CN111607052B - Preparation method of melanin-like granules and melanin-like granules - Google Patents
Preparation method of melanin-like granules and melanin-like granules Download PDFInfo
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- CN111607052B CN111607052B CN201910139957.7A CN201910139957A CN111607052B CN 111607052 B CN111607052 B CN 111607052B CN 201910139957 A CN201910139957 A CN 201910139957A CN 111607052 B CN111607052 B CN 111607052B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/10—Melamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
Abstract
The invention discloses a preparation method of melanin-like particles and the melanin-like particles. The method comprises the following steps: (1) dissolving a monomer with a catechol functional group in water at 20-60 ℃ and reacting the monomer with an aldehyde group-containing compound under an alkaline condition of pH 8-11 for 0.5-3 h; (2) dissolving an amino compound with a conjugated structure in water, and reacting and dissolving the amino compound with an aldehyde group-containing compound at 70-85 ℃ to obtain a transparent solution; (3) adding the solution in the step (1) into the solution in the step (2), and fully stirring for 30-90 min at 20-60 ℃; (4) adjusting the pH value of the solution to be less than or equal to 6, and heating to 70-90 ℃ to react for 10-48 h. The melanoid particles exhibit a pronounced spherical shape. The catechol group endows the film with more functions such as ultraviolet shielding, adhesion, corrosion resistance and the like, has low cost and can be used for later industrial application.
Description
Technical Field
The invention relates to the technical field of melanin-like synthesis, and further relates to a preparation method of melanin-like particles and the melanin-like particles.
Background
Melanin (Melanin) is a structurally irregular macromolecular compound widely distributed in animals, plants and microorganisms, and is a general name of Melanin and brown macromolecular compounds generated in the oxidation and polymerization processes of phenolic substances. Because melanin contains abundant functional groups on the surface, it has a wide application prospect in cosmetics, hair dyes, ultraviolet radiation protection, free radical scavenging, amorphous semiconductors, and photo-protective agents for biopesticides. In addition, the melanin also has important significance for the research of pathology and taxonomy. However, the price of the substrate is generally high, and taking dopamine hydrochloride as an example, the dosage of the substrate is about 6-10 yuan per gram, which greatly limits the industrial application of melanin.
Catechol is an important multifunctional building block for the design of mussel synthetic adhesives and coatings. Indeed, their ability to interact with organic and inorganic substrates facilitates catechol as a versatile group for surface modification. In addition to the critical role in the adhesive interface, catechol has recently been a powerful building block group for the production of polymeric materials with specific structures and excellent properties.
Studies have shown that catechol and amine groups are two key groups for oxidative polymerization of dopamine to form strong adhesion, and molecules with amine and catechol groups can have dopamine-like properties. The xu Jian subject group of Chinese academy of sciences university uses low-cost catechol and polyamine instead of dopamine for surface modification of polypropylene separators (ACS Applied Materials & Interfaces,2014,6(8):5602), and this method is that catechol and polyamine are polymerized under alkaline condition and deposited on the surface of material, and can not form regular shape, which limits its application. The Hongdong group of the university of the Qilu industry, which uses melamine and formaldehyde, prepared monodisperse microspheres for the adsorption of heavy metals (Chemical Engineering Journal,2016,288: 745-.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a melanin-like granule and the melanin-like granule. The invention utilizes monomer containing catechol group, melamine and formaldehyde to prepare the melanin-like particles which are obviously spherical. The catechol group endows the film with more functions such as ultraviolet shielding, adhesion, corrosion resistance and the like, has low cost and can be used for later industrial application.
One of the objects of the present invention is to provide a method for preparing melanin-like granules.
The method comprises the following steps:
(1) dissolving a monomer with a catechol functional group in water at 20-60 ℃ and reacting the monomer with an aldehyde group-containing compound under an alkaline condition of pH 8-11 for 0.5-3 h;
(2) dissolving an amino compound with a conjugated structure in water, and reacting and dissolving the amino compound with an aldehyde group-containing compound at 70-85 ℃ to obtain a transparent solution;
(3) adding the solution in the step (1) into the solution in the step (2), and fully stirring for 30-90 min at 20-60 ℃;
(4) adjusting the pH value of the solution to be less than or equal to 6, and heating to 70-90 ℃ to react for 10-48 h.
