CN111777787A - Preparation method and application of surface functionalization of 3D structure - Google Patents
Preparation method and application of surface functionalization of 3D structure Download PDFInfo
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Abstract
The invention discloses a preparation method and application of surface functionalization of a 3D structure, wherein the preparation method comprises the following steps: performing vinylation treatment to obtain a 3D structure with a surface modified with double bonds; and secondly, carrying out double bond-mercaptan click chemical reaction to obtain the 3D structure with the functionalized surface. The application is the application of the functionalized 3D structure in surface hydrophilicity and hydrophobicity, surface antibiosis and surface metal deposition. The preparation method is rapid, various active groups can be endowed on the surface of the 3D structure, the material does not depend on functional groups carried by the material, the effect can be achieved on most materials, and no additional micro-nano structure can be formed on the surface of the material; the preparation method has simple reaction conditions and quick reaction, realizes the functionalization of 3D structures with different scales and sizes within a few minutes, has strong universality and can be used for large-scale production.
Description
Technical Field
The invention belongs to the field of functionalized structures, and particularly relates to a preparation method and application of surface functionalization of a 3D structure.
Background
3D printing is one of the rapid prototyping techniques, also known as additive manufacturing, which is a technique of building objects by layer-by-layer printing or 3D direct writing, based on digital model files, from inorganic powders or polymer pre-polymerized liquids, etc. as materials. Is a very popular 3D structure processing means in the current society.
Among the many methods of 3D printing, two-photon lithography is a very promising approach. The femtosecond pulsed laser is focused by an optical element into a photosensitive resin that can be crosslinked (negative photoresist) or degraded (positive photoresist) under high-energy illumination. If the laser energy is sufficiently high, the resin may undergo two-photon (or multi-photon) absorption (or polymerization). This phenomenon of multiphoton absorption is nonlinear, and the probability of occurrence is proportional to the square (or higher) of the intensity of the excitation light. The area where light is converged can be limited to one point (the focus of laser) in a three-dimensional space, a three-dimensional structure can be directly written by continuously moving the focus, the resolution ratio of hundreds of nanometers can be achieved, and the printing precision is greatly improved. Besides polymer resins, two-photon lithography is also expected to be used for 3D printing of many materials such as glass, metal, ceramics, and the like.
Although two-photon lithography can create complex structures quickly, the chemical functionality of the 3D structure surface is greatly limited due to the small amount of photoresist that can be used. In order to further expand the application field of 3D structures, it is important to find a rapid and universal surface functional modification method.
Common methods for constructing functional 3D structures are: modifying and synthesizing functional photoresist by utilizing residual groups on the surface of the structure, and the like. The method of modifying with surface residual groups is often limited to residual groups with lower density on the polymer surface, and it is difficult to increase the density of the desired functional groups. The method has the advantages that the corresponding functionalized photoresist is directly synthesized, and the functional component is introduced into the photoresist, so that the method generally has higher functional density, but in general, the functional component is introduced into the photoresist, and the material strength, printing precision or printing speed and other material properties of the photoresist are often reduced. The general commercial photoresist has balanced performances in all aspects, but the composition is not disclosed, and the material composition is various, which makes great hindrance to the development of the surface modification technology.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide a preparation method for surface functionalization of a 3D structure, which has strong universality, is simple and rapid, and can be applied to large-scale production, and the invention also aims to provide application of the functionalized 3D structure in surface hydrophilicity and hydrophobicity, surface antibiosis and surface metal deposition.
The technical scheme is as follows: the invention relates to a preparation method for surface functionalization of a 3D structure, which comprises the following steps:
step one, vinylation treatment: respectively adding a catalyst, double bond silane and a neutralizing agent into the first solvent to prepare a silane solution, completely immersing the 3D structure into the prepared silane solution, stirring for 5-10 min, washing the 3D structure with ethanol or acetone, and drying with nitrogen to obtain a 3D structure with a surface modified with double bonds, wherein the 3D structure has strong universality;
step two, double bond-thiol click chemistry reaction: respectively adding a photoinitiator and mercaptan into a second solvent to prepare a mercaptan solution, immersing the 3D structure with the surface modified with double bonds obtained in the first step into the mercaptan solution, standing, reacting for 5-10 s under ultraviolet light, washing with ethanol or acetone, and drying with nitrogen to obtain the 3D structure with the functionalized surface. Such as the structure of surface modified perfluoro group, hydroxyl, alkyl, carboxyl, amino, polyethylene glycol group, etc.
