CN103435830A - Modification method for functionalizing surface of material - Google Patents

Abstract

The invention discloses a modification method for material surface functionalization. The operation steps include: a) preparing dopamine functional monomer; b) reacting the material with an alkaline solution containing dopamine functional monomer in a reaction device; c) After the reaction described in the above step b) is completed, the material with carbon-carbon double bonds on the surface is obtained; d) In the reaction device, the material with carbon-carbon double bonds on the surface obtained in the above step c) is combined with the material containing The monomer solution of the initiator is subjected to a free radical graft copolymerization reaction; e) After the graft copolymerization reaction described in the above step d) is completed, a material with surface functional modification is obtained, and the surface functional modification of the material is completed , the present invention is easy to operate and has strong universal applicability.

Description

A modification method for material surface functionalization

technical field

The invention relates to material modification technology, in particular to a modification method for material surface functionalization.

Background technique

Polymer materials, inorganic non-metallic and metallic materials are widely used in human activities, and it is of great significance to precisely control the physical and chemical properties of the surface of these materials in the fields of materials science, chemistry and biotechnology. For example: the sensitivity of a biosensing chip mainly depends on the chemical properties of the chip surface; the surface properties of medical devices and drug delivery carriers determine their biocompatibility and therapeutic effect; the type and size of molecules bound to the surface of nanomaterials determine the size and shape etc. Under normal circumstances, the material surface itself often does not have the required specific chemical properties. Therefore, functional modification of the material surface to obtain a material surface with specific chemical properties has become an important measure to promote the development of applications in the fields of materials and devices.

However, most existing modification strategies often involve multi-step reactions and only target a certain material, and for materials lacking functional groups on the surface, they must first be subjected to plasma, ozone oxidation, γ-ray irradiation, electron beam or laser irradiation. and so on, so as to introduce functional groups on the surface of the material and carry out functional modification on the surface of the material. These modification methods not only require more expensive special equipment, but also are more complicated to operate, difficult to control process parameters, and not universal.

The prior art closest to the present invention is the Chinese patent with the publication number CN101538373A, which discloses a method for copolymerization and graft modification of the surface of polyurethane materials, in which polymerizable carbon is chemically attached to the surface of polyurethane materials. Carbon double bonds, in the presence of initiators and vinyl monomers, graft and modify the surface of polyurethane materials through free radical graft copolymerization, but because the patent uses acryloyloxyisothiocyanate solution and methyl The acryloxyisothiocyanate solution acts on the surface of the polyurethane material to achieve a carbon-carbon double bond on the surface of the polyurethane material. Although this method solves the problem of surface improvement of the polyurethane material, as mentioned above, it is only for the polyurethane material. , still cannot be used for surface modification of other kinds of materials.

Since the various improvement technologies disclosed at present can only realize the surface modification technology of a specific single material, this obviously greatly restricts the popularization and application of the surface improvement technology. , A universal modification method for surface functionalization of materials.

Contents of the invention

The purpose of the present invention is to provide a modification method for material surface functionalization, which is easy to operate and strong in universal applicability.

Before proposing the technical solution of the present invention, based on the applicant's professional knowledge in the field of material surface functional modification technology and years of research and development experience, it was found that it is necessary to obtain a modification of material surface functionalization that is easy to operate and has universal applicability. In order to create a radical method, first of all, it is necessary to obtain a universal reaction that can generate free radicals on the surface of materials, so as to facilitate the creation of free radical graft copolymerization reactions. After theoretical research and combined with experiments, it was found that dopamine functional monomer Under aerobic conditions, it will interact with the material, so that the surface of the material is connected with a polymerizable carbon-carbon double bond. Therefore, it is a feasible solution to generate free radicals on the surface of the material with universality.

However, the use of dopamine in the current prior art is still limited to forming a composite layer with strong adhesion on specific materials, such as the Chinese patent with publication number CN102614783A, which improves the anti-pollution or hydrophilic ability of the material through the composite layer. Obviously, the use of dopamine is still relatively limited, and at the same time, it is not universal. After a lot of experiments, the applicant proposed the technical solution of the present invention. Please refer to the following for details.