Wherein the content of the first and second substances,
the structural formula of the monomer with the catechol functional group is as follows:
R1、R2is a hydrogen atom, a fluorine atom, an alkyl group (C)mH2m) Alkoxy (C)mH2m-O), phenyl (C)mHm-2) A tertiary butyl group,
Said monomer bearing a catechol function is preferably: catechol, 4-tert-butylcatechol, 3-fluorocatechol;
the aldehyde group-containing compound is one or a combination of formaldehyde, paraformaldehyde, glutaraldehyde, glyoxal, furfural and terephthalaldehyde; preferably formaldehyde, paraformaldehyde;
the structural formula of the amino compound with the conjugated structure is as follows:
R-(NH2)n，
r is a structure with a pi-pi conjugated system, a p-pi conjugated system and a super conjugated system;
n is 1 to 20.
The amino compound having a conjugated structure is preferably: melamine, m-phenylenediamine and aniline.
Step (1), adjusting the pH to 8-11 by adopting one or a combination of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal bicarbonate, alkaline earth metal bicarbonate, alkali metal acetate, alkali metal phosphate, alkali metal alkoxide, ammonia gas, ammonia water and amine;
the weight ratio of the catechol monomer to the aldehyde group-containing compound to the water is 1 (0.5-3) to 10-100; more preferably 1 (1 to 1.5): (50 to 90)
Step (2), the weight ratio of the amino compound with the conjugated structure, the compound containing aldehyde group and water is 1: (0.5-4): (5-100); more preferably 1: (1.5-2.5): (30-80).
And (3) the weight ratio of the catechol to the amino compound with the conjugated structure is 1: (0.1-2); more preferably 1: (0.3-1.2).
And (4) adjusting the pH value of the system to be less than or equal to 6 by using a hydrochloric acid aqueous solution.
Another object of the present invention is to provide melanin-like particles.
The melanoid particles are spherical; the average particle size is 0.05 to 5 μm.
The invention is characterized in that the melanin-like nanoparticles with obvious spherical shape can be prepared, and the particle diameter is between 0.05 and 5 mu m. Specifically, the molar ratio of the aqueous solution to the raw material is adjusted so that the dispersibility of the melanoid is better. Adjusting the molar ratio of monomer to formaldehyde can make the spheres more regular. The spherical shape of the particles can be controlled by adjusting the pH and the reaction time.
Compared with the prior synthesis method, the invention has the following innovation points:
compared with melanin, the melanin-like particles prepared by the invention are lower in price.
The melanin-like particles prepared by the method are more regular in shape, are obviously spherical and are uniform in particle size.
The melanin-like nanoparticles prepared by the method have good dispersion effect in aqueous solution.
The melanin-like nanoparticles prepared by the method can be applied to the aspects of modified functional materials, biomedical materials and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a low-cost melanin-like nanoparticle prepared in example 1;
fig. 2 is an infrared spectrum of the low-cost melanin-like nanoparticles prepared in example 1.
At 3350cm-1The central expansion peak indicates that intermolecular hydrogen bonds exist between hydroxyl and amino groups on catechol, indicating that the two groups are reacted and connected.
Detailed Description
The present invention will be further described with reference to the following examples.
The starting materials used in the examples are all commercially available.
Example 1
0.55 part of catechol (AR, Shanghai Aladdin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the mixture was reacted at 20 ℃ for 1 hour. 0.63 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 20 parts of water, and 1.23 parts of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 2
0.55 part of catechol (AR, specification: Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.42 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 20 parts of water, and 0.82 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 3
0.55 part of catechol (AR, Shanghai Aladdin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the mixture was reacted at 60 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 4
0.55 part of catechol (AR, specification, Shanghai Aladdin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 30 minutes. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.5 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 5
0.55 part of catechol (AR, specification: Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 15 parts of water, and 0.315 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 6
0.55 part of catechol (AR, specification, Shanghai Aladdin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 3 hours. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 75 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 4 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 7
0.55 part of catechol (AR, specification: Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 85 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 6 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 8
0.55 part of catechol (AR, specification: Shanghai Aladdin Biotechnology Co., Ltd.) was weighed out and dissolved in 28 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 8, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 9
0.55 part of catechol (AR, specification: Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed out and dissolved in 39 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 8.5, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of m-phenylenediamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 10
0.55 part of catechol (AR, Shanghai Allan Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.55 part of formaldehyde was added thereto, pH was adjusted to 9, and the mixture was reacted at 40 ℃ for 1 hour. 0.21 part of aniline (specification: CP, national chemical group chemical Co., Ltd.) was dissolved in 10 parts of water, and 0.41 part of formaldehyde was added thereto and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 20 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 11
0.55 part of catechol (AR, Shanghai Aladdin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.68 part of formaldehyde was added thereto, pH was adjusted to 9, and the mixture was reacted at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 24 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 12
0.55 part of catechol (AR, specification, Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed and dissolved in 50 parts of water, 0.808 part of terephthalaldehyde was added thereto, and the mixture was reacted at 40 ℃ for 1 hour with the pH adjusted to 9. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 45 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 75 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 13
0.55 part of catechol (AR, specification, Shanghai Aladdin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of furfural was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 50 ℃ for 50min, then adjusted to pH 5 with acid solution, heated to 85 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 14
0.55 part of catechol (AR, specification: Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed and dissolved in 50 parts of water, 0.808 part of glyoxal was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 60min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 h, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 15
0.55 part of 3-fluorocatechol (AR, specification, Shanghai Allan Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of glutaraldehyde was added thereto, the pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Example 16
0.55 part of 4-tert-butylcatechol (specification: AR, Shanghai Allantin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of paraformaldehyde was added thereto, the pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 5 with acid solution, heated to 80 ℃ and reacted for 16 hours, and the particle size of the obtained low-cost melanin-like particles is shown in Table 1.