Wherein the catalyst is 4-dimethylamino pyridine, the double-bond silane is vinyl trichlorosilane, the neutralizing agent is triethylamine, and the first solvent is dichloromethane. The mass of the catalyst is 23.9-26.5 mg, and the mass ratio of the double bond silane, the neutralizer and the solvent I is 13-25: 14-29: 2399-3310.
The 3D structure is a photoresist structure obtained by stereolithography 3D printing, and the 3D structure is made of any one of titanium alloy, hydroxyapatite, glass and nylon.
The photoinitiator is benzoin dimethyl ether, the mercaptan is any one of 1H, 1H, 2H, 2H-perfluorodecanethiol, n-dodecanethiol, mercaptoethanol, 3-mercaptopropionic acid, beta-mercaptoethylamine, cysteamine hydrochloride and methoxypolyethylene glycol mercapto, and the solvent II is toluene or DMF. The mass of the photoinitiator is 0.5-1 mg, and the mass ratio of the mercaptan to the second solvent is 10-20: 87.
The application of the functionalized 3D structure in surface hydrophilic and hydrophobic water.
Application of the functionalized 3D structure in surface antibiosis.
Use of a functionalized 3D structure in cell culture.
The preparation principle is as follows: the vinyltrichlorosilane used in the preparation method has high reactivity and can react with a plurality of groups such as hydroxyl, carboxyl, amino and the like. Most photoresist materials have a certain amount of active groups on the surface, and the active groups are easy to react with vinyl trichlorosilane to graft double bonds. For a few photoresist materials with inert surfaces, active groups such as hydroxyl, carboxyl and the like can be grafted in a simple surface oxygen plasma treatment mode, and then the reactive groups react with vinyl trichlorosilane to graft double bonds, so that the method has strong universality. After the double bond grafting is successful, any required functional group can be grafted by a mercapto-vinyl click chemical reaction.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the preparation is rapid, various active groups can be endowed on the surface of a 3D structure, the material does not depend on functional groups carried by the material, the effect can be achieved on most materials, and an additional micro-nano structure cannot be formed on the surface of the material;
2. the preparation method has the advantages of simple reaction conditions, quick reaction, low cost, higher modification density than the reported method, wide application, realization of functionalization of 3D structures of different materials with different scales in a few minutes, endowment of the structures with various chemical functionalities, strong universality and capability of large-scale production.
Drawings
FIG. 1 is a schematic diagram of the preparation of the present invention, wherein a is a 3D printing structure, b is a vinyl structure, and c is a functionalized structure;
FIG. 2 is a diagram of a water droplet supported by the hydrophilic-hydrophobic columnar array of the present invention, wherein a is a non-modified structure, b is a structure obtained by modifying a hydroxyl group on the surface, and c is a structure obtained by modifying a perfluorocarbon chain group on the surface;
FIG. 3 is a physical diagram of the polymer sheet after copper deposition, wherein a is the deposition effect of the polymer sheet without modification before metal deposition, c is the deposition effect of the polymer sheet modified by cysteamine hydrochloride, and d is the deposition effect of the polymer sheet modified by dodecyl mercaptan;
FIG. 4 is a drawing of the antibacterial modified object on the surface of the polymer sheet of the present invention, wherein a is no modification, and b is modified with mercaptoethylamine.
Detailed Description
In the following examples, the raw materials were purchased and used as received. The 3D structure is a photoresist structure obtained by stereolithography 3D printing, the 3D structure comprises but is not limited to a photosensitive resin structure, a titanium alloy structure, a hydroxyapatite structure, a nylon structure, a glass structure and the like, and the universality is high.