According to the modification method of a kind of material surface functionalization that object of the present invention proposes, its operation step comprises:

a), preparation of dopamine functional monomer;

b) In the reaction device, the material is reacted with an alkaline solution containing dopamine functional monomer;

c), after the reaction described in the above step b) is completed, a material with a carbon-carbon double bond attached to the surface is obtained;

d) In the reaction device, the material with carbon-carbon double bonds on the surface obtained in the above step c) is subjected to free radical graft copolymerization with the monomer solution containing the initiator;

e) After the graft copolymerization reaction described in the above step d) is completed, a material with surface functional modification is obtained, and the surface functional modification of the material is completed.

Preferably, said step a) includes:

a10), in the reaction device, slowly drop methacryloyl chloride or acryloyl chloride into an alkaline solution containing borax and dopamine hydrochloride and having a pH value of 9-10, at a temperature of 0-30°C Next, react for 10-24 hours to obtain a reaction solution;

a20), adjusting the reaction solution obtained in the above step a10) to an acidic reaction solution with a pH value of 2-4, and extracting and separating the acidic reaction solution with ethyl acetate to obtain an organic phase;

a30), the organic phase obtained in the above step a20) is subjected to rotary evaporation, recrystallization and purification to obtain the dopamine functional monomer.

Preferably, in step b), the pH of the alkaline solution is 8-9, the reaction temperature is 15-45°C, and the reaction time is 5-24 hours.

Preferably, in step b), the mass/volume percentage concentration of the dopamine functional monomer in the alkaline solution is 3-10%, and the alkaline solution is tris-hydrochloric acid buffered aqueous solution.

Preferably, in step d), the monomer solution is a vinyl monomer solution, the mass molar ratio of the initiator to the vinyl monomer is 1:100-1:400, and the reaction temperature The temperature is 60-80°C, and the reaction time is 2-6 hours.

Preferably, in step a10), the mass molar ratio of methacryloyl chloride or acryloyl chloride to dopamine hydrochloride is 1:1-1:1.2, and the mass molar ratio of borax to dopamine hydrochloride 1:1-1:1.2, the alkaline solution is an alkaline aqueous solution.

Preferably, in step a20), hydrochloric acid is used to adjust the reaction solution obtained in step a10) to an acidic reaction solution with a pH value of 2-4.

Preferably, the vinyl monomer is selected from oligoethylene glycol methacrylate, acrylic acid, methacrylic acid, (2-hydroxy) ethyl methacrylate, N-vinylpyrrolidone, methacrylic acid shrink A mixture of one or more of glycerol esters, (N,N-dimethylamino)ethyl methacrylate, and N-isopropylacrylamide.

Preferably, the initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanonitrile, dibenzoyl peroxide, diethylhexyl peroxydicarbonate, cumene hydroperoxide, persulfuric acid A mixture of one or more of the potassium-sulfite system or the hydrogen peroxide-ferrite system.

Preferably, the solvent of the vinyl monomer solution is selected from a mixture of one or more of acetonitrile, toluene, methanol, acetone, N,N-dimethylformamide, and water.

Preferably, the material is a solid material, and its shape is granular or film-like or tube-like or rod-like.

Preferably, the material is an organic polymer material or an inorganic non-metal material or a metal material.

It should also be noted that the range of reaction temperature, the range of reaction time and the pH range of the reaction solution or solution involved in the present invention are all preferred reaction parameter ranges. Undoubtedly, adopting the preferred reaction parameter range in the present invention Within or within the range of similar parameters, all should be regarded as the same or equivalent technical effects, and all belong to the scope of protection of the present invention.