Comparative example 1
0.55 part of catechol (AR, Shanghai Allantin Biotechnology Co., Ltd.) was weighed out and dissolved in 50 parts of water, and then 0.808g of formaldehyde was added thereto, and the mixture was reacted at 40 ℃ for 1 hour without adjusting pH. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. And then, adding the reacted solution containing the catechol into a melamine solution, stirring for 40min at 40 ℃, layering the solution in the stirring process, and solidifying a part of the solution at the bottom to prevent continuous reaction.
Comparative example 2
0.55 part of catechol (AR, specification: Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Subsequently, the reacted catechol-containing solution was added to a melamine solution, stirred at 40 ℃ for 40min, and then adjusted to pH 2 with an acidic solution, and reacted at 80 ℃ for 1 hour. The product obtained had no apparent spherical shape.
Comparative example 3
0.55 part of catechol (AR, specification: Shanghai Aladdin Biochemical technology Co., Ltd.) was weighed out and dissolved in 50 parts of water, 0.808 part of formaldehyde was added thereto, pH was adjusted to 9, and the reaction was carried out at 40 ℃ for 1 hour. 0.21 part of melamine (specification: CP, national chemical group chemical Co., Ltd.) was weighed out and dissolved in 10 parts of water, and 0.41 part of formaldehyde was added and dissolved at 80 ℃ until the solution was transparent. Then, the reacted solution containing catechol was added to a melamine solution, stirred at 40 ℃ for 40min, then adjusted to pH 7 with an acid solution, heated to 80 ℃ for 14 hours, and reacted at 85 ℃ for 3 hours. The product obtained had no apparent spherical shape.
TABLE 1 Melanin-like particle size
TABLE 2 application Properties of Melanin-like particles
| Dispersibility | Ultraviolet shielding propertya | Adhesion and corrosivenessb | |
| Example 1 | Standing for 48 hr without precipitate | √√ | Level 1 |
| Example 2 | Standing for 48 hr with precipitate | √ | Stage 2 |
| Example 12 | Standing for 48 hr without precipitate | √√√ | |
| Comparative example 1 | Agglomerated precipitate | × | Grade 5 |
aX: the ultraviolet shielding is less than 5%; v: ultraviolet shielding 5-20% (excluding 20%); v: ultraviolet shielding 20-50% (excluding 50%); v √: ultraviolet shielding is 50% or more.
bNational standard GB/T14834-2009.
In conclusion, the prepared low-cost melanin granules have uniform grain diameter, obvious spherical shape, good dispersibility in water, excellent ultraviolet shielding property, excellent adhesion and excellent corrosion resistance.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (8)
1. A method for preparing melanin-like granules, which comprises:
(1) dissolving a monomer with a catechol functional group in water at 20-60 ℃ and reacting the monomer with an aldehyde group-containing compound under an alkaline condition of pH 8-11 for 0.5-3 h;
the weight ratio of the monomer with the catechol functional group to the compound containing aldehyde group to the water is 1 (0.5-3) to 10-100;
(2) dissolving an amino compound with a conjugated structure in water, and reacting and dissolving the amino compound with an aldehyde group-containing compound at 70-85 ℃ to obtain a transparent solution;
the weight ratio of the amino compound with the conjugated structure, the compound containing aldehyde group and the water is 1: (0.5-4): (5-100);
(3) adding the solution in the step (1) into the solution in the step (2), and fully stirring for 30-90 min at 20-60 ℃;
the weight ratio of the monomer with the catechol functional group to the amino compound with the conjugated structure is 1: (0.1-2);
(4) adjusting the pH value of the solution to be less than or equal to 6, heating to 70-90 ℃, and reacting for 10-48 h;
the structural formula of the monomer with the catechol functional group is as follows:
R1、R2is a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, a phenyl group,
The aldehyde group-containing compound is one or a combination of formaldehyde, paraformaldehyde, glutaraldehyde, glyoxal, furfural and terephthalaldehyde;
the structural formula of the amino compound with the conjugated structure is as follows:
R-(NH2)n，
r is a structure with a pi-pi conjugated system, a p-pi conjugated system and a super conjugated system;
n is 1 to 20.
