CN119351027B - A method for preparing an environmentally friendly adhesive for aluminum alloys - Google Patents
A method for preparing an environmentally friendly adhesive for aluminum alloysInfo
- Publication number
- CN119351027B CN119351027B CN202411626660.0A CN202411626660A CN119351027B CN 119351027 B CN119351027 B CN 119351027B CN 202411626660 A CN202411626660 A CN 202411626660A CN 119351027 B CN119351027 B CN 119351027B
- Authority
- CN
- China
- Prior art keywords
- adhesive
- polycarboxylic acid
- aluminum alloy
- reaction
- water
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, and discloses a preparation method of an environment-friendly adhesive for aluminum alloy, which comprises the steps of adding water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate and isooctyl alcohol sodium sulfate into a reaction kettle, and uniformly stirring to obtain the environment-friendly adhesive for aluminum alloy. The 8-hydroxyquinoline group contained in the 8-hydroxyquinoline polycarboxylic acid adhesive can interact with the surface of aluminum alloy or tinplate in a coordinated mode, meanwhile, carboxyl contained in the polycarboxylic acid adhesive and carboxyl and other groups in the aqueous acrylic resin emulsion have the effects of hydrogen bonding and the like, so that the polycarboxylic acid adhesive plays a role in bridging the groups of aluminum alloy and the like with an acrylic resin paint film, the adhesive force and the adhesive property between the polycarboxylic acid adhesive and the acrylic resin paint film and a substrate are enhanced, better adhesive force grade is shown, and the T peel strength is higher.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a preparation method of an environment-friendly adhesive for aluminum alloy.
Background
In the past industrial production, aluminum alloys have been increasingly used, and problems have been caused by poor bonding of acrylic resins to metal substrates such as aluminum alloys. For example, in the metal processing process, the phenomena of coating falling off, infirm adhesion and the like are easy to occur, so that the appearance quality of the product is affected, and the service life and the stability of the product are reduced. In the field of surface treatment, insufficient adhesion also makes the protective effect greatly compromised, increasing the risk of corrosion and damage to the metal. Some industrial production links with high requirements on bonding strength, such as automobile manufacturing, aerospace and the like, and the performance defect severely restricts the progress of the process and the quality of products. Therefore, in order to solve the long-standing troublesome problems, a preparation method of the environment-friendly adhesive for aluminum alloy is developed.
Disclosure of Invention
The invention provides a preparation method of an environment-friendly adhesive for aluminum alloy, aiming at the defects of the prior art, and the adhesive force and the cohesive force between acrylic resin and metal materials such as aluminum alloy can be improved.
Adding water into a reaction vessel, adding water with the molar ratio of (0.05-0.06) 1 (0.08-0.14) (0.07-0.08) allyl polyoxyethylene ether, methacrylic acid, 5- (2-methylallyloxy methylene) -8-quinoline hydrochloride, ammonium persulfate, heating to 75-85 ℃ in an N 2 atmosphere, stirring and reacting for 4-6h, drying and dehydrating after the reaction, and washing with ethanol to obtain the 8-hydroxyquinoline polycarboxylic acid adhesive.
(2) Adding water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate and isooctyl alcohol sodium sulfate into a reaction kettle, heating to 40-60 ℃, uniformly stirring, cooling and discharging to obtain the environment-friendly adhesive for aluminum alloy.
Preferably, in the step (2), the mass ratio of water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate and isooctyl alcohol sodium sulfate is (26-32): (17-20): (0.7-1.3): (4-6): (13-18): (10-14): (6-10): (4-7): (1.5-2.2).
Preferably, the preparation method of the 5- (2-methylallyloxymethylene) -8-quinoline hydrochloride comprises the steps of adding 1, 4-dioxane, 2-methylallyl alcohol, sodium acetate, water and 5- (chloromethyl) -8-quinoline hydrochloride into a reaction vessel, heating to 80-95 ℃ in N 2 atmosphere, reacting for 3-5h, concentrating under reduced pressure, filtering, washing with water, and drying to obtain the 5- (2-methylallyloxymethylene) -8-quinoline hydrochloride.