The present invention reacts the alkaline solution containing the dopamine functional monomer with the material so that polymerizable carbon-carbon double bonds can be connected to the surface of various materials including organic polymer materials, inorganic non-metallic materials or metal materials, and then Mix the material with carbon-carbon double bond on the surface with the initiator-monomer mixed solution. The initiator first makes the carbon-carbon double bond generate free radicals, and then under the action of free radicals, the surface of the material is grafted with the monomer The copolymerization reaction is used to realize the surface functional modification of the material. The present invention can change the physical and/or chemical characteristics of the material surface according to the properties of the grafted polymer, such as grafting poly(N-iso When using propyl) acrylamide, a material surface with high temperature sensitivity can be obtained; when polyacrylic acid is grafted on the material surface, a material surface with high pH value sensitivity can be obtained, and the universality is extremely strong; in addition, the material provided by the invention The modification method of surface functionalization is a pure chemical solution reaction method, which does not need to use more expensive special equipment such as ion plasma and ozone generator to obtain surface functional groups as in the prior art, for some materials lacking functional groups on the surface. The invention is simple to operate, the process parameters are easier to control and the implementation cost is low, and at the same time, the invention can perform good modification on the surface functionalization of solid materials of various shapes, so the invention is very suitable for surface functional modification of various materials Large-scale promotion and application.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments described in the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.

Fig. 1 is a comparison chart of the surface hydrophilic properties of the unmodified polyvinyl chloride diaphragm and the polyvinyl chloride diaphragm modified by Example 4 of the present invention.

Detailed ways

The embodiment of the present invention discloses a modification method for material surface functionalization, the operation steps of which include:

a), preparation of dopamine functional monomer;

b) In the reaction device, the material is reacted with an alkaline solution containing dopamine functional monomer;

c), after the reaction of the above step b) is completed, a material with a carbon-carbon double bond on the surface is obtained;

d) In the reaction device, the material with carbon-carbon double bonds on the surface obtained in the above step c) is subjected to free radical graft copolymerization with the monomer solution containing the initiator;

e) After the graft copolymerization reaction in the above step d) is completed, a material with surface functional modification is obtained, and the surface functional modification of the material is completed.

In the embodiment of the present invention, polymerizable carbon-carbon double bonds can be attached to the surface of various materials including organic polymer materials, inorganic non-metallic materials or metal materials through the reaction of alkaline solutions containing dopamine functional monomers and materials , and then mix the material with carbon-carbon double bonds on the surface with the initiator-monomer mixed solution, the initiator first makes the carbon-carbon double bonds generate free radicals, and then under the initiation of free radicals, the surface of the material and the monomers are formed. graft copolymerization reaction to realize the surface functional modification of the material, the embodiment of the present invention can change the physical and/or chemical characteristics of the material surface according to the performance of the grafted polymer, such as grafting on the material surface according to the embodiment of the present invention When grafting poly(N-isopropyl) acrylamide, a material surface with high temperature sensitivity can be obtained; when polyacrylic acid is grafted on the material surface, a material surface with high pH sensitivity can be obtained, which is extremely universal; in addition The modification method of material surface functionalization provided by the embodiment of the present invention is a pure chemical solution reaction method, which does not require the use of more expensive special equipment such as ion plasma and ozone generator as in the prior art for some materials lacking functional groups on the surface Treatment is performed to obtain surface functional groups, so the embodiment of the present invention is simple to operate, the process parameters are easier to control, and the implementation cost is low. At the same time, the embodiment of the present invention can perform good modification on the surface functionalization of solid materials of various shapes. Therefore, the present invention The embodiment of the invention is very suitable for large-scale popularization and application in the surface function modification of various materials.

