CN113512159A - Aqueous single-component modified epoxy resin and preparation method and application thereof - Google Patents
Aqueous single-component modified epoxy resin and preparation method and application thereof Download PDFInfo
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- CN113512159A CN113512159A CN202110859401.2A CN202110859401A CN113512159A CN 113512159 A CN113512159 A CN 113512159A CN 202110859401 A CN202110859401 A CN 202110859401A CN 113512159 A CN113512159 A CN 113512159A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
The invention provides a waterborne single-component modified epoxy resin and a preparation method and application thereof. The waterborne single-component modified epoxy resin provided by the invention comprises the raw materials of epoxy resin, a modifier, an adhesion promoter, a catalyst, an initiator, a hydrophilic monomer, a cosolvent and a neutralizing agent, wherein the epoxy resin comprises at least one of E20, E44, E51, E54, F51 and E12. The waterborne single-component modified epoxy resin has the advantages of convenient use, long service time, quick drying, high gloss, good salt spray resistance, good adhesion to substrates which are difficult to adhere, such as galvanized plates, aluminum plates and the like, wide universality and environmental friendliness. The invention also provides a coating composition and a coating product containing the waterborne one-component modified epoxy resin.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a waterborne single-component modified epoxy resin, and a preparation method and application thereof.
Background
Epoxy resins (Epoxy resins) are high molecular oligomers which contain two or more Epoxy groups and form a practical thermosetting product by reaction of the Epoxy groups with an alicyclic or aromatic organic compound as a backbone. The single epoxy resin has little use value, and the application value can be reflected only by the polymer which reacts with the curing agent to generate a three-dimensional network structure, and the epoxy resin belongs to thermosetting resin. There are three main types of epoxy resins commonly used: bisphenol a type epoxy resins, novolac epoxy resins, and bisphenol F type epoxy resins. Epoxy resins contain active groups such as epoxy groups, hydroxyl groups, ether bonds, and polar groups, and have many very excellent properties. Epoxy resin can be used only by matching with a curing agent.
With the increasing awareness of environmental issues and the increasing emergence of indoor and outdoor air quality standards, some solvent-based coatings with high Volatile Organic Compound (VOC) content have presented significant challenges. The water-based resin is a hotspot and a focus of research and development at present based on the characteristics of environmental protection and low VOC emission, and has a wide application prospect. Among them, the aqueous one-component epoxy dispersion is a film-forming material for preparing aqueous industrial coatings, and the preparation method thereof generally comprises an external emulsification method and a self-emulsification method.
In the related art, CN101463180B discloses a preparation method of an aqueous single-component external emulsified epoxy resin emulsion, which adopts a nonionic emulsifier and an anionic emulsifier to emulsify epoxy resin, and although the operation process is simple, the disadvantage is that the external emulsification method has large particle size of the prepared epoxy resin emulsion and poor storage stability. CN108424521A discloses a preparation method of an aqueous self-emulsifying single-component epoxy resin emulsion, which adopts unsaturated fatty acid modified epoxy resin, has high unsaturated fatty acid content, slow drying speed and poor adhesion to substrates difficult to adhere, such as galvanized plates, aluminum materials and the like. Therefore, there is still a need for further improvements in the existing aqueous one-component modified epoxy resin dispersions.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the waterborne single-component modified epoxy resin provided by the invention is convenient to use, long in service life, quick-drying, high in gloss, good in salt spray resistance, particularly good in adhesion to substrates difficult to adhere, such as galvanized plates, aluminum plates and the like, wide in universality and environment-friendly.
The invention also provides a preparation method of the waterborne single-component modified epoxy resin.
The invention also provides application of the waterborne single-component modified epoxy resin.
The invention provides a waterborne single-component modified epoxy resin, which is prepared from the following raw materials of epoxy resin, a modifier, an adhesion promoter, a catalyst, an initiator, a hydrophilic monomer, a cosolvent and a neutralizing agent;
the epoxy resin includes at least one of E20, E44, E51, E54, F51, and E12.
The waterborne single-component modified epoxy resin disclosed by the invention at least has the following beneficial effects:
compared with a two-component aqueous epoxy system, the single-component epoxy resin has the advantages of larger molecular weight, more convenient use and long service time, and chemical reagents such as phosphoric acid, polyphosphoric acid adhesion promoters and the like are reacted and combined with the epoxy system through chemical modification, so that the water-based single-component modified epoxy resin has the characteristic of good adhesion to substrates difficult to adhere such as galvanized plates, aluminum plates and the like.
