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

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

Info

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
Authority
CN
China
Prior art keywords
lignin
protective coating
based metal
metal protective
reagent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201711443343.5A
Other languages
Chinese (zh)
Other versions
CN108003792A (en
Inventor
夏南南
孔凡功
吴芹
王守娟
孙浩东
许仃仃
赵鑫
陈洪雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Jiqing Technology Service Co ltd
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN201711443343.5A priority Critical patent/CN108003792B/en
Publication of CN108003792A publication Critical patent/CN108003792A/en
Application granted granted Critical
Publication of CN108003792B publication Critical patent/CN108003792B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711443343.5A CN108003792B (en) 2017-12-27 2017-12-27 Lignin-based metal protective coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711443343.5A CN108003792B (en) 2017-12-27 2017-12-27 Lignin-based metal protective coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108003792A CN108003792A (en) 2018-05-08
CN108003792B true CN108003792B (en) 2020-05-15

Family

ID=62061588

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711443343.5A Expired - Fee Related CN108003792B (en) 2017-12-27 2017-12-27 Lignin-based metal protective coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108003792B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113651963B (en) * 2021-07-16 2022-05-24 华南理工大学 Hyperbranched lignin-based cationic starch multifunctional composite flocculant and preparation and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2406733C1 (en) * 2009-04-27 2010-12-20 Закрытое акционерное общество "Тауер Бизнес Групп" Method of obtaining base for composite anticorrosion coating material and method of obtaining composite anticorrosion coating material using said base
CA2893088C (en) * 2012-12-18 2020-10-20 Akzo Nobel Coatings International B.V. Lignin based coating compositions
CN106220841B (en) * 2016-08-18 2018-06-08 三明学院 Based on Fe3+Amine-modified polyalcohol hydrogel of DOPA and preparation method thereof
CN107354463A (en) * 2017-06-28 2017-11-17 常州杰轩纺织科技有限公司 A kind of vapour phase inhibitor and preparation method thereof

Also Published As

Publication number Publication date
CN108003792A (en) 2018-05-08

Similar Documents

Publication Publication Date Title
CN109181490B (en) Water-based epoxy anticorrosive paint and preparation method thereof
CN110922803A (en) Graphene-doped water-based conductive anticorrosive coating composition for surface of steel bar in concrete and preparation method thereof
CN110964410A (en) Water-based graphene heavy-duty anticorrosive paint
CN103614016B (en) A kind of water-based antirust agent
CN112778817B (en) Corrosion-resistant coating for steel bar for marine concrete and preparation method of corrosion-resistant coating
CN104140739B (en) Steel structure with water-base epoxy with rust anti-corrosive primer preparation method
CN108531006A (en) The waterborne anti-corrosive primer and preparation method thereof of graphene enhancing
CN109161340A (en) A kind of environmental friendly, anti-corrosive composite coating
CN108003792B (en) Lignin-based metal protective coating and preparation method thereof
CN108531043B (en) Rare earth modified graphene water-based zinc-rich primer
CN108624191B (en) Green antirust pretreatment film forming solution for steel plate
CN112500764B (en) Solvent-free epoxy zinc-rich anticorrosive paint and preparation method thereof
CN116239935B (en) Solvent-free self-repairing anticorrosive paint based on lithium salt and preparation and use methods thereof
CN110776802A (en) Epoxy modified acrylic acid environment-friendly paint for hardware parts and preparation method thereof
CN111423752A (en) Water-based inorganic zinc-rich primer for heavy corrosion protection
CN112852260B (en) Durable epoxy resin anticorrosive paint and preparation method and application thereof
CN104449089A (en) Water-based highly chloridized polypropylene anticorrosive primer and preparation method thereof
CN109535939B (en) Antirust primer and application thereof
CN114181609A (en) Zinc-aluminum-magnesium alloy modified water-based cold-spraying zinc coating and preparation method thereof
CN107099218A (en) A kind of high solid selfreparing corrosion-resistant epoxy paint and preparation method thereof
CN102876196B (en) Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment
CN104530937B (en) Exempt from the anti-corrosive primer and preparation method thereof of steel pre-treatment
CN110982384A (en) Special gas-phase anticorrosive paint and preparation method thereof
CN117210087A (en) Iron-based surface anti-corrosion spraying liquid and preparation method and application thereof
CN115322607B (en) Chlorinated polyester alloy heat-resistant anticorrosive paint and preparation process thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20221215

Address after: 250306 Room 3115, No. 135, Ward Avenue, Ping'an Street, Changqing District, Jinan City, Shandong Province

Patentee after: Shandong Jiqing Technology Service Co.,Ltd.

Address before: 250353 Qilu Industrial University, 3501 University Road, Changqing District, Ji'nan, Shandong

Patentee before: Qilu University of Technology

TR01 Transfer of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200515

CF01 Termination of patent right due to non-payment of annual fee