Preferably, the molar ratio of 2-methylallyl alcohol, 5- (chloromethyl) -8-quinoline hydrochloride and sodium acetate is (2.5-3.4): 1 (1-1.1).
The invention has the beneficial technical effects that 5- (chloromethyl) -8-quinolyl alcohol hydrochloride and 2-methallyl alcohol are utilized to generate 5- (2-methallyloxy methylene) -8-quinolyl alcohol hydrochloride under the condition of taking sodium acetate as a catalyst, then the 5- (2-methallyloxy methylene) -8-quinolyl alcohol hydrochloride and allyl polyoxyethylene ether and methacrylic acid are subjected to polymerization reaction to obtain the 8-hydroxyquinolyl polycarboxylic acid adhesive, and finally the 8-hydroxyquinolyl polycarboxylic acid adhesive is compounded with water, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, sulfosuccinate, isooctyl alcohol sodium sulfate and the like to obtain the environment-friendly adhesive for aluminum alloy.
The environment-friendly adhesive contains the 8-hydroxyquinoline polycarboxylic acid adhesive, wherein the 8-hydroxyquinoline group contained in the adhesive can interact with the surface of aluminum alloy or tin plate in a coordinated mode, and meanwhile carboxyl contained in the polycarboxylic acid adhesive and carboxyl and other groups in aqueous acrylic resin emulsion are subjected to hydrogen bonding and other actions, so that the polycarboxylic acid adhesive plays a role in bridging the groups of aluminum alloy and the like with an acrylic resin paint film, enhances the adhesive force and adhesive property between the polycarboxylic acid adhesive and the acrylic resin paint film and a substrate, shows better adhesive force grade and greater T peel strength.
Drawings
FIG. 1 is a reaction scheme for the preparation of 5- (2-methylallyloxymethylene) -8-quinolinolate hydrochloride.
Detailed Description
Example 1
(1) To the reaction vessel were added 10mL of 1, 4-dioxane, 7.5mmo of 2-methallyl alcohol, 3.1mmo of sodium acetate, 10mL of water, 3mmo of 5- (chloromethyl) -8-quinoline hydrochloride, and in an atmosphere of N 2, the mixture was heated to 85℃to conduct the reaction for 4 hours, concentrated under reduced pressure, filtered, washed with water, and dried to obtain 5- (2-methallyloxymethylene) -8-quinoline hydrochloride.
(2) Adding water into a reaction vessel, adding 0.15 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid and 0.3 mmol of 5- (2-methylallyloxy methylene) -8-quinoline hydrochloride, heating to 80 ℃ in an N 2 atmosphere, adding 0.24 mmol of ammonium persulfate, stirring for reaction for 6 hours, drying for water removal after reaction, and washing with ethanol to obtain the 8-hydroxyquinoline polycarboxylic acid adhesive.
(3) 32G of water, 17g of potassium hydroxide, 0.9g of sodium chloride, 6g of sodium gluconate, 13g of anhydrous tripotassium phosphate, 12g of polyether DF-20, 6g of 8-hydroxyquinoline polycarboxylic acid adhesive, 4g of sulfosuccinate and 1.5g of isooctyl alcohol sodium sulfate are added into a reaction kettle, heated to 45 ℃, stirred uniformly, cooled and discharged to obtain the environment-friendly adhesive for aluminum alloy.
Example 2
(1) To the reaction vessel, 10mL of 1, 4-dioxane, 8 mmoles of 2-methallyl alcohol, 3.3 mmoles of sodium acetate, 10mL of water, 3 mmoles of 5- (chloromethyl) -8-quinolinolate hydrochloride were added, and the mixture was heated to 95℃in an atmosphere of N 2 to react for 3 hours, concentrated under reduced pressure, filtered, washed with water, and dried to give 5- (2-methallyloxymethylene) -8-quinolinolate hydrochloride.
