CN108003792B - Lignin-based metal protective coating and preparation method thereof - Google Patents

Lignin-based metal protective coating and preparation method thereof Download PDF

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Publication number
CN108003792B
CN108003792B CN201711443343.5A CN201711443343A CN108003792B CN 108003792 B CN108003792 B CN 108003792B CN 201711443343 A CN201711443343 A CN 201711443343A CN 108003792 B CN108003792 B CN 108003792B
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lignin
protective coating
based metal
metal protective
reagent
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CN108003792A (en
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夏南南
孔凡功
吴芹
王守娟
孙浩东
许仃仃
赵鑫
陈洪雷
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Shandong Jiqing Technology Service Co ltd
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Qilu University of Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D197/00Coating compositions based on lignin-containing materials
    • C09D197/005Lignin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention provides a lignin-based metal protective coating and a preparation method thereof, belonging to the technical field of metal coatings. The paint mainly utilizes the characteristic functional group in the functional reagent and metal ions to generate coordinate bonds under alkaline conditions, and the coordinate bonds have dynamic exchange performance under the action of water to play a role on metal. The lignin-based metal protective coating can play a role in protecting metal under a dry condition and can also play a role in protecting metal in a wet state.

Description

Lignin-based metal protective coating and preparation method thereof
Technical Field
The invention relates to the technical field of metal coatings, in particular to a lignin-based metal protective coating and a preparation method thereof.
Background
The metal material is spread in the aspects of human life, great convenience is provided for daily life, however, the metal material is easily damaged by the influence of surrounding media, and metal corrosion is caused. Generally, corrosion of metal materials is mainly caused by chemical or electrochemical multiphase reactions occurring on the metal surface, which causes the metal to be converted into an oxidized (ionic) state. Therefore, the mechanical properties of the material such as strength, plasticity, toughness and the like are reduced, the geometric shape of a metal component is damaged, the abrasion among parts is increased, the physical properties of electricity, optics and the like are deteriorated, the service life of equipment is shortened, and even disastrous accidents such as fire, explosion and the like are caused. Therefore, solving the problem of corrosion prevention of metal materials is an important issue in relation to daily life and industrial development.
At present, the anticorrosion measures of metal materials mainly comprise: (1) covering a protective layer on the metal surface, such as: painting paint, galvanizing, tinning, chrome plating and the like, or preparing an oxide film; (2) attaching to the metal to be protected a metal which is more susceptible to losing electrons than the metal; (3) changing the internal organization of metals, such as: the steel is made into stainless steel.
However, since these methods mainly use other metals or noble metals as the protective layer, which is expensive, they are not suitable for wide applications, and in most cases, the metal material is not in a dry environment and a galvanic cell is easily formed, there is a need for a new solution to the corrosion problem of the metal material.
Disclosure of Invention
The technical task of the invention is to solve the defects of the prior art and provide a lignin-based metal protective coating and a preparation method thereof.
The technical scheme is realized in the following way, and the lignin-based metal protective coating is obtained by firstly dissolving alkaline lignin in water to prepare a lignin solution, adding a functional reagent into the lignin solution after the alkaline lignin is uniformly dissolved, uniformly stirring and mixing, then adding a cationic flocculant into the mixed solution, and stirring and flocculating to obtain the lignin-based metal protective coating.
The coating is prepared by mixing alkali lignin as a matrix material, water as a solvent, a compound containing a catechol structure as a functional reagent, and a cationic flocculant as a crosslinking reagent.
The formula and the proportion used in the preparation of the coating are as follows:
3-12 parts of alkaline lignin; 1-10 parts of a functional reagent; 0.01-1 part of a crosslinking reagent;
firstly, dissolving 3-12 parts by weight of alkali lignin in distilled water to prepare a lignin solution with the mass concentration of 10-30%, adding 1-10 parts of a compound containing a catechol structure as a functional reagent after uniform dissolution, stirring and mixing uniformly, then adding 0.01-1 part of a cationic flocculant as a crosslinking reagent into the mixed solution, and stirring and flocculating for 0.5-24 hours to obtain the lignin-based metal protective coating.
The preparation method of the lignin-based metal protective coating comprises the following steps: the lignin-based metal protective coating is prepared by taking lignin as a base material, a cationic flocculant as a crosslinking reagent, a compound containing a catechol structure as a functional reagent and water as a solvent, dissolving and mixing, and effectively combining the lignin containing negative charges with the functional reagent by the cationic flocculant under the electrostatic action.