The waterborne single-component modified epoxy resin disclosed by the invention can be cured without a waterborne epoxy curing agent as a two-component waterborne epoxy system in the using process, and in addition, the two-component epoxy system also has the problem of an activation period.
In the preparation of raw materials:
one of the functions of the modifier is to react with an epoxy group, introduce a double bond and react with an acrylate monomer.
The adhesion promoter has the function of reacting with epoxy resin, thereby having better adhesion to the base material difficult to adhere and enabling the base material to become a single component.
The function of the catalyst is to catalyze the reaction to occur.
The function of the initiator is as follows: initiating unsaturated double bonds to carry out free radical polymerization.
One of the functions of the hydrophilic monomer is to make the epoxy resin water-borne.
One of the functions of the cosolvent is to reduce the viscosity during the reaction and prevent imploding gel, and the cosolvent is used as a dispersion medium.
The function of the neutralizer is as follows: and the neutralization reaction is carried out with acid in the waterborne epoxy resin, and the pH value of the medium is adjusted.
One of the functions of deionized water is as a dispersion medium.
In the raw materials, the epoxy resin comprises at least one of E20, E44, E51, E54, F51 and E12.
According to some embodiments of the invention, the method comprises the following raw materials in parts by weight:
epoxy resin: 300 to 1000 parts by weight of a water-soluble polymer,
modifying agent: 150 to 600 parts of (A) by weight,
an adhesion promoter: 5 to 20 parts of (A) a water-soluble polymer,
catalyst: 0.5 to 2 parts by weight of a stabilizer,
initiator: 0.2 to 15 portions of
Hydrophilic monomer: 2 to 80 parts by weight of a stabilizer,
co-solvent: 150 to 400 parts by weight of a stabilizer,
neutralizing agent: 80-120 parts of (a) a water-soluble polymer,
deionized water: 300-2000 parts.
According to some embodiments of the invention, the modifier comprises at least one of linseed oil fatty acid, methacrylate ester, bisphenol a, benzoic acid, coconut oil fatty acid, dehydrated castor oil fatty acid, soybean oil fatty acid.
According to some embodiments of the invention, the adhesion promoter comprises at least one of an epoxy phosphate, a dimer acid, a phosphoric acid, and a polyphosphoric acid.
According to some embodiments of the invention, the catalyst comprises at least one of zinc peroxide, boron trifluoride amine complex, boric acid, boron trifluoride etherate complex, triphenylphosphine, and tetrabutylammonium bromide.
According to some embodiments of the invention, the initiator comprises at least one of DTAP, AIBN, BPO, TBPO, TBPB, DTBP.
According to some embodiments of the invention, the hydrophilic monomer comprises at least one of maleic anhydride, polyether sulfonate, polyester sulfonate, acrylic acid, methacrylic acid, polyethylene glycol 2000, polyethylene glycol 4000, and polyethylene glycol 6000.
According to some embodiments of the invention, the co-solvent comprises at least one of propylene glycol butyl ether, ethylene glycol tertiary butyl ether and isopropyl alcohol.
According to some embodiments of the invention, the neutralizing agent comprises triethylamine.
The second aspect of the present invention provides a method for preparing the above aqueous one-component modified epoxy resin, comprising the steps of:
s1: mixing the epoxy resin, part of the modifier, the adhesion promoter, the catalyst and the hydrophilic monomer according to the proportion, and then heating for reaction;
s2: cooling the product of the step S1, and adding the cosolvent, the initiator and the residual modifier;
s3: and (5) cooling the product obtained in the step S2, and adding a neutralizing agent and deionized water for dispersing and emulsifying.
The third aspect of the present invention provides a coating composition comprising the above aqueous one-component modified epoxy resin.
In a fourth aspect, the present invention provides a coated product comprising a substrate, and an aqueous one-component modified epoxy resin coated on the substrate.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment prepares the aqueous single-component modified epoxy resin, and the specific preparation process comprises the following steps:
putting 800g of E12 epoxy resin, 200g of linseed oil fatty acid sesame, 72g of soybean oil fatty acid and 1.1g of zinc oxide catalyst into a reaction kettle, heating to 140 ℃, and reacting until the acid value is less than 3; 355g of ethylene glycol tert-butyl ether and 14g of epoxy phosphate are added and uniformly stirred, a mixture of 7g of DTAP initiator and 280g of methyl methacrylate is dropwise added at the temperature of 150 ℃ for 3-4h, a mixture of 2g of DTAP initiator and 65g of acrylic acid is dropwise added at 0.5-1h, the temperature is kept at 150 ℃ for 1h, then 1g of DTAP initiator is supplemented for the first time, the temperature is kept for 1h, then 1g of DTAP initiator is supplemented for the second time, the temperature is kept for 1h, and the temperature is kept for 2-3h by supplementing 1g of DTAP initiator for the third time. Cooling to 80 ℃, dripping 91g of triethylamine neutralizer within 30 minutes, dripping 1790g of deionized water within 1.5 hours, starting the rotation speed to 600-800r/min, stirring for 1.5 hours, and then obtaining the aqueous single-component modified epoxy resin dispersoid through phase transformation.