Example 1
As shown in fig. 1, the preparation method of the 3D structure surface functionalization comprises the following steps:
(1) treatment of double bond silane: under the environment of a fume hood, respectively adding 25.63mg of 4-dimethylaminopyridine, 0.13g of vinyltrichlorosilane, 0.15g of triethylamine and 33.1g of dichloromethane into a centrifuge tube or other closed containers, stirring to prepare a double-bond silane solution, completely immersing the columnar array printed by the IP-S photoresist into the silane solution, stirring for 5min, slightly washing by using ethanol, and drying by using nitrogen to obtain the columnar array with the surface modified with double bonds;
(2) thiol-olefin click chemistry: respectively adding 4.88mg of benzoin dimethyl ether and 0.17g of 1H, 1H, 2H, 2H-perfluorodecanethiol or 0.18g of mercaptoethanol into 0.87g of toluene to prepare a mercaptan solution, then soaking the double-bond columnar array obtained in the step (1) in the mercaptan solution, turning on an ultraviolet irradiation system and placing the structure under ultraviolet light for reaction for 10s, then turning off the ultraviolet irradiation system and taking out the structure;
(3) cleaning: and washing with ethanol and drying with nitrogen to obtain the functionalized columnar array, wherein the structure modified by the perfluorinated decyl mercaptan shows high hydrophobicity, and the structure modified by the mercaptoethanol shows good hydrophilicity.
The prepared functionalized columnar array can be applied to the field of droplet control, the hydrophilicity and hydrophobicity of the surface of the structure are controlled, as shown in fig. 2, the hydroxyl modified columnar array (fig. 2b) is immersed in the droplets, and the perfluoro modified columnar array (fig. 2c) can support the droplets.
Example 2
(1) Treatment of double bond silane: under the environment of a fume hood, respectively adding 33.1g of dichloromethane, 24.33mg of 4-dimethylaminopyridine, 0.18g of triethylamine and 0.16g of vinyl trichlorosilane into a centrifuge tube or other closed container, stirring to prepare a double-bond silane solution, completely immersing the IP-L780 photoresist 3D structure with a proper size into the silane solution, stirring for 6min, washing with ethanol and drying with nitrogen to obtain the IP-L780 photoresist 3D structure with double bonds modified on the surface;
(2) thiol-olefin click chemistry: respectively adding 5.2mg of benzoin dimethyl ether and 0.1g of n-dodecyl mercaptan into 0.87g of toluene to prepare a mercaptan solution, then dropwise adding the mercaptan solution onto the double-bond structure obtained in the step (1) to completely immerse the structure, opening an ultraviolet irradiation system and placing the structure under ultraviolet light for reacting for 6s, then closing the ultraviolet irradiation system and taking out the structure;
(3) cleaning: washing with ethanol and blowing with nitrogen to obtain the final productFunctionalization C12Modification or ammonium salt modification of the IP-L780 structure.
The prepared functionalized IP-L780 structure can be applied to the field of metal deposition, as shown in FIG. 3, FIG. 3a shows that before metal deposition, metal copper deposition is not uniform on a non-modified surface (FIG. 3b), metal copper deposition is uniform on a cysteamine hydrochloride-modified IP-L780 material surface (FIG. 3c), and metal copper deposition is not on an n-dodecyl mercaptan-modified surface (FIG. 3 d).
Wherein 0.1g of n-dodecyl mercaptan in step (2) may be replaced with 0.1g of cysteamine hydrochloride.
Example 3
(1) Treatment of double bond silane: under the environment of a fume hood, respectively adding 33.1g of dichloromethane, 23.99mg of 4-dimethylaminopyridine, 0.22g of triethylamine and 0.19g of vinyltrichlorosilane into a centrifuge tube or other closed container, stirring to prepare a double-bond silane solution, completely immersing an IP-Dip photoresist structure with a proper size into the silane solution, stirring for 7min, washing the structure with ethanol, and drying with nitrogen to obtain a structure with a surface modified with double bonds;
(2) thiol-olefin click chemistry: respectively adding 5.33mg of benzoin dimethyl ether and 0.13g of mercaptoethanol into 0.87g of toluene to prepare a mercaptan solution, then dropwise adding the mercaptan solution onto the double-bond structure obtained in the step (1) to completely immerse the structure, opening an ultraviolet irradiation system, placing the structure under ultraviolet light for reaction for 7s, then closing the ultraviolet irradiation system and taking out the structure;
(3) cleaning: and washing with ethanol and drying with nitrogen to obtain the functionalized hydroxyl IP-Dip structure with hydrophilic surface.