(2) Adding water into a reaction vessel, adding 0.18mmo of allyl polyoxyethylene ether, 3mmo of methacrylic acid, 0.42mmo of 5- (2-methylallyloxy methylene) -8-quinoline hydrochloride, heating to 85 ℃ in an N 2 atmosphere, adding 0.21mmo of ammonium persulfate, stirring for reaction for 4 hours, drying for water removal after reaction, and washing with ethanol to obtain the 8-hydroxyquinoline polycarboxylic acid adhesive.
(3) 28G of water, 17g of potassium hydroxide, 0.7g of sodium chloride, 5g of sodium gluconate, 15g of anhydrous tripotassium phosphate, 10g of polyether DF-20, 7g of 8-hydroxyquinoline polycarboxylic acid adhesive, 5g of sulfosuccinate and 2.2g of isooctyl alcohol sodium sulfate are added into a reaction kettle, heated to 40 ℃, stirred uniformly, cooled and discharged to obtain the environment-friendly adhesive for aluminum alloy.
Example 3
(1) To the reaction vessel were added 10mL of 1, 4-dioxane, 10.2mmo of 2-methallyl alcohol, 3mmo of sodium acetate, 10mL of water, 3mmo of 5- (chloromethyl) -8-quinolinolate hydrochloride, and the mixture was heated to 80℃in an atmosphere of N 2 to conduct the reaction for 5 hours, concentrated under reduced pressure, filtered, washed with water, and dried to give 5- (2-methallyloxymethylene) -8-quinolinolate hydrochloride.
(2) Adding water into a reaction vessel, adding 0.17 mmol of allyl polyoxyethylene ether, 3mmol of methacrylic acid and 0.24 mmol of 5- (2-methylallyloxy methylene) -8-quinoline hydrochloride, heating to 75 ℃ in an N 2 atmosphere, adding 0.24 mmol of ammonium persulfate, stirring and reacting for 5 hours, drying and dehydrating after the reaction, and washing with ethanol to obtain the 8-hydroxyquinoline polycarboxylic acid adhesive.
(3) 30G of water, 18g of potassium hydroxide, 1.1g of sodium chloride, 4g of sodium gluconate, 18g of anhydrous tripotassium phosphate, 13g of polyether DF-20, 8.5g of 8-hydroxyquinoline polycarboxylic acid adhesive, 6g of sulfosuccinate and 2g of isooctyl alcohol sodium sulfate are added into a reaction kettle, heated to 55 ℃, stirred uniformly, cooled and discharged to obtain the environment-friendly adhesive for aluminum alloy.
Example 4
(1) To the reaction vessel were added 10mL of 1, 4-dioxane, 9 mmoles of 2-methallyl alcohol, 3.1 mmoles of sodium acetate, 10mL of water, 3 mmoles of 5- (chloromethyl) -8-quinolinolate hydrochloride, and the mixture was heated to 85℃in an atmosphere of N 2 to conduct a reaction for 4 hours, concentrated under reduced pressure, filtered, washed with water, and dried to give 5- (2-methallyloxymethylene) -8-quinolinolate hydrochloride.
(2) Adding water into a reaction vessel, adding 0.18mmo of allyl polyoxyethylene ether, 3mmo of methacrylic acid and 0.36mmo of 5- (2-methylallyloxy methylene) -8-quinoline hydrochloride into the reaction vessel, heating to 75 ℃ in an N 2 atmosphere, adding 0.23mmo of ammonium persulfate into the reaction vessel, stirring the reaction vessel for 4 hours, drying the reaction vessel to remove water, and washing the reaction vessel with ethanol to obtain the 8-hydroxyquinoline polycarboxylic acid adhesive.
