阅读说明：本技术 一种3d结构表面功能化的制备方法及其应用 (Preparation method and application of surface functionalization of 3D structure ) 是由 顾忠泽 张峻宁 杜鑫 于 2020-06-16 设计创作，主要内容包括：本发明公开了一种3D结构表面功能化的制备方法及其应用,所述制备方法包括以下步骤：步骤一,乙烯基化处理,得到表面修饰有双键的3D结构；步骤二,双键-硫醇点击化学反应,得到所述的具有功能化表面的3D结构。所述应用为功能化3D结构在表面亲疏水、表面抗菌、表面金属沉积中的应用。本发明制备快速,可以赋予3D结构表面各种活性基团,且不依赖于材料本身所带的官能团,对绝大多数材料都能起效,且不会在材料表面形成额外的微纳结构；制备方法的反应条件简单、反应快速,在几分钟内实现不同尺度不同大小的3D结构的功能化,且该方法具有很强的通用性,可进行大规模生产。(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.)

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.

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.