The lignin-based metal protective coating is prepared from 3-12 parts by weight of lignin, 1-10 parts by weight of a compound containing a catechol structure as a functional reagent, 0.0001-0.01 part by weight of a cationic flocculant as a crosslinking reagent and distilled water as a solvent;
the preparation method comprises the following steps: dissolving 3-12 parts by weight of lignin in distilled water to prepare a solution with the mass concentration of 10-30%, uniformly dissolving, adding 1-10 parts of a compound containing a catechol structure as a functional reagent, uniformly stirring and mixing, adding 0.0001-0.01 part of a cationic flocculant as a crosslinking reagent into the mixed solution, and stirring and flocculating for 0.5-24 hours to obtain the lignin-based metal protective coating.
The lignin-based metal protective coating is prepared by effectively combining lignin containing negative charges with a functional reagent by a cationic flocculant under the action of static electricity and hydrogen bonds, or generating a large number of hydrogen bonds between a large number of hydroxyl groups or amino groups in the cationic flocculant and the functional reagent to prepare the lignin-based self-repairing coating; the lignin-based metal protective coating utilizes characteristic functional groups in a functional reagent and metal ions to generate coordination bonds under the alkaline condition, and the coordination bonds have dynamic exchange performance under the action of water and play a role in protecting metals.
The lignin is water soluble alkaline lignin.
The compound containing catechol structure is one or more of tannic acid, tea polyphenol, dopamine hydrochloride and 3, 4-dihydroxy benzoic acid; but is not limited thereto.
The cationic flocculant is a polymer containing amine groups or ammonium groups, such as cationic polyacrylamide, cationic starch and chitosan, or a mixture of polymers containing amine groups or ammonium groups; but is not limited thereto.
The molecular weight of the cationic polyacrylamide is between 10 and 1500 ten thousand; the deacetylation degree of the chitosan is between 75 and 97 percent.
Compared with the prior art, the invention has the following beneficial effects:
the lignin-based metal protective coating and the preparation method thereof utilize a catechol structure to form a coordination compound with metal ions under an alkaline condition, and the coordination compound can present a dynamic exchange effect under the action of water molecules and has the characteristic of self-repairing function; and dopamine containing catechol structure secreted by marine mussels can firmly fix the mussels on the surfaces of various organic, inorganic and metal materials, and a compound containing catechol structure is used as a metal surface coating.
According to the invention, the biomass resource lignin is used as the matrix material of the coating, the surface of the material contains a large amount of negative charges, and the matrix material is combined with a compound containing a catechol structure under the electrostatic action and the hydrogen bond action of a cationic polymer and a functional monomer, so that the environment-friendly metal protective coating with a self-repairing function is prepared.
Lignin is a complex phenolic polymer formed from three alcohol monomers (p-coumaryl alcohol, coniferyl alcohol, sinapyl alcohol) and contains a large number of hydroxyl groups in its structure. The lignin is used as a base material, the feasible selection of the conditions can be met, and meanwhile, the functional monomer containing the catechol structure also contains a large amount of negative charges to meet the design requirement, so compounds containing the catechol structure such as tannic acid, tea polyphenol, dopamine hydrochloride, 3, 4-dihydroxybenzoic acid and the like are used as the functional monomer, but the invention is not limited to the functional monomer. Under the electrostatic action, the cationic flocculant effectively combines lignin containing negative charges with a functional reagent to prepare the lignin-based self-repairing coating; the lignin-based metal protective coating utilizes characteristic functional groups in a functional reagent and metal ions to generate coordination bonds under the alkaline condition, and the coordination bonds have dynamic exchange performance under the action of water and play a role in protecting metals.
The coordination bond formed between catechol and a metal ion may be a tridentate bond, a bidentate bond or a monodentate bond.
The lignin-based metal protective coating disclosed by the invention forms a coordination compound with metal ions, so that the surface of the metal ions is prevented from being oxidized or corroded, and the lignin-based metal protective coating can play a role in protecting the metal under a dry condition and also can play a role in protecting the metal in a wet state.
The paint solvent is water solvent or water solvent, has no environmental pollution, is environment friendly, and has less environmental pollution and less environmental damage.
Drawings
FIG. 1 is the main chemical structure of lignin according to the present invention.
Detailed Description
The lignin-based metal protective coating and the preparation method thereof according to the present invention will be described in detail below with reference to the accompanying drawings.