Through preliminary tests, the waterborne single-component modified epoxy resin prepared by the invention has the following characteristics:
solid content: 40 percent of the total weight of the mixture,
viscosity (25 ℃) mpa.s: is less than or equal to 2000 percent,
storage stability: the layers are not layered for six months,
appearance: the white-white blue-light liquid,
particle size: less than or equal to 0.3 mu m.
Example 2
The embodiment prepares the aqueous single-component modified epoxy resin, and the specific preparation process comprises the following steps:
380g of E51 epoxy resin, 6g of F51 novolac epoxy resin, 4.5g of polyether sulfonate, bisphenol A185g, 40g of benzoic acid, 10g of coconut oil fatty acid and 6.25g of epoxy phosphate are heated to 100 ℃, stirred and mixed uniformly, 0.9g of boron trifluoride amine complex is added, the mixture reacts for 2 hours at the temperature of 120-130 ℃, and the epoxy value is measured by sampling;
when the theoretical value is reached, 269g of ethylene glycol tert-butyl ether is added and uniformly stirred, 359g of deionized water is slowly dropped when the temperature is reduced to 60 ℃, the rotation speed is started to 1200r/min, and after stirring for 2 hours, the aqueous single-component modified epoxy resin dispersoid is obtained through phase transition.
Through preliminary tests, the waterborne single-component modified epoxy resin prepared by the invention has the following characteristics:
solid content: the content of the active carbon is 49.8%,
viscosity (25 ℃) mpa.s: is less than or equal to 3000 percent,
storage stability: the layers are not layered for six months,
appearance: the white liquid is a milky white liquid,
particle size: less than or equal to 0.4 mu m.
Example 3
The embodiment prepares the aqueous single-component modified epoxy resin, and the specific preparation process comprises the following steps:
putting 800g of E12 epoxy resin, 150g of dehydrated castor fatty acid hemp, 122g of soybean oil fatty acid and 1.1g of zinc oxide catalyst into a reaction kettle, heating to 140 ℃, and reacting until the acid value is less than 3; 355g of ethylene glycol tert-butyl ether and 14g of epoxy phosphate are added and uniformly stirred, a mixture of 7g of DTAP initiator and 280g of methyl methacrylate is dropwise added at the temperature of 150 ℃ for 3-4h, a mixture of 2g of DTAP initiator and 65g of acrylic acid is dropwise added at 0.5-1h, the temperature is kept at 150 ℃ for 1h, then 1g of DTAP initiator is supplemented for the first time, the temperature is kept for 1h, then 1g of DTAP initiator is supplemented for the second time, the temperature is kept for 1h, and the temperature is kept for 2-3h by supplementing 1g of DTAP initiator for the third time. Cooling to 80 ℃, dripping 91g of triethylamine neutralizer within 30 minutes, dripping 1790g of deionized water within 1.5 hours, starting the rotation speed to 600-800r/min, stirring for 1.5 hours, and then obtaining the aqueous single-component modified epoxy resin dispersoid through phase transformation.
Through preliminary tests, the waterborne single-component modified epoxy resin prepared by the invention has the following characteristics:
solid content: 40 percent of the total weight of the mixture,
viscosity (25 ℃) mpa.s: is less than or equal to 2000 percent,
storage stability: the layers are not layered for six months,
appearance: the white-white blue-light liquid,
particle size: less than or equal to 0.3 mu m.
Comparative example 1
This example prepared an aqueous one-component modified epoxy resin, which differs from example 1 in that no epoxy phosphate was added.
Example of detection
The preparation raw material specifications of the modified epoxy aqueous dispersions prepared in examples 1 to 3 are shown in table 1.
TABLE 1
In example 2, the polyether sulfonate contains a neutralizing agent, so that the neutralizing agent triethylamine is not required to be added.
The basic properties of the aqueous one-component modified epoxy resin paints prepared in examples 1 to 3 and comparative example 1 on galvanized and stainless steel sheets were further tested as shown in table 2.
