CN104211979A - Preparation method for amine-group-rich polymerization film - Google Patents

Abstract

The invention discloses a method for preparing an amino-rich polymeric film, which is characterized in that: organic amine compounds having double-terminal amino functional groups are copolymerized with polyphenol compounds containing catechols, and by adjusting and controlling the reaction conditions, the base material A thin film rich in amine functional groups was obtained on the surface. The polymer film prepared by the invention has relatively large amount of amine groups on the surface, and can be used for fixing various biomolecules. The prepared film has good stability, and the catechol compound and the base material have a strong binding force, and the introduction of the organic amine compound will increase the crosslinking degree of the film, thereby enhancing the stability of the film. The preparation method is simple and easy, can be deposited on the surface of various materials, does not require complicated equipment, and has low process cost, which lays a foundation for the application of the thin film to the surface modification of biological materials.

Description

A kind of preparation method of rich amine-based polymer film

technical field

The invention relates to a method for preparing a polymeric film with abundant amino functional groups, which is applied to the surface modification of biological materials.

Background technique

Surface modification of biomaterials is a technology that improves the surface properties of materials or enhances special surface properties without affecting the properties of the material itself. It plays an irreplaceable role in the fields of chemistry, biology, materials science, and applied science, engineering, and technology. effect. Existing methods for functional modification of material surfaces include self-assembled thin films, silanization, physical/chemical vapor deposition, and surface grafting. Although these methods are commonly used in research, many methods have many limitations in wide application. For example, the requirements for interface modification and chemical specificity between surfaces, complex equipment used, requirements for the shape and size of substrate materials, complex operations, etc. Therefore, it is very important and necessary to find a simple and easy way to modify the surface of various materials.

Depositing organic films with reactive functional groups on the surface of materials to immobilize biomolecules is a research hotspot, especially dopamine films based on polyphenols have attracted attention. Dopamine films have been greatly developed in the field of biomaterial modification due to their advantages of being able to bind firmly with almost all kinds of materials and providing reaction sites for biomolecular grafting. This provides a platform for modifying different types of materials and preparing functional composites through simple chemistry. However, the secondary reactivity of the dopamine film is limited to biomolecules with sulfhydryl or amine groups, because the secondary reactivity of the dopamine film is based on the combination of the phenolic hydroxyl or quinone groups retained on the dopamine film with the biomolecules. Amino or sulfhydryl groups are based on Michael addition or Schiff base reactions. For the grafting of biomolecules with groups such as carboxyl groups such as heparin, the dopamine film lacks reactive functional groups such as primary amino groups. In addition, an appropriate amount of amine functional groups has the property of promoting cell adhesion, and it is very necessary to obtain amine functional groups for skin repair materials, bone and cartilage repair materials.

Based on this, we prepared an amine-rich functional film. This kind of film is inspired by the adhesion proteins secreted by mussels, among which mussel podoprotein-3 and mutilin-5 are generally considered as the key adhesive agents mediating the binding of mussels to the surface of materials. Contains a high proportion of dopa and rich lysine. Existing research results indicated that the strong binding of mussels to the material surface is based on the strong covalent and non-covalent interactions between the phenolic hydroxyl groups or quinone groups of dopa and the substrate materials. In addition, lysine plays an important role in the cross-linking reaction, which leads to the solidification of the liquid protein adhesive secreted by mussels.