In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described The embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

Example 1: Functional modification of glass slide surface temperature sensitivity

a), preparation of dopamine functional monomer:

a10), 3.83g of borax, 1.9g of dopamine hydrochloride, and 100mL of water were placed in a 250mL reaction device, stirred and dissolved, and the pH value was adjusted to 9-10 with aqueous sodium carbonate;

Slowly drop 1.05 g of methacryloyl chloride into the reaction device, and stir and react for 24 hours at room temperature to obtain a reaction solution;

a20), using concentrated hydrochloric acid to adjust the reaction solution obtained in the above step a10) to an acidic reaction solution with a pH value of 2, use ethyl acetate to extract and separate the acidic reaction solution, the number of extractions is selected for 3 times, and of course 4 times or More than 4 times, the organic phases obtained by each extraction were combined to obtain the organic phase;

a30), the organic phase obtained in the above step a20) is dried over anhydrous magnesium sulfate, and then subjected to vacuum rotary evaporation to remove ethyl acetate to obtain a crude product, which is then purified by recrystallization from a mixed solvent of ethyl acetate/methanol to obtain dopamine function monomer;

b) In the reaction device, mix 30 glass slides (thickness: 0.7 mm) with a length and width of 0.5 cm and tris-hydrochloric acid buffer containing dopamine functional monomers with a pH value of 8.5 The aqueous solution was stirred and reacted for 20 hours at room temperature, wherein the mass/volume concentration of the dopamine functional monomer in tris-hydrochloric acid buffered aqueous solution was 5%;

c), after the reaction described in the above step b) is completed, take out the glass slide, wash with deionized water and dry to obtain a glass slide with carbon-carbon double bond on the surface;

d) Mix the 20 glass slides with carbon-carbon double bonds on the surface obtained in the above step c) with an initiator-ethylene composed of 0.028g of azobisisobutyronitrile, 2.26g of N-isopropylacrylamide, and 15mL of methanol. The mixed solution of radical monomers was placed in a 50mL reaction device together, under the conditions of nitrogen gas protection atmosphere, stirring, and heating to 65°C and keeping warm, the free radical graft copolymerization reaction was carried out, and the reaction time was 6 hours;

e) After the graft copolymerization reaction described in the above step d) is completed, the glass slide is taken out, washed with methanol and water and dried to obtain poly(N-isopropyl)acrylamide with high surface temperature sensitivity Graft modified glass slides to complete the functional modification of the temperature sensitivity of the glass slide surface.

Embodiment 2: the functional modification of antibacterial performance on the surface of stainless steel sheet

a), preparation of dopamine functional monomer:

a10), 3.83g of borax, 1.9g of dopamine hydrochloride, and 100mL of water were placed in a 250mL reaction device, stirred and dissolved, and the pH value was adjusted to 9-10 with aqueous sodium carbonate;

Slowly drop 1.05 g of methacryloyl chloride into the reaction device, and stir and react for 24 hours at room temperature to obtain a reaction solution;

a20), using concentrated hydrochloric acid to adjust the reaction solution obtained in the above step a10) to an acidic reaction solution with a pH value of 2, use ethyl acetate to extract and separate the acidic reaction solution, the number of extractions is selected for 3 times, and of course 4 times or More than 4 times, the organic phases obtained by each extraction were combined to obtain the organic phase;

a30), the organic phase obtained in the above step a20) is dried over anhydrous magnesium sulfate, and then subjected to vacuum rotary evaporation to remove ethyl acetate to obtain a crude product, which is then purified by recrystallization from a mixed solvent of ethyl acetate/methanol to obtain dopamine function monomer;

b) In the reaction device, 10 pieces of stainless steel sheets (thickness: 1.0 mm) with a length and width of 1.0 cm were mixed with tris-hydrochloric acid buffer containing dopamine functional monomer and pH value of 8.5 The aqueous solution was stirred and reacted for 20 hours at room temperature, wherein the mass/volume concentration of the dopamine functional monomer in tris-hydrochloric acid buffered aqueous solution was 5%;

c), after the reaction described in the above step b) is completed, the stainless steel sheet is taken out, washed with deionized water and dried to obtain a stainless steel sheet with a carbon-carbon double bond on the surface;