The lignin-based metal protective coating and the preparation method thereof are prepared by taking 3-12 kg of lignin, 1-10 kg of catechol structure-containing compound as a functional reagent, 0.0001-0.01 kg of cationic flocculant as a crosslinking reagent and distilled water as a solvent in parts by weight.
The preparation method comprises the following steps: dissolving lignin with the weight of 3 kg-12 kg in distilled water to prepare a solution with the mass concentration of 10% -30%, adding 1-10 kg of a compound containing a catechol structure as a functional reagent after uniform dissolution, stirring and mixing uniformly, then adding 0.0001-0.01 kg of a cationic flocculant as a crosslinking reagent into the mixed solution, and stirring and flocculating for 0.5-24 hours to obtain the lignin-based metal protective coating.
The lignin-based metal protective coating is prepared by effectively combining lignin containing negative charges and a functional reagent by a cationic flocculant under the action of static electricity or hydrogen bonds to prepare a lignin-based self-repairing coating; the lignin-based metal protective coating utilizes characteristic functional groups in a functional reagent and metal ions to generate coordination bonds under the alkaline condition, and the coordination bonds have dynamic exchange performance under the action of water and play a role in protecting metals.
The lignin is mainly alkaline lignin soluble in water.
The catechol structure-containing compounds include: compounds having a catechol structure such as tannic acid, tea polyphenol, dopamine hydrochloride, 3, 4-dihydroxybenzoic acid, but are not limited thereto.
The cationic flocculant includes cationic polyacrylamide, cationic starch, chitosan, and other polymers having amine or ammonium groups, but is not limited thereto.
The molecular weight of the cationic polyacrylamide is from 10 ten thousand to 1500 ten thousand.
The deacetylation degree of the chitosan is between 75 and 97 percent.
The coordination bond formed between catechol and a metal ion may be a tridentate bond, a bidentate bond or a monodentate bond.
The coating can not only play a role in protecting metal under a dry condition, but also play a role in protecting metal in a wet state.
The coating solvent is a hydrosolvent or a water-based solvent, and cannot cause pollution to the environment.
Example 1:
dissolving 3kg of alkali lignin in distilled water, coordinating with a solution with the mass concentration of 10%, uniformly dissolving, adding 1kg of functional reagent tannic acid, uniformly stirring and mixing, then adding 0.0001kg of cationic polyacrylamide with the molecular weight of 10 ten thousand into the mixed solution, and stirring and flocculating for 0.5h to obtain the required coating.
Example 2:
dissolving 12kg of alkali lignin in distilled water, coordinating with a solution with the mass concentration of 10%, after uniformly dissolving, adding 10kg of functional reagent tea polyphenol, stirring and uniformly mixing, then adding 0.01kg of cationic starch into the mixed solution, stirring and flocculating for 24h to obtain the required coating.
Example 3:
dissolving 6kg of alkali lignin in distilled water, coordinating with a solution with the mass concentration of 5%, adding 5kg of functional reagent tea polyphenol after uniform dissolution, stirring and mixing uniformly, then adding 0.005kg of chitosan with the deacetylation degree of 75% into the mixed solution, stirring and flocculating for 12h to obtain the required coating.
Example 4:
dissolving 8kg of alkali lignin in distilled water, coordinating with a solution with the mass concentration of 9%, adding 6kg of functional reagent tea polyphenol after uniform dissolution, stirring and mixing uniformly, then adding 0.001kg of chitosan with the deacetylation degree of 99% into the mixed solution, stirring and flocculating for 6h to obtain the required coating.
Example 5:
dissolving 5kg of alkali lignin in distilled water, adding 8% solution of coordination mass concentration, adding 5kg of dopamine hydrochloride serving as a functional reagent after uniform dissolution, stirring and mixing uniformly, then adding 0.005kg of cationic polyacrylamide with molecular weight of 1000 ten thousand into the mixed solution, stirring and flocculating for 2 hours to obtain the required coating.
Example 6:
dissolving 7kg of alkali lignin in distilled water, adding a solution with the coordination mass concentration of 20%, adding 5kg of functional reagent 3, 4-dihydroxybenzoic acid after the alkali lignin is uniformly dissolved, stirring and mixing uniformly, then adding 0.0005kg of cationic polyacrylamide with the molecular weight of 500 ten thousand into the mixed solution, stirring and flocculating for 4 hours to obtain the required coating.
The coatings prepared in examples 1 to 6 were each drawn down on a 10X 10 inch iron plate using a No. 7 draw down bar. Drying the obtained composition in a 60 ℃ blast dryer until the solvent is completely volatilized, forming a layer of cured film on the iron sheet, scratching the cured film by using a sharp blade, completely eliminating scratches after 2 hours under a humid condition, repairing the cured film, and removing the cured film from the iron sheet. And the cured protective coating has a toughness that does not crack under a 20 inch pound reverse impact. After observing 2d, 4d, 6d, 8d, 10d and 60d, the coated iron sheet is intact in a wet state, and the coating itself is not changed obviously.
The above examples demonstrate that the coating prepared by the invention can effectively exert the protection effect on metal.

