阅读说明：本技术 一种基于盐酸多巴胺和3,4-二羟基苯甲醛生成新型产物的方法 (Method for generating novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde ) 是由 周利峰 曹静诗 李利红 于 2021-09-13 设计创作，主要内容包括：本发明公开了一种基于盐酸多巴胺和3,4-二羟基苯甲醛生成新型产物的方法,在原有工艺基础上进行了创新性的改进,采用盐酸多巴胺与3,4-二羟基苯甲醛的反应并自聚生成聚多巴胺,采用水洗涤,除去产品中副产物和残留溶剂,使产品收率和纯度大大提高,同时提高了产物的各项性能。(The invention discloses a method for generating a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde, which is innovatively improved on the basis of the original process, wherein dopamine hydrochloride is adopted to react with the 3, 4-dihydroxybenzaldehyde and generate poly-dopamine by self-polymerization, and the poly-dopamine is washed by water to remove byproducts and residual solvents in the product, so that the yield and purity of the product are greatly improved, and various performances of the product are improved.)

1. A method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde, characterized by the following steps:

s1, dissolving dopamine hydrochloride and 3, 4-dihydroxy benzaldehyde in a solvent, and stirring and fully dissolving the dopamine hydrochloride and the 3, 4-dihydroxy benzaldehyde in the solvent;

s2, slowly adding triethylamine into the solution dropwise, condensing, refluxing and stirring, gradually forming yellow precipitates in the reaction process, and after the reaction is finished, filtering, washing and drying to obtain yellow precipitate products;

and S3, adding the solid product prepared in the S2 into a weak alkaline solution, stirring, carrying out suction filtration and drying to obtain a novel product of poly-dopamine generated by surface self-polymerization.

2. The method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde according to claim 1, characterized in that in step S1, dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde are distributed according to a molar ratio of 1: 1.

3. The method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde according to claim 1, characterized in that, in step S1, the solvent is selected from one of methanol, acetone, dimethylformamide, dimethylacetamide, formamide and acetamide.

4. The method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde according to claim 1, characterized in that, in step S1, the mixture is stirred and heated by oil, water bath and magnetic force, the stirring rate is 200-300 r/min, and the temperature is 20-60 ℃.

5. The method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde according to claim 1, characterized in that, in step S2, filtration is performed by using a centrifuge or suction filtration, and washing is performed by using ethanol aqueous solution.

6. The method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde according to claim 1, characterized in that in step S3, one of the weak alkaline solutions is prepared by tris, ammonia water and sodium hydroxide, and the PH of the solution is adjusted by hydrochloric acid.

7. The method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde according to claim 1, characterized in that in step S3, the solid product obtained in step S2 is added together with dopamine hydrochloride into a weakly alkaline solution.

Technical Field

The invention relates to a method for producing novel products based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde.

Background

Under the oxidation condition, dopamine is easy to generate self-polymerization in aqueous solution to generate a polydopamine coating firmly attached to the surfaces of various materials, and the bionic characteristic of the dopamine opens up a new way for surface modification of inert materials; at present, dopamine and polymers thereof are widely used for surface modification of various materials to endow the materials with brand-new surface properties, and the surface modification technology is mainly characterized in that the surface of the materials can be endowed with the properties depending on PDA coatings through one-step modification of dopamine aqueous solution; because the formation process of the PDA coating is in-situ oxidative polymerization, the PDA coating can uniformly modify the inner and outer surfaces of the material and the inside of the hole at the same time; messersmith et al successfully achieve the most direct effect of surface modification of a series of organic-inorganic materials such as noble metal oxides, non-metallic inorganic oxides, polymers and the like on surface coating of PDA for hydrophobic materials by adopting a dopamine aqueous solution coating method, namely achieving hydrophilization of the material surface; lee and other researches find that after dopamine aqueous solution surface coating modification is carried out on surfaces such as PE, PTFE and the like which are not adhered to cells originally, hydrophilicity of the material surfaces is improved, and adhesion of osteoblasts MC3T3-E1 on the material surfaces is obviously improved; tsai et al also prove that after the surface of the articular cartilage stent made of materials such as polyamide is coated and modified by dopamine aqueous solution, the adhesion and growth of cells on the surface of the stent can be remarkably promoted. This shows that the PDA coating has important function for improving the surface biocompatibility of the material and expanding the application of the material in the biomedical field; but traditionally, dopamine hydrochloride is generally added into a weak alkaline aqueous solution, and polydopamine obtained by self-polymerization of dopamine hydrochloride has extremely low yield and low efficiency; in addition, the compatibility between the filler and the polymer is improved by treating the filler with a coupling agent, but the operation is complex and the environment is polluted; the existing process also exposes the defects of poor adhesion, poor secondary functionalization, poor mechanical property and the like of the polydopamine.