d) Mix the 5 stainless steel sheets with carbon-carbon double bonds on the surface obtained in the above step c) with 0.028g of azobisisobutyronitrile, 3mL of (N,N-dimethylamino)ethyl methacrylate, and 20mL of methanol The mixed solution of the initiator-vinyl monomer formed together is placed in a 50mL reaction device, under the conditions of nitrogen gas protection atmosphere, stirring, and heating to 65°C and heat preservation, the free radical graft copolymerization reaction is carried out, and the reaction The time is 6 hours;

e) After the graft copolymerization reaction described in the above step d) is completed, the stainless steel sheet is taken out, washed with methanol and water and dried to obtain poly(N,N-dimethylamino)ethyl methacrylate grafted After further quaternization, the stainless steel sheet with good antibacterial performance can be obtained, and the functional modification of the antibacterial performance of the surface of the stainless steel sheet can be completed.

Example 3: Functional Modification of Surface pH Sensitivity of Polyurethane Tubes

a), preparation of dopamine functional monomer:

a10), 3.83g of borax, 1.9g of dopamine hydrochloride, and 100mL of water were placed in a 250mL reaction device, stirred and dissolved, and the pH value was adjusted to 9-10 with aqueous sodium carbonate;

Slowly drop 1.05 g of methacryloyl chloride into the reaction device, and stir and react for 24 hours at room temperature to obtain a reaction solution;

a20), using concentrated hydrochloric acid to adjust the reaction solution obtained in the above step a10) to an acidic reaction solution with a pH value of 2, use ethyl acetate to extract and separate the acidic reaction solution, the number of extractions is selected for 3 times, and of course 4 times or More than 4 times, the organic phases obtained by each extraction were combined to obtain the organic phase;

a30), the organic phase obtained in the above step a20) is dried over anhydrous magnesium sulfate, and then subjected to vacuum rotary evaporation to remove ethyl acetate to obtain a crude product, which is then purified by recrystallization from a mixed solvent of ethyl acetate/methanol to obtain dopamine function monomer;

b) In the reaction device, 10 polyurethane tubes with a length of 1 cm and an inner diameter of 5 mm were reacted with tris-hydrochloric acid buffered aqueous solution containing dopamine functional monomer and having a pH value of 8.5 at room temperature 20 hours, wherein, the mass/volume percentage concentration of dopamine functional monomer in tris-hydrochloric acid buffered aqueous solution is 5%;

c) After the reaction described in the above step b) is completed, the polyurethane tube is taken out, washed with deionized water and dried to obtain a polyurethane tube with a carbon-carbon double bond on the surface;

d) A mixed solution of initiator-vinyl monomer composed of 8 polyurethane tubes with carbon-carbon double bonds on the surface obtained in the above step c), 0.040g of dibenzoyl peroxide, 1.4mL of acrylic acid, and 15mL of acetone Put them together in a 25mL reaction device, and carry out free radical graft copolymerization reaction under the conditions of nitrogen gas protection atmosphere, stirring, heating to 70°C and keeping warm, and the reaction time is 3 hours;

e) After the graft copolymerization reaction in the above step d) is completed, the polyurethane tube is taken out, washed with water and dried to obtain a polyacrylic acid graft-modified polyurethane tube with high surface pH sensitivity, and the completion Functional modification of the surface pH sensitivity of polyurethane tubing.

Embodiment 4: Functional modification of the hydrophilic properties of the surface of polyvinyl chloride membrane

a), preparation of dopamine functional monomer:

a10), 3.83g of borax, 1.9g of dopamine hydrochloride, and 100mL of water were placed in a 250mL reaction device, stirred and dissolved, and the pH value was adjusted to 9-10 with aqueous sodium carbonate;