(3) 26G of water, 20g of potassium hydroxide, 1.3g of sodium chloride, 6g of sodium gluconate, 18g of anhydrous tripotassium phosphate, 14g of polyether DF-20, 10g of 8-hydroxyquinoline polycarboxylic acid adhesive, 7g of sulfosuccinate and 1.5g of isooctyl alcohol sodium sulfate are added into a reaction kettle, heated to 60 ℃, stirred uniformly, cooled and discharged to obtain the environment-friendly adhesive for aluminum alloy.
Comparative example 1
(1) 32G of water, 17g of potassium hydroxide, 0.9g of sodium chloride, 6g of sodium gluconate, 13g of anhydrous tripotassium phosphate, 12g of polyether DF-20, 4g of sulfosuccinate and 1.5g of isooctyl alcohol sodium sulfate are added into a reaction kettle, heated to 45 ℃, stirred uniformly, cooled and discharged to obtain the environment-friendly adhesive for aluminum alloy.
Comparative example 2
(1) Adding water into a reaction vessel, adding 0.15mmo of allyl polyoxyethylene ether and 3mmo of methacrylic acid, heating to 80 ℃ in an N 2 atmosphere, adding 0.24mmo of ammonium persulfate, stirring for reaction for 6 hours, drying for dewatering after reaction, and washing with ethanol to obtain the polycarboxylic acid adhesive.
(2) 32G of water, 17g of potassium hydroxide, 0.9g of sodium chloride, 6g of sodium gluconate, 13g of anhydrous tripotassium phosphate, 12g of polyether DF-20, 6g of polycarboxylic acid adhesive, 4g of sulfosuccinate and 1.5g of isooctyl alcohol sodium sulfate are added into a reaction kettle, heated to 45 ℃, stirred uniformly, cooled and discharged to obtain the environment-friendly adhesive for aluminum alloy.
3G of an environment-friendly adhesive for aluminum alloy is weighed and added into 100mL of aqueous acrylic resin emulsion, the emulsion is sprayed on the surface of an aluminum alloy plate or a tinplate substrate after stirring, and the aluminum alloy is dried at 120 ℃ to prepare a paint film.
With reference to the method of GB/T9286-2021, the adhesion rating between the paint film and the substrate is tested.
The T peel strength between the paint film and the substrate was tested with reference to the method of GB/T2791-1995.
TABLE 1
TABLE 2
As shown in tables 1 to 2, examples 1 to 4 of the present invention were good in adhesion rating and high in T peel strength. The environment-friendly adhesive for aluminum alloy in the embodiment contains the 8-hydroxyquinoline polycarboxylic acid adhesive, wherein the 8-hydroxyquinoline group contained in the adhesive can coordinate with the surface of aluminum alloy or tin plate and the like, and meanwhile, the carboxyl group contained in the polycarboxylic acid adhesive and the carboxyl group and other groups in the aqueous acrylic resin emulsion have the function of hydrogen bonding and the like, so that the polycarboxylic acid adhesive plays a role of bridging the groups of aluminum alloy and the like with an acrylic resin paint film, enhances the adhesive force and the adhesive property between the polycarboxylic acid adhesive and the acrylic resin paint film and a substrate, shows better adhesive force grade and larger T peel strength.
In comparative example 1, the adhesion grade between the adhesive and a metal material such as aluminum alloy was lower and the peel strength was smaller, as compared with example 1, in which no 8-hydroxyquinoline polycarboxylic acid adhesive was added.
Comparative example 2 is different from example 1 in that the 8-hydroxyquinoline based polycarboxylic acid adhesive is replaced with a polycarboxylic acid adhesive, the polycarboxylic acid adhesive lacks an 8-hydroxyquinoline group, the interaction force between a base material such as aluminum alloy and the adhesive is low, the adhesion and the adhesive property between the acrylic resin paint film and the base material are poor, resulting in poor adhesion grade, and lower T peel strength.