2. The method for preparing melanoid granules according to claim 1, wherein:
step (1), adjusting the pH to 8-11 by adopting one or a combination of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal bicarbonate, alkaline earth metal bicarbonate, alkali metal acetate, alkali metal phosphate, alkali metal alkoxide, ammonia gas, ammonia water and amine;
the monomer with catechol functional group is catechol, 4-tert-butyl catechol or 3-fluoro catechol.
3. The method for preparing melanoid granules according to claim 1, wherein:
the weight ratio of the monomer with the catechol functional group to the compound containing aldehyde group and water is 1 (1-1.5) to 50-90.
4. The method for preparing melanoid granules according to claim 1, wherein:
and (2) the amino compound with the conjugated structure is melamine, m-phenylenediamine or aniline.
5. The method for preparing melanoid granules according to claim 1, wherein:
and (2) the weight ratio of the amino compound with the conjugated structure, the compound containing aldehyde group and water is 1: (1.5-2.5): (30-80).
6. The method for preparing melanoid granules according to claim 1, wherein:
and (3) the weight ratio of the monomer with the catechol functional group to the amino compound with the conjugated structure is 1: (0.3-1.2).
7. The method for preparing melanoid granules according to claim 1, wherein:
and (4) adjusting the pH value of the system to be less than or equal to 6 by using a hydrochloric acid aqueous solution.
8. Melanoid granules obtained by the process according to any one of claims 1 to 7, characterized in that:
the melanoid particles are spherical; the average particle size is 0.05 to 5 μm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES291964A1 (en) * | 1962-10-18 | 1964-01-16 | Bayer Ag | Procedure to increase stability in the light of rutile pigments in melanin-formaldehyde and urea-formaldehyde resins (Machine-translation by Google Translate, not legally binding) |
| JPH03265619A (en) * | 1990-03-16 | 1991-11-26 | Mitsui Toatsu Chem Inc | Powdery phenolic cocondensation resin |
| JPH03265618A (en) * | 1990-03-16 | 1991-11-26 | Mitsui Toatsu Chem Inc | New phenolic cocondensation resin and its preparation |
| JPH04292612A (en) * | 1991-03-19 | 1992-10-16 | Mitsui Toatsu Chem Inc | New phenolic cocondensed resin having improved water-solubility and its production |
| CN107999023A (en) * | 2017-11-23 | 2018-05-08 | 河南师范大学 | Carry the preparation method of cobalt ordered mesoporous carbon material and its application in Oxone rhodamine B degradation waste water is catalyzed |
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2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES291964A1 (en) * | 1962-10-18 | 1964-01-16 | Bayer Ag | Procedure to increase stability in the light of rutile pigments in melanin-formaldehyde and urea-formaldehyde resins (Machine-translation by Google Translate, not legally binding) |
| JPH03265619A (en) * | 1990-03-16 | 1991-11-26 | Mitsui Toatsu Chem Inc | Powdery phenolic cocondensation resin |
| JPH03265618A (en) * | 1990-03-16 | 1991-11-26 | Mitsui Toatsu Chem Inc | New phenolic cocondensation resin and its preparation |
| JPH04292612A (en) * | 1991-03-19 | 1992-10-16 | Mitsui Toatsu Chem Inc | New phenolic cocondensed resin having improved water-solubility and its production |
| CN107999023A (en) * | 2017-11-23 | 2018-05-08 | 河南师范大学 | Carry the preparation method of cobalt ordered mesoporous carbon material and its application in Oxone rhodamine B degradation waste water is catalyzed |
Non-Patent Citations (1)
| Title |
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| "Decoupling microporosity and nitrogen content to optimize CO2 adsorption in melamine-resorcinol-formaldehyde xerogels";Principe, I. A. et al.;《MATERIALS TODAY CHEMISTRY》;20181102;第195-205页 * |
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