Disclosure of Invention

Aiming at the defects of the prior art, the invention solves the problems that: the method for generating the novel product based on the dopamine hydrochloride and the 3, 4-dihydroxybenzaldehyde has the advantages of high yield and purity, environmental friendliness, good adhesion and secondary functionalization performance, good mechanical performance, good heat conductivity, improvement of heat deformation temperature and good flame retardance.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

a method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde comprises the following steps:

s1, dissolving dopamine hydrochloride and 3, 4-dihydroxy benzaldehyde in a solvent, and stirring and fully dissolving the dopamine hydrochloride and the 3, 4-dihydroxy benzaldehyde in the solvent;

s2, slowly adding triethylamine into the solution dropwise, condensing, refluxing and stirring, gradually forming yellow precipitates in the reaction process, and after the reaction is finished, filtering, washing and drying to obtain yellow precipitate products;

and S3, adding the solid product prepared in the S2 into a weak alkaline solution, stirring, carrying out suction filtration and drying to obtain a novel product of poly-dopamine generated by surface self-polymerization.

Further, in step S1, dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde are distributed according to a molar ratio of 1: 1.

Further, in the step S1, the solvent is selected from one of methanol, acetone, dimethylformamide, dimethylacetamide, formamide and acetamide.

Further, in the step S1, oil, water bath and magnetic force are adopted for stirring and heating, the stirring speed is 200-300 r/min, and the temperature is 20-60 ℃.

Further, in step S2, the mixture is filtered by a centrifuge or suction filtration, and washed with an ethanol aqueous solution.

Further, in step S3, tris, ammonia water, and sodium hydroxide are used to prepare one of the weak alkaline solutions, and hydrochloric acid is used to adjust the PH of the solution.

Further, in the step S3, the solid product obtained in the step S2 and dopamine hydrochloride are added together into a weak alkaline solution.

The chemical reaction equation of the invention is as follows:

the invention has the following beneficial effects:

1. the invention is innovatively improved on the basis of the original process, polydopamine is generated by adopting the reaction and self-polymerization of dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde, and by-products and residual solvents in the product are removed by adopting water washing, so that the yield and the purity of the product are greatly improved.

2. Reacting dopamine hydrochloride with 3, 4-dihydroxy benzaldehyde to obtain more products, and performing auto-polymerization on the products to obtain a new product containing polydopamine, wherein the new product has adhesiveness and secondary functionalization; because the surface of the PDA contains a large number of catechol reaction groups, the surface of the material can be bonded with functional molecules again through secondary reaction, so that further functional modification of the surface of the material is realized, for example, metal or metal oxide is deposited on the surface of the PDA, graft polymerization reaction is initiated on the surface, functional molecules are fixed on the surface, and the like.

3. The compatibility between the filler and the polymer is improved by using a coupling agent in the prior art, but the operation is complex and the environment is polluted, and a polydopamine nano-layer generated by self-polymerization of the biomass material dopamine is adhered with an organic or inorganic filler, so that the adhesiveness between the polydopamine nano-layer and the polymer is enhanced, the interface action between the polydopamine nano-layer and the polymer is enhanced, and meanwhile, the mechanical property of the blended material can be effectively improved by thickening the interface layer.

4. The polydopamine has high carbon yield, is favorable for the transmission of electrons and phonons when being added into a polymer, is favorable for improving the heat conductivity, thereby improving the heat deformation temperature, and has certain flame retardance due to the nitrogen; according to the invention, dopamine hydrochloride is added into the high polymer material, so that the composite material has better flame retardance and heat resistance, and the toughness of the composite material is greatly enhanced.