TABLE 2 aqueous one-component modified epoxy resin base Properties
In Table 2, the paint film surface dry test is based on GB/T1728, the adhesion test is based on GB/T1720, the paint film gloss test is based on GB/T9754, the paint film hardness test is based on GB/T6739, the water resistance test is based on GB/T1733, and the salt spray test is based on GB/T1771.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (11)
1. The waterborne single-component modified epoxy resin is characterized in that the preparation raw materials comprise epoxy resin, a modifier, an adhesion promoter, a catalyst, an initiator, a hydrophilic monomer, a cosolvent and a neutralizing agent;
the epoxy resin includes at least one of E20, E44, E51, E54, F51, and E12.
2. The waterborne single-component modified epoxy resin of claim 1, comprising the following raw materials in parts by weight:
epoxy resin: 300 to 1000 parts by weight of a water-soluble polymer,
modifying agent: 150 to 600 parts of (A) by weight,
an adhesion promoter: 5 to 20 parts of (A) a water-soluble polymer,
catalyst: 0.5 to 2 parts by weight of a stabilizer,
initiator: 0.2 to 15 portions of
Hydrophilic monomer: 2 to 80 parts by weight of a stabilizer,
co-solvent: 150 to 400 parts by weight of a stabilizer,
neutralizing agent: 80-120 parts of (a) a water-soluble polymer,
deionized water: 300-2000 parts.
3. The waterborne one-component modified epoxy resin of claim 1 or 2, wherein the modifier comprises at least one of linseed oil fatty acid, methacrylate ester, bisphenol a, benzoic acid, coconut oil fatty acid, dehydrated castor oil fatty acid, soybean oil fatty acid.
4. The waterborne one-component modified epoxy resin according to claim 1 or 2, wherein the adhesion promoter comprises at least one of epoxy phosphate, phosphoric acid, and polyphosphoric acid.
5. The aqueous one-component modified epoxy resin according to claim 1 or 2, wherein the catalyst comprises at least one of zinc peroxide, boron trifluoride amine complex, boric acid, boron trifluoride etherate complex, triphenylphosphine, and tetrabutylammonium bromide.
6. The waterborne one-component modified epoxy resin of claim 1 or 2, wherein the initiator comprises at least one of DTAP, AIBN, BPO, TBPO, TBPB, DTBP.
7. The waterborne one-component modified epoxy resin according to claim 1 or 2, wherein the hydrophilic monomer comprises at least one of maleic anhydride, polyether sulfonate, polyester sulfonate, acrylic acid, methacrylic acid, polyethylene glycol 2000, polyethylene glycol 4000 and polyethylene glycol 6000.
8. The waterborne one-component modified epoxy resin according to claim 1 or 2, wherein the co-solvent comprises at least one of propylene glycol butyl ether, ethylene glycol tertiary butyl ether and isopropyl alcohol.
9. A process for preparing the aqueous one-component modified epoxy resin according to any one of claims 1 to 8, comprising the steps of:
s1: mixing the epoxy resin, part of the modifier, the adhesion promoter, the catalyst and the hydrophilic monomer according to the proportion, and then heating for reaction;
s2: cooling the product of the step S1, and adding the cosolvent, the initiator and the residual modifier;
s3: and (5) cooling the product obtained in the step S2, and adding a neutralizing agent and deionized water for dispersing and emulsifying.
10. A coating composition comprising the aqueous one-component modified epoxy resin according to any one of claims 1 to 8.
11. A coated product comprising a substrate and the aqueous one-component modified epoxy resin according to any one of claims 1 to 8 applied to the substrate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980578A (en) * | 2021-12-03 | 2022-01-28 | 绵阳麦思威尔科技有限公司 | Single-component epoxy dispersion and preparation method thereof |
| CN114133496A (en) * | 2022-01-06 | 2022-03-04 | 上海广沣科技有限公司 | Water-based epoxy resin and preparation method thereof |
| CN114163898A (en) * | 2021-12-29 | 2022-03-11 | 无锡普天铁心股份有限公司 | Water-based high-temperature-resistant heavy-duty resin composition and preparation method and application thereof |
| CN115960567A (en) * | 2023-01-18 | 2023-04-14 | 江苏科麦特科技发展有限公司 | High-thermal-conductivity high-adhesion epoxy plastic packaging material and preparation method thereof |
| CN116694178A (en) * | 2023-06-06 | 2023-09-05 | 广东腐蚀科学与技术创新研究院 | Low-VOC quick-drying aqueous single-component epoxy ester modified acrylate dispersion, and preparation method and application thereof |
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