Based on this, we use dopa-like catechol compounds (take dopamine as an example) and organic amine compounds with double-terminal amine functional groups (take hexamethylenediamine as an example) to prepare a highly cross-linked rich amine base copolymer film. Hexamethylenediamine, chemical formula NH ₂ (CH ₂ ) ₆ NH ₂ , is a small molecular organic compound containing amine functional groups, which can be used in organic synthesis, polymerization of polymer compounds, curing agent for epoxy resin, and organic crosslinking agent. Under the action of alkaline environment and oxygen, the catechol group in the dopamine structure can be oxidized into active quinones or semiquinones. This one-step reaction involves the equilibrium process of phenol and quinone group in aqueous solution. In an alkaline environment, the reaction balance shifts to the direction of quinone group, which is beneficial to the spontaneous oxidation reaction of dopamine. The amine group of hexamethylenediamine will undergo Michael addition reaction or Schiff base reaction with the active quinone group, causing mutual crosslinking between molecules. At the same time, dopamine-benzoquinone undergoes cyclization to form a five-membered ring, further oxidation, molecular rearrangement, and intermolecular cross-linking. By adjusting the reaction conditions, a film with a higher density of amine groups on the surface can be obtained. However, there is no report on the introduction of hexamethylenediamine and dopamine copolymerization to prepare films.

Inspired by the protein secreted by mussels, the present invention proposes a simple and novel method to prepare polymeric films with abundant amine functional groups, providing a platform for further grafting of biomolecules to substrate materials. Can be widely used in biomedical metal-based materials (Fe and its alloys, magnesium-based materials, 316L SS, Ti, Ti alloys, Ni-Ti alloys and CoCr alloys, etc.), inorganic materials (Ti-O, TiN, etc.), polymer materials (such as: PET, PTFE, PDMS, etc.) and surface modification of degradable tissue engineering scaffold materials (such as PLA, PLGA, and PCL, etc.).

Contents of the invention

The invention provides a method for preparing an amine-rich polymer film. The film prepared by the method can not only provide abundant amine functional groups for grafting target molecules, but also has good stability.

The technical solution adopted by the present invention to solve its technical problems is: a preparation method of amine-rich polymer film, which introduces organic amine compounds and catechol compounds with amine functional groups to copolymerize, and adjusts the reaction conditions. A thin film rich in amine functional groups was obtained on the surface of the material.

Based on this, the typical steps are:

A. Material preparation.

Substrate materials that will need to be modified include but are not limited to: Fe and its alloys, magnesium and its alloys, 316L SS, Ti, Ti alloys, Ni-Ti alloys and CoCr alloys, Si, Ti-O, TiN, PET, PTFE, PDMS, PLA, PLGA, PCL, Au, Ag, Pt, Pd, Cu, hydroxyapatite, calcium phosphate, bioglass, alumina, silica, PS, PE, PC, PEEK, PU, cleaned, dry, ready to use;

B. Film preparation.

Dissolve 0.01-20mg/ml catechol compounds and 0.01-40mg/ml organic amine compounds in alkaline Tris-base buffer, soak the base material prepared in A into the solution after the reactants are uniformly mixed and react 1-48h, then fully rinsed with distilled water, and dried to obtain a target film with a surface amine group density of 1-200nmol/cm ² .

The inventive method compared with prior art, beneficial effect is:

1. The surface of the prepared polymer film has a large amount of amine groups, which can be used for immobilization of various biomolecules.

2. The prepared film has good stability, and the catechol compound and the base material have a strong binding force, and the introduction of the organic amine compound will increase the cross-linking degree of the film, thereby enhancing the stability of the film.

3. The preparation method is simple and easy, and it can be used in a variety of materials including noble metals (Au, Ag, Pt, Pd), oxides (Cu, titanium oxide, aluminum oxide, silicon oxide, stainless steel, CoCrMo alloy, NiTi alloy), ceramics, Surface deposition of semiconductor materials, polymers (PS, PE, PC, PET, PTFE, PDMS, PLA, PLGA, PCL, PEEK, PU) does not require complicated equipment, and the process cost is low. The surface modification of the material lays the foundation.

Detailed ways

Example 1

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Polish, clean, and dry the base material 316L SS that needs surface modification, and then use it;

B. Film preparation.

Dissolve 1mg/ml dopamine and 20mg/ml hexamethylenediamine in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are uniformly mixed and react for 48h, then fully rinse with distilled water and dry , that is, a film rich in amine groups on the surface.