Slowly drop 1.05 g of methacryloyl chloride into the reaction device, and stir and react for 24 hours at room temperature to obtain a reaction solution;

a20), using concentrated hydrochloric acid to adjust the reaction solution obtained in the above step a10) to an acidic reaction solution with a pH value of 2, use ethyl acetate to extract and separate the acidic reaction solution, the number of extractions is selected for 3 times, and of course 4 times or More than 4 times, the organic phases obtained by each extraction were combined to obtain the organic phase;

a30), the organic phase obtained in the above step a20) is dried over anhydrous magnesium sulfate, and then subjected to vacuum rotary evaporation to remove ethyl acetate to obtain a crude product, which is then purified by recrystallization from a mixed solvent of ethyl acetate/methanol to obtain dopamine function monomer;

b) In the reaction device, 30 pieces of polyvinyl chloride diaphragms with a diameter of about 5 mm (thickness 0.5 mm) were mixed with tris-hydrochloric acid buffer containing dopamine functional monomers and having a pH value of 8.5 The aqueous solution was stirred and reacted for 20 hours at room temperature, wherein the mass/volume concentration of the dopamine functional monomer in tris-hydrochloric acid buffered aqueous solution was 5%;

c), after the reaction described in the above step b) is completed, the polyvinyl chloride diaphragm is taken out, washed with deionized water and dried to obtain a polyvinyl chloride diaphragm with a carbon-carbon double bond on the surface;

d) Initiator composed of 20 pieces of polyvinyl chloride diaphragms with carbon-carbon double bonds on the surface obtained in the above step c) and 0.028g of azobisisobutyronitrile, 2.22g of N-vinylpyrrolidone, and 15mL of methanol- The mixed solution of vinyl monomers is placed in a 50mL reaction device together, under the conditions of nitrogen gas protection atmosphere, stirring, and heating to 65°C and keeping warm, carry out free radical graft copolymerization reaction, and the reaction time is 5 hours;

e) After the graft copolymerization reaction described in the above step d) is completed, the polyvinyl chloride diaphragm is taken out, washed with methanol and water and dried to obtain a polyvinylpyrrolidone graft modified polyvinylpyrrolidone with good hydrophilic properties on the surface. Permanent polyvinyl chloride diaphragm, complete the functional modification of the surface hydrophilic properties of polyvinyl chloride diaphragm.

As shown in Figure 1, the surface static water contact angle α1 of the unmodified polyvinyl chloride diaphragm 1 is about 78°, while the surface static water contact angle α2 of the polyvinylpyrrolidone modified polyvinyl chloride diaphragm 2 is about It is 30°, so it can be further explained that the surface of the polyvinyl chloride diaphragm obtained through the modification of Example 4 of the present invention has very good hydrophilic properties.

In summary, the functional modification method of the present invention uses an alkaline solution containing dopamine functional monomer to act on the surface of the material under aerobic conditions, so that the surface of the material forms a polymerizable carbon-carbon double bond, and then contacts the surface Materials with carbon-carbon double bonds are subjected to free radical graft copolymerization with monomer solutions containing initiators, and different monomer solutions and initiators are selected according to different materials to obtain different graft polymers, thereby realizing Modify the physical and/and chemical properties of the surface of different materials, and because the modification method of the material surface functionalization provided by the present invention is a pure chemical solution reaction method, the present invention is not only applicable to various organic polymer materials , The modification of the surface functionalization of inorganic non-metallic materials or metal materials, and it is suitable for the modification of the surface functionalization of solid materials of various shapes, with strong universality.

It will be apparent to those skilled in the art that the invention is not limited to the details of the above-described exemplary embodiments, but that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Accordingly, the embodiments should be regarded in all points of view as exemplary and not restrictive, the scope of the invention being defined by the appended claims rather than the foregoing description, and it is therefore intended that the scope of the invention be defined by the appended claims rather than by the foregoing description. All changes within the meaning and range of equivalents of the elements are embraced in the present invention. Any reference sign in a claim should not be construed as limiting the claim concerned.

In addition, it should be understood that although this specification is described according to implementation modes, not each implementation mode only contains an independent technical solution, and this description in the specification is only for clarity, and those skilled in the art should take the specification as a whole , the technical solutions in the various embodiments can also be properly combined to form other implementations that can be understood by those skilled in the art.

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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