Claims (3)
1. The preparation method of the environment-friendly adhesive for the aluminum alloy is characterized by comprising the following steps of:
(1) Adding water, allyl polyoxyethylene ether, methacrylic acid and 5- (2-methylallyloxy methylene) -8-quinolyl hydrochloride into a reaction container, heating to a reaction temperature in an N 2 atmosphere, adding ammonium persulfate, stirring for reaction, drying for removing water after the reaction, and washing with ethanol to obtain an 8-hydroxyquinolyl polycarboxylic acid adhesive;
(2) Adding water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate and isooctyl alcohol sodium sulfate into a reaction kettle, heating to 40-60 ℃, uniformly stirring, cooling and discharging to obtain an environment-friendly adhesive for aluminum alloy;
In the step (1), the mol ratio of allyl polyoxyethylene ether, methacrylic acid, 5- (2-methylallyloxymethylene) -8-quinoline hydrochloride and ammonium persulfate is (0.05-0.06): 1 (0.08-0.14): 0.07-0.08);
In the step (2), the mass ratio of water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate and isooctyl alcohol sodium sulfate is (26-32): (17-20): (0.7-1.3): (4-6): (13-18): (10-14): (6-10): (4-7): (1.5-2.2);
The preparation method of the 5- (2-methylallyloxymethylene) -8-quinoline hydrochloride comprises the steps of adding 1, 4-dioxane, 2-methylallyl alcohol, sodium acetate, water and 5- (chloromethyl) -8-quinoline hydrochloride into a reaction vessel, reacting in an N 2 atmosphere, concentrating under reduced pressure, filtering, washing with water, and drying to obtain 5- (2-methylallyloxymethylene) -8-quinoline hydrochloride;
the molar ratio of the 2-methallyl alcohol to the 5- (chloromethyl) -8-quinoline hydrochloride to the sodium acetate is (2.5-3.4) 1 (1-1.1).
2. The method for producing an environmentally friendly adhesive for aluminum alloys according to claim 1, wherein in the step (1), the reaction temperature is 75-85 ℃ and the reaction time is 4-6 hours.
3. The method for producing an environment-friendly adhesive for aluminum alloy according to claim 1, wherein in the method for producing 5- (2-methylallyloxymethylene) -8-quinolinolato hydrochloride, the reaction temperature is 80-95 ℃ and the reaction time is 3-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411626660.0A CN119351027B (en) | 2024-11-14 | 2024-11-14 | A method for preparing an environmentally friendly adhesive for aluminum alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411626660.0A CN119351027B (en) | 2024-11-14 | 2024-11-14 | A method for preparing an environmentally friendly adhesive for aluminum alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN119351027A CN119351027A (en) | 2025-01-24 |
| CN119351027B true CN119351027B (en) | 2025-12-05 |
Family
ID=94307455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411626660.0A Active CN119351027B (en) | 2024-11-14 | 2024-11-14 | A method for preparing an environmentally friendly adhesive for aluminum alloys |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119351027B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919953A (en) * | 2005-08-25 | 2007-02-28 | 国家淀粉及化学投资控股公司 | Quinolinols and quinolinol derivatives as adhesion promoters in die attach adhesives |
| CN111183998A (en) * | 2020-02-28 | 2020-05-22 | 吉林农业科技学院 | A kind of bactericidal composition containing 8-hydroxyquinoline calcium for preventing and treating downy mildew and late blight |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH59415A (en) * | 1912-08-30 | 1913-05-02 | Farbenfab Vorm Bayer F & Co | Process for the preparation of 2-phenylquinoline-4-carboxylic acid |
| DE2439202C3 (en) * | 1974-08-16 | 1979-09-27 | Friedr. Blasberg Gmbh & Co Kg, 5650 Solingen | Alkaline aqueous bath for etching aluminum and aluminum alloys |