Example 2

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Clean and dry PTFE, the substrate material that needs to be modified, for use;

B. Film preparation.

Dissolve 2mg/ml dopamine and 15mg/ml ethylenediamine in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are uniformly mixed and react for 24h, then fully rinse with distilled water, and dry , that is, a film rich in amine groups on the surface.

Example 3

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Polish, clean, and dry the base material 316LSS that needs to be modified, and wait for use;

B. Film preparation.

Dissolve 1mg/ml dopamine and 20mg/ml polylysine (PLL) in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are evenly mixed and react for 12h, then use Rinse thoroughly with distilled water and dry to obtain a film rich in amine groups on the surface.

Example 4

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Clean and dry PTFE, the substrate material that needs to be modified, for use;

B. Film preparation.

Dissolve 1mg/ml dopamine and 20mg/ml polyetherimide (PEI) in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are uniformly mixed and react for 12h, then use Rinse thoroughly with distilled water and dry to obtain a film rich in amine groups on the surface.

Example 5

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Polish, clean, and dry the base material 316LSS that needs to be modified, and wait for use;

B. Film preparation.

Dissolve 1mg/ml catechol and 2mg/ml hexamethylenediamine in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are evenly mixed and react for 24h, then fully rinse with distilled water Rinse and dry to obtain a film rich in amine groups on the surface.

Example 6

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Clean and dry PTFE, the substrate material that needs to be modified, for use;

B. Film preparation.

Dissolve 1mg/ml catechol and 2mg/ml ethylenediamine in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are uniformly mixed and react for 12h, and then fully wash with distilled water Rinse and dry to obtain a film rich in amine groups on the surface.

Example 7

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Polish, clean, and dry the base material 316LSS that needs to be modified, and wait for use;

B. Film preparation.

Dissolve 1mg/ml catechol and 10mg/ml polylysine (PLL) in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are uniformly mixed and react for 12h , then fully rinsed with distilled water, and dried to obtain a film rich in amine groups on the surface.

Example 8

A preparation method of a rich amine-based polymeric film, the steps of which are:

A. Material preparation.

Clean and dry PTFE, the substrate material that needs to be modified, for use;

B. Film preparation.

Dissolve 1mg/ml catechol and 20mg/ml polyetherimide (PEI) in alkaline Tris-base buffer, soak the base material prepared in A in the solution after the reactants are uniformly mixed and react for 48h , then fully rinsed with distilled water, and dried to obtain a film rich in amine groups on the surface.

Claims (4)

1. the preparation method of a rich amido polymer thin film, it is characterized in that: will there is both-end amidine functional group organic amine compound and the polyphenolic substance copolymerization containing pyrocatechol, by regulation and control reaction conditions, obtain on base material surface the film being rich in amidine functional group.

2. the preparation method of a kind of rich amido polymer thin film according to claim 1, the steps include:

A, material prepare

The base material carrying out modification will be needed, include but not limited to: Fe and alloy, magnesium and alloy thereof, 316L SS, Ti, Ti alloy, Ni-Ti alloy and CoCr alloy, Si, Ti-O, TiN, PET, PTFE, PDMS, PLA, PLGA, PCL, Au, Ag, Pt, Pd, Cu, hydroxyapatite, calcium phosphate, bio-vitric, aluminum oxide, silicon oxide, PS, PE, PC, PEEK, PU, through cleaning, drying, stand-by;

The preparation of B, film

0.01-20mg/ml catechol and 0.01-40mg/ml organic amine compound are dissolved in alkaline Tris-base damping fluid, 1-48h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, drying, obtains surface amine groups density 1-200nmol/cm ²target compound film.

3. the preparation method of a kind of rich amido polymer thin film according to claim 1, is characterized in that, the described polyphenolic substance containing pyrocatechol comprises Dopamine HCL, pyrocatechol.

4. the preparation method of a kind of rich amido polymer thin film according to claim 1, is characterized in that, described in there is double-end amino functional group organic amine compound comprise hexanediamine, quadrol, poly-lysine, polyetherimide (PEI).