CN111777742A - Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof - Google Patents
Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof Download PDFInfo
- Publication number
- CN111777742A CN111777742A CN202010675200.2A CN202010675200A CN111777742A CN 111777742 A CN111777742 A CN 111777742A CN 202010675200 A CN202010675200 A CN 202010675200A CN 111777742 A CN111777742 A CN 111777742A
- Authority
- CN
- China
- Prior art keywords
- acid
- resin
- oleic acid
- modified epoxy
- epoxy acrylate
- 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.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C09D163/10—Epoxy resins modified by unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses vegetable oleic acid modified epoxy acrylate light-cured resin and a preparation method thereof. The method comprises the steps of utilizing vegetable oil fatty acid containing unsaturated double bonds to carry out ring-opening reaction on glycidyl ether type epoxy resin to prepare the epoxy oil resin, and simultaneously forming hydroxyl in a molecular structure. The generated hydroxyl reacts with maleic anhydride to prepare half ester containing carboxyl, and then the half ester reacts with glycidyl methacrylate to prepare the vegetable oleic acid modified epoxy acrylate resin with photocuring activity. Contains long-chain grease structure and has good wettability to coated base materials and added pigments and fillers. After the ring opening of the common bisphenol A epoxy resin and carboxyl, the number of hydroxyl groups in the molecular structure is usually more than 2, so that the functionality of the prepared vegetable oleic acid modified epoxy acrylate resin can be more than 2. Unsaturated fatty acid with molecular structure can catalyze, oxidize, solidify and crosslink, thereby forming a dual-curing crosslinking network and further improving the performance of the coating.
Description
Technical Field
The invention belongs to the field of preparation of resin for a light-cured coating, and particularly relates to vegetable oleic acid modified epoxy acrylate light-cured resin and a preparation method thereof.
Technical Field
The photo-curing coating is a coating which utilizes ultraviolet light to decompose a photoinitiator to generate active species and initiate monomer polymerization so as to cure a coating. The adopted resin has low molecular weight, and small molecular monomers are used as reactive diluents, so that the coating system has low content of organic volatile matters and is environment-friendly. With the increasing emphasis on environmental protection, the research on environmental-friendly coatings is increasing. The variety of resins for photo-curable coating materials is increasing, and the resins used in large amounts include epoxy acrylate resins, polyester acrylate resins, urethane acrylate resins, and the like. However, with the expansion of the application field of the photo-curing coating and the gradual increase of the requirements on the performance of the photo-curing coating, the demand for the photo-curing resin with high performance is increasingly urgent.
Epoxy resins are one of the resin types commonly used in coating resins. However, cured films of aromatic ring-containing epoxy resins are generally poor in flexibility and the coatings are easily brittle. The variety of modified epoxy resins aiming at the brittleness problem of the epoxy resin is more, for example, vegetable oil acid dimer acid is adopted to open the epoxy resin, and a flexible fatty chain is introduced into the structure of the epoxy resin. However, due to the chain extension reaction, the molecular weight of the epoxy resin is greatly increased, and the viscosity of the reaction system is improved, so that the dosage of the solvent is increased, and the environment friendliness is not facilitated. Chinese patent CN 104710598A discloses another method for modifying epoxy resin with vegetable oleic acid: vegetable oleic acid is adopted to react with epoxy resin, part of epoxy groups are reserved for crosslinking and curing of the epoxy resin, and meanwhile, part of epoxy groups are sacrificed to react with flexible oleic acid to obtain flexibility. The modified epoxy resin prepared by this reaction is similar to the epoxy oil resin.
The epoxy oil resin is modified by vegetable oleic acid, and the cured coating of the epoxy oil resin has the characteristics of high adhesiveness, good mechanical strength, high flexibility of alkyd resin and good performance adjustability of the epoxy resin. The epoxy oil resin is prepared by the ring-opening oxygen reaction of vegetable oil acid. The prepared resin is crosslinked by catalytic oxidation curing to form a crosslinked network. However, compared with the epoxy resin system cured by the traditional epoxy curing agent, the strength of the epoxy oil resin cured film is obviously reduced, the crosslinking density is small, and the application range is limited.