The prepared functionalized hydroxyl IP-Dip structure can be applied to the field of cell culture.
Example 4
(1) Treatment of double bond silane: under the environment of a fume hood, respectively adding 33.1g of dichloromethane, 26.12mg of 4-dimethylaminopyridine, 0.25g of triethylamine and 0.22g of vinyltrichlorosilane into a centrifuge tube or other closed container, stirring to prepare a double-bond silane solution, completely immersing a titanium alloy 3D structure with a proper size into the silane solution, stirring for 8min, washing with ethanol, and drying with nitrogen to obtain a titanium alloy structure with a surface modified with double bonds;
(2) thiol-olefin click chemistry: respectively adding 5.36mg of benzoin dimethyl ether and 0.16g of 3-mercaptopropionic acid into 0.87g of toluene to prepare a mercaptan solution, then dropwise adding the mercaptan solution onto the double-bond structure obtained in the step (1) to completely immerse the structure, opening an ultraviolet irradiation system and placing the structure under ultraviolet light for reacting for 8s, then closing the ultraviolet irradiation system and taking out the structure;
(3) cleaning: and washing with ethanol and drying with nitrogen to obtain the functionalized carboxyl titanium alloy structure.
The prepared functionalized carboxyl titanium alloy structure can be applied to the field of cell culture.
Example 5
(1) Treatment of double bond silane: under the environment of a fume hood, respectively adding 33.1g of dichloromethane, 25.63mg of 4-dimethylaminopyridine, 0.29g of triethylamine and 0.25g of vinyltrichlorosilane into a centrifuge tube or other closed container, stirring to prepare a double-bond silane solution, completely immersing a hydroxyapatite 3D structure with a proper size into the silane solution, stirring for 9min, washing with ethanol, and drying with nitrogen to obtain a hydroxyapatite structure with a surface modified with double bonds;
(2) thiol-olefin click chemistry: respectively adding 4.79mg of benzoin dimethyl ether and 0.16g of beta-mercaptoethylamine into 0.87g of toluene to prepare a mercaptan solution, then dropwise adding the mercaptan solution onto the double-bond structure obtained in the step (1) to completely immerse the structure, opening an ultraviolet irradiation system and placing the structure under ultraviolet light for reaction for 9s, then closing the ultraviolet irradiation system and taking out the structure;
(3) cleaning: and washing with ethanol and drying with nitrogen to obtain the functionalized amino hydroxyapatite structure.
The prepared functionalized amino-hydroxyapatite structure can be applied to the fields of bacterial adhesion and cell culture, and as shown in figure 4, the surface of the material modified with ethylamine has no escherichia coli adhesion, and the surface of the material without modification has escherichia coli adhesion.
Example 6
(1) Treatment of double bond silane: under the environment of a fume hood, respectively adding 33.1g of dichloromethane, 26.25mg of 4-dimethylaminopyridine, 0.14g of triethylamine and 0.13g of vinyltrichlorosilane into a centrifuge tube or other closed container, stirring to prepare a double-bond silane solution, completely immersing a nylon 3D structure with a proper size into the silane solution, stirring for 10min, washing the structure with ethanol, and drying the structure with nitrogen to obtain a nylon structure with a surface modified with double bonds;
(2) thiol-olefin click chemistry: respectively adding 4.66mg of benzoin dimethyl ether and 0.2g of methoxy polyethylene glycol sulfydryl into 0.87g of toluene to prepare a mercaptan solution, then dropwise adding the mercaptan solution onto the double-bond structure obtained in the step (1) to completely immerse the structure, opening an ultraviolet irradiation system and placing the structure under ultraviolet light for reaction for 10s, then closing the ultraviolet irradiation system and taking out the structure;
(3) cleaning: and washing with ethanol and drying with nitrogen to finally obtain the functionalized polyethylene glycol anti-fouling nylon 3D structure with hydrophilic surface.
The prepared functionalized polyethylene glycol anti-fouling nylon structure can be applied to the fields of anti-fouling materials and cell culture.