Detailed Description

The present invention will be described in further detail below.

Example 1

A method for producing a novel product based on dopamine hydrochloride and 3, 4-dihydroxybenzaldehyde comprises the following steps:

s1, dissolving 2.84g of dopamine hydrochloride and 2.07g of 3, 4-dihydroxybenzaldehyde in 150ml of methanol solvent, and stirring and fully dissolving the dopamine hydrochloride and the 3, 4-dihydroxybenzaldehyde in the solvent; stirring and heating by adopting oil, water bath and magnetic force, wherein the stirring speed is 250r/min, and the temperature is 25 ℃.

S2, dropwise adding 2.1ml of triethylamine to the solution obtained in the step S1 step by step, condensing, refluxing, stirring, gradually generating precipitates, filtering, washing and drying to obtain a golden yellow product 3.5g, wherein the yield is 71%; filtering with centrifuge or suction filtration, and washing with ethanol water solution.

S3, adding 3g of cleaned and dried golden yellow product P1 powder into 100ml of Tris-HCL buffer solution with the pH value of 8.5, mechanically stirring the mixture in an open flask for 24 hours at the temperature of 35 ℃ in an air atmosphere, and performing suction filtration and drying to obtain a polydopamine product with the surface having the thickness of 1-40 nm; after suction filtration, washing and drying, 2.5g of a new product containing poly-dopamine generated by self-polymerization is obtained, and the yield is 83 percent.

Example 2

S1, dissolving 2.84g of dopamine hydrochloride and 2.07g of 3, 4-dihydroxybenzaldehyde in 150ml of methanol solvent, and stirring and fully dissolving the dopamine hydrochloride and the 3, 4-dihydroxybenzaldehyde in the solvent; stirring and heating by adopting oil, water bath and magnetic force, wherein the stirring speed is 280r/min, and the temperature is 30 ℃.

S2, dropwise adding 2.1ml of triethylamine to the step S1 step by step, condensing, refluxing, stirring, gradually generating precipitates, filtering, washing and drying to obtain 3.5g of a golden yellow product P1, wherein the yield is 71%; filtering with centrifuge or suction filtration, and washing with ethanol water solution.

S3, adding 3g of cleaned and dried golden yellow product P1 powder and 0.2g of dopamine hydrochloride into 100ml of Tris-HCl buffer solution with the pH value of 8.5, mechanically stirring the mixture for 24 hours in an open flask at the temperature of 35 ℃ in the air atmosphere, and performing suction filtration and drying to obtain a polydopamine product with the thickness of 1-40 nm on the surface; after suction filtration, washing and drying, 2.7g of a new product containing poly-dopamine generated by self-polymerization is obtained, and the yield is 84%.

The chemical reaction equation of the invention is as follows:

dopamine hydrochloride is added into a weak alkaline aqueous solution, so that polydopamine obtained through self-polymerization of dopamine hydrochloride is extremely low in yield and low in efficiency. More products are obtained through the reaction of dopamine hydrochloride and 3, 4-dihydroxy benzaldehyde, and then a new product containing polydopamine is obtained through self-polymerization of the products, so that the polydopamine-containing product has adhesiveness and secondary functionalization; because the surface of the PDA contains a large number of catechol reaction groups, the surface of the material can be bonded with functional molecules again through secondary reaction, so that further functional modification of the surface of the material is realized, for example, metal or metal oxide is deposited on the surface of the PDA, graft polymerization reaction is initiated on the surface, functional molecules are fixed on the surface, and the like; the compatibility between the filler and a polymer is improved by using a coupling agent in the prior art, but the operation is complex and the environment is polluted, and a polydopamine nano-layer generated by self-polymerization of a biomass material dopamine is adhered with an organic or inorganic filler, so that the adhesiveness between the polydopamine nano-layer and the polymer is enhanced, the interface action between the polydopamine nano-layer and the polymer is enhanced, and meanwhile, the mechanical property of the blended material can be effectively improved by thickening the interface layer; the polydopamine has high carbon yield, is favorable for the transmission of electrons and phonons when added into a polymer, is favorable for improving the heat conductivity, thereby improving the heat deformation temperature, and has certain flame retardance due to the nitrogen.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.