Disclosure of Invention
The invention aims to provide vegetable oleic acid modified epoxy acrylate light-cured resin and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the chemical structural general formula of the vegetable oleic acid modified epoxy acrylate light-cured resin is as follows:
wherein R1 is a fatty acid ester or acrylate structure;
r2 is-H or
The preparation method of the vegetable oleic acid modified epoxy acrylate photocureable resin comprises the following steps:
1) weighing epoxy resin in a three-neck flask, adding vegetable oleic acid-based unsaturated fatty acid, adding 1-3 wt% of tetrabutylammonium bromide catalyst, stirring, introducing N2Heating to 100-120 ℃, reacting at constant temperature for 2h, testing the acid value, cooling to 90-110 ℃ when the acid value is less than 10mgKOH/g, dropwise adding acrylic acid for dissolving 500ppm of p-hydroxyanisole, and reacting at constant temperature after dropwise adding until the acid value of the system is reduced to 10 mgKOH/g;
2) adding maleic anhydride into the reaction system in the step 1), reacting at 90-100 ℃, testing the acid value every 1h, adding glycidyl methacrylate into the reaction system when the acid value difference measured in two consecutive times is less than 5mgKOH/g, adding a polymerization inhibitor and a catalyst, reacting at 100-115 ℃ until the acid value of the system is less than 10mgKOH/g, stopping the reaction, and discharging when the temperature is cooled to 80 ℃.
Preferably, the epoxy resin in the step 1) is bisphenol a epoxy resin E51.
Specifically, the vegetable oil acid radical unsaturated fatty acid in the step 1) is one or more of oleic acid, linoleic acid and dehydrated ricinoleic acid.
Preferably, the molar ratio of the vegetable oil acid-based unsaturated fatty acid to the acrylic acid in the step 1) is 1: 0.5-1, wherein the molar ratio of the total carboxyl of the epoxy resin to the added vegetable oleic acid-based unsaturated fatty acid and acrylic acid is 1: 1-1.05.
Preferably, in the step 2), maleic anhydride is added according to 30-50% of the total mole number of the vegetable oleic acid-based unsaturated fatty acid and the acrylic acid added in the step 1); glycidyl Methacrylate (GMA) was added equimolar to the measured acid number.
Preferably, the polymerization inhibitor in the step 2) is p-hydroxyanisole, and the addition amount of the polymerization inhibitor is 0.1-0.5 wt% of glycidyl methacrylate; the catalyst is one or a mixture of more of tetrabutylammonium bromide, tetramethylammonium chloride or triphenylphosphine, and the addition amount of the catalyst is 1-3 wt% of the total mass of the reaction system.
Taking oleic acid as an example, the reaction process according to the charging ratio of oleic acid to acrylic acid of 1:1 is as follows:
the grafting position and the grafting rate of the maleic anhydride are not fixed, and the grafting degree can be adjusted through the reaction batch ratio, so that the grafting rate of the GMA is adjusted.
The invention has the following beneficial effects: the invention utilizes the hydroxyl of the epoxy oil resin structure to graft methacrylate double bonds on the side chain of the molecular structure, thus preparing the vegetable oleic acid modified epoxy acrylate resin. Vegetable oil fatty acid is introduced into the molecular structure, so that the brittleness problem of the epoxy acrylate is improved. Contains long-chain grease structure and has good wettability to coated base materials and added pigments and fillers. After the ring opening of the common bisphenol A epoxy resin and carboxyl, the number of hydroxyl groups in the molecular structure is usually more than 2, so that the functionality of the prepared vegetable oleic acid modified epoxy acrylate resin can be more than 2. The molecular structure contains an unsaturated fatty acid structure, can be cured by adopting a catalytic oxidation drying method, and can obtain a dual-curing cross-linked network by combining photocuring, so that the performance is more excellent; the grafted vegetable oil long carbon chain structure plays a plasticizing role and can obviously reduce the viscosity of the epoxy acrylate resin.