| US5936071A (en) * | 1998-02-02 | 1999-08-10 | Clariant Finance (Bvi) Limited | Process for making a photoactive compound and photoresist therefrom |
| CN101595000B (en) * | 2006-12-07 | 2011-04-06 | 爱克发-格法特公司 | Method for manufacturing information carrier |
| BRPI0912020A2 (en) * | 2008-05-16 | 2019-03-06 | Procter & Gamble | photocatalyst compositions and methods of incorporation |
| CN106146396B (en) * | 2015-04-27 | 2018-11-02 | 中国石油化工股份有限公司 | Quinoline type derivative and corrosion inhibiting and descaling agent and its application and oil-field flooding pit shaft corrosion protection method of scale inhibition |
-
2024
- 2024-11-14 CN CN202411626660.0A patent/CN119351027B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919953A (en) * | 2005-08-25 | 2007-02-28 | 国家淀粉及化学投资控股公司 | Quinolinols and quinolinol derivatives as adhesion promoters in die attach adhesives |
| CN111183998A (en) * | 2020-02-28 | 2020-05-22 | 吉林农业科技学院 | A kind of bactericidal composition containing 8-hydroxyquinoline calcium for preventing and treating downy mildew and late blight |
Also Published As
| Publication number | Publication date |
|---|---|
| CN119351027A (en) | 2025-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111285962A (en) | Water-based environment-friendly acrylic emulsion pressure-sensitive adhesive for protective film and preparation method thereof | |
| CN112795711A (en) | A kind of multifunctional high absorption chrome tanning aid and its preparation method and application | |
| CN119351027B (en) | A method for preparing an environmentally friendly adhesive for aluminum alloys | |
| CN112048716A (en) | Concentrated silane coating agent and preparation method thereof | |
| CN107746441B (en) | Efficient preparation method of polyvinyl butyral resin | |
| CN111234727A (en) | Waterborne environmental protection acrylic emulsion pressure sensitive adhesive protection film | |
| CN112759693A (en) | Single-component emulsion suitable for coating surface of PP (polypropylene) artificial synthetic paper and synthetic method thereof | |
| CN115490668A (en) | Pyrimidyl imidazole compound, preparation method thereof and organic weldable protective agent | |
| CN103013202A (en) | Impact-resistant epoxy resin paint | |
| CN102632672B (en) | Color-coated plate and method for manufacturing same | |
| CN112920299A (en) | Preparation method of automobile-grade PVB resin for improving yellowing resistance | |
| CN114671984B (en) | Oil-resistant acrylic acid adhesive and preparation method thereof | |
| CN100400551C (en) | Improved manufacturing method of polyvinyl alcohol-β-cyanoethyl ether | |
| CN113136156A (en) | Formula and production process of novel glue | |
| CN114940884A (en) | Adhesive for increasing binding force between copper surface and dielectric material of printed circuit board | |
| CN115181471A (en) | A kind of organic passivator for silver-plated layer of copper-free silver-plated glass mirror and preparation method thereof | |
| CN115304479B (en) | Preparation method and application of water-washing-free solvent-free modified UV monomer | |
| CN115477881B (en) | Water-based wear-resistant transparent antifogging resin polymer and preparation method thereof | |
| CN113072443A (en) | Novel production process of liquid hindered phenol antioxidant 1135 | |
| CN120059558B (en) | A method for preparing high-temperature resistant epoxy gel coat for wind turbine blade mold | |
| CN111961155A (en) | Method for preparing low-viscosity anionic surfactant | |
| CN120623377B (en) | Polyvinyl alcohol and preparation method thereof | |
| CN116288363B (en) | Long-acting water-based antirust agent and preparation method and application thereof | |
| CN104762020B (en) | The method preparing fire bond with aluminium alloy extrusions factory oxidized waste water mud | |
| CN1089292A (en) | The manufacture method of white glue with vinyl |
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 |