technologies Soochow University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190521 Address after: Room 02, 2nd floor, 14 Yannan Road, Chengguan District, Lanzhou City, Gansu Province, 730010 Patentee after: Lanzhou Honghui Medical Devices Co., Ltd. Address before: 215123 No. 8 Jixue Road, Xiangcheng District, Suzhou City, Jiangsu Province Patentee before: Soochow University |
|
| TR01 | Transfer of patent right |