Drawings
FIG. 1 is an IR spectrum of a vegetable oil-modified epoxy acrylate resin prepared according to example 1.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Weighing epoxy resin E51100g in a three-neck flask, adding 72g of oleic acid, 1.0g of tetrabutylammonium bromide and introducing N2And the temperature is raised to 100 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 90 ℃. After the temperature was stabilized, 18.4g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved was added dropwise. Reacting until the acid value of the system is less than 10 mgKOH/g. Maintaining the temperature at 90 ℃, adding 15.0g of refined maleic anhydride into the reaction system, and reacting for 1 hour to test the acid value. When the difference of the acid value is less than 5mgKOH/g, 0.02g of p-hydroxyanisole and 1.0g of tetrabutylammonium bromide are added into the system, then 21.7g of Glycidyl Methacrylate (GMA) is added dropwise, the reaction is carried out at constant temperature of 100 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out. The infrared spectrum of the obtained vegetable oil modified epoxy acrylate resin is shown in figure 1.
Example 2
Epoxy resin E51100g was weighed into a three-necked flask, 72g of linoleic acid was added, and 1.0g of tetrabutylammonium bromide was added. General formula (N)2And the temperature is raised to 100 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 90 ℃. After the temperature is stabilized, dropwise adding18.4g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved. Reacting until the acid value of the system is less than 10 mgKOH/g. Maintaining the temperature at 90 ℃, adding 15.0g of refined maleic anhydride into the reaction system, and reacting for 1 hour to test the acid value. When the difference of the acid value is less than 5mgKOH/g, 0.02g of p-hydroxyanisole and 1.0g of tetramethylammonium chloride are added into the system, then 21.7g of Glycidyl Methacrylate (GMA) is dripped, the reaction is carried out at the constant temperature of 110 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out.
Example 3
Epoxy resin E51100g was weighed into a three-necked flask, 72g of linoleic acid was added, and 1.0g of tetrabutylammonium bromide was added. General formula (N)2And the temperature is raised to 100 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 90 ℃. After the temperature was stabilized, 18.4g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved was added dropwise. Reacting until the acid value of the system is less than 10 mgKOH/g. Maintaining the temperature at 90 ℃, adding 15.0g of refined maleic anhydride into the reaction system, and reacting for 1 hour to test the acid value. When the difference of the acid value is less than 5mgKOH/g, 0.02g of p-hydroxyanisole and 1.0g of tetrabutylammonium bromide are added into the system, then 21.7g of Glycidyl Methacrylate (GMA) is added dropwise, the reaction is carried out at the constant temperature of 115 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out.
Example 4
Epoxy resin E51100g was weighed into a three-necked flask, 72g of dehydrated ricinoleic acid was added, and 1.0g of tetrabutylammonium bromide was added. General formula (N)2And the temperature is raised to 120 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 100 ℃. After the temperature was stabilized, 18.4g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved was added dropwise. Reacting until the acid value of the system is less than 10 mgKOH/g. Maintaining the temperature at 100 ℃, adding 15.0g of refined maleic anhydride into the reaction system, and reacting for 1 hour to test the acid value. When the difference of the acid value is less than 5mgKOH/g, 0.02g of p-hydroxyanisole and 1.0g of tetrabutylammonium bromide are added into the system, then 21.7g of Glycidyl Methacrylate (GMA) is added dropwise, the reaction is carried out at constant temperature of 100 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out.
Example 5
Epoxy resin E51100g was weighed into a three-necked flask, 97g of oleic acid was added, and 3.0g of tetrabutylammonium bromide was added. General formula (N)2And the temperature is raised to 110 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 100 ℃. After the temperature was stabilized, 12.2g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved was added dropwise. Reacting until the acid value of the system is less than 10 mgKOH/g. The temperature