Example 7
1. Treatment of double bond silane: under the environment of a fume hood, respectively adding 33.1g of dichloromethane, 25mg of 4-dimethylaminopyridine, 0.14g of triethylamine and 0.13g of vinyltrichlorosilane into a centrifugal tube or other closed containers, stirring to prepare a double-bond silane solution, completely immersing a glass 3D structure with a proper size into the silane solution, stirring for 5min, washing the structure with ethanol, and drying the structure with nitrogen to obtain a structure with a surface modified with double bonds;
2. thiol-olefin click reaction: respectively adding 5mg of benzoin dimethyl ether and 0.18g of mercaptoethanol into 0.87g of toluene to prepare a mercaptan solution, then dropwise adding the mercaptan solution onto the double-bond glass structure obtained in the step (1) to completely immerse the structure, turning on an ultraviolet irradiation system, placing the glass structure under ultraviolet light for reaction for 5s, then turning off the ultraviolet irradiation system and taking out the structure. After the reaction is finished, washing the structure with ethanol and drying the structure with nitrogen;
the prepared functional hydroxyl glass can be applied to the fields of glass chips and cell culture.
Claims (9)
1. A preparation method for surface functionalization of a 3D structure is characterized by comprising the following steps:
step one, respectively adding a catalyst, double bond silane and a neutralizing agent into a solvent I to prepare a silane solution, completely immersing the 3D structure into the prepared silane solution, stirring for 5-10 min, washing the 3D structure with ethanol or acetone, and drying with nitrogen to obtain a 3D structure with a surface modified with double bonds;
and step two, respectively adding a photoinitiator and mercaptan into a solvent II to prepare a mercaptan solution, immersing the 3D structure with the surface modified with the double bonds obtained in the step one in the mercaptan solution, standing, reacting for 5-10 s under ultraviolet light, washing with ethanol or acetone, and drying with nitrogen to obtain the 3D structure with the functionalized surface.
2. The method for preparing the surface functionalization of the 3D structure according to claim 1, wherein: the catalyst is 4-dimethylamino pyridine, the double-bond silane is vinyl trichlorosilane, the neutralizing agent is triethylamine, and the first solvent is dichloromethane.
3. The method for preparing the surface functionalization of the 3D structure according to claim 1, wherein: the mass of the catalyst is 23.9-26.5 mg, and the mass ratio of the double-bond silane to the neutralizer to the solvent I is 13-25: 14-29: 2399-3310.
4. The method for preparing the surface functionalization of the 3D structure according to claim 1, wherein: the 3D structure is a photoresist structure obtained through stereolithography 3D printing, and the 3D structure is made of any one of titanium alloy, hydroxyapatite, glass and nylon.
5. The method for preparing the surface functionalization of the 3D structure according to claim 1, wherein: the photoinitiator is benzoin dimethyl ether, the mercaptan is any one of 1H, 1H, 2H, 2H-perfluorodecanethiol, n-dodecanethiol, mercaptoethanol, 3-mercaptopropionic acid, beta-mercaptoethylamine, cysteamine hydrochloride and methoxypolyethylene glycol mercapto, and the solvent II is toluene or DMF.
6. The method for preparing the surface functionalization of the 3D structure according to claim 1, wherein: the mass of the photoinitiator is 0.5-1 mg, and the mass ratio of the mercaptan to the second solvent is 10-20: 87.
7. The application of the functionalized 3D structure prepared by the method according to any one of claims 1 to 6 in surface hydrophilicity and hydrophobicity.
8. The application of the functionalized 3D structure prepared by the method according to any one of claims 1 to 6 in surface antibiosis.
9. Use of a functionalized 3D structure prepared according to any one of claims 1 to 6 in cell culture.
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| CN114588956A (en) * | 2020-12-03 | 2022-06-07 | 中国科学院大连化学物理研究所 | Microfluidic chip glutathione local hydrophilic modification method based on laminar flow effect |
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| CN104003345A (en) * | 2013-02-25 | 2014-08-27 | 国家纳米科学中心 | Carrier with three dimension micro-nanometer structure surface, and preparation method and application thereof |
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| CN104003345A (en) * | 2013-02-25 | 2014-08-27 | 国家纳米科学中心 | Carrier with three dimension micro-nanometer structure surface, and preparation method and application thereof |
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