Claims (8)

1. A lignin-based metal protecting paint is prepared through dissolving alkaline lignin in water to obtain lignin solution, adding functional reagent to said lignin solution, and features that the compound containing catechol structure as functional reagent includes: one or more of tannin, tea polyphenol, dopamine hydrochloride and 3, 4-dihydroxy benzoic acid; stirring and mixing uniformly, and then adding a cationic flocculant serving as a crosslinking reagent into the mixed solution, wherein the cationic flocculant is a polymer containing amino or ammonium groups: stirring and flocculating the cationic polyacrylamide, cationic starch, chitosan or a mixture thereof to obtain lignin-based metal protective coating;
the formula used in the preparation of the coating comprises the following components in parts by weight:
3-12 parts of alkaline lignin; 1-10 parts of a functional reagent; 0.0001-0.01 part of a crosslinking reagent.
2. A lignin-based metal protective coating according to claim 1, wherein:
dissolving 3-12 parts by weight of alkaline lignin in distilled water to prepare a lignin solution with the mass concentration of 10-30%, adding 1-10 parts of a compound containing a catechol structure as a functional reagent after uniform dissolution, stirring and mixing uniformly, adding 0.0001-0.01 part of a cationic flocculant as a crosslinking reagent into the mixed solution, and stirring and flocculating for 0.5-24 hours to obtain the lignin-based metal protective coating.
3. A lignin-based metal protective coating according to claim 2, wherein:
the lignin is water-soluble alkaline lignin;
the compound containing catechol structure is one or more of tannic acid, tea polyphenol, dopamine hydrochloride and 3, 4-dihydroxy benzoic acid;
the cationic flocculant is cationic polyacrylamide, cationic starch, chitosan or a mixture thereof.
4. A method of preparing a lignin-based metal protective coating according to claim 1, wherein: the preparation method comprises the following steps: dissolving and mixing lignin serving as a base material, a cationic flocculant serving as a crosslinking reagent, a compound containing a catechol structure serving as a functional reagent and water serving as a solvent, and effectively combining the lignin containing negative charges and the functional reagent by the cationic flocculant under the electrostatic action to prepare the lignin-based metal protective coating;
the formula used in the preparation of the coating comprises the following components in parts by weight:
3-12 parts of alkaline lignin; 1-10 parts of a functional reagent; 0.0001-0.01 part of a crosslinking reagent.
5. A method of preparing a lignin-based metal protective coating according to claim 1, wherein: the lignin-based metal protective coating is prepared from 3-12 parts by weight of lignin, 1-10 parts by weight of a compound containing a catechol structure as a functional reagent, 0.0001-0.01 part by weight of a cationic flocculant as a crosslinking reagent and distilled water as a solvent;
the preparation method comprises the following steps: dissolving 3-12 parts by weight of lignin in distilled water to prepare a solution with the mass concentration of 10-30%, uniformly dissolving, adding 1-10 catechol structure-containing compounds as functional reagents, uniformly stirring and mixing, adding 0.0001-0.01 part of cationic flocculant as a crosslinking reagent into the mixed solution, and stirring and flocculating for 0.5-24 hours to obtain the lignin-based metal protective coating.
6. A method of making a lignin-based metal protective coating according to claim 5, wherein: the lignin-based metal protective coating is prepared by effectively combining lignin containing negative charges and a functional reagent by a cationic flocculant under the action of static electricity to prepare a lignin-based self-repairing coating; the lignin-based metal protective coating utilizes characteristic functional groups in a functional reagent and metal ions to generate coordination bonds under the alkaline condition, and the coordination bonds have dynamic exchange performance under the action of water and play a role in protecting metals.
7. A method of making a lignin-based metal protective coating according to claim 5, wherein: the compound containing catechol structure is one or more of tannic acid, tea polyphenol, dopamine hydrochloride and 3, 4-dihydroxy benzoic acid;
the cationic flocculant is cationic polyacrylamide, cationic starch, chitosan or a mixture thereof.
8. A method of making a lignin-based metal protective coating according to claim 7, wherein: the molecular weight of the cationic polyacrylamide is between 10 and 1500 ten thousand; the deacetylation degree of the chitosan is between 75 and 97 percent.
CN201711443343.5A 2017-12-27 2017-12-27 Lignin-based metal protective coating and preparation method thereof Expired - Fee Related CN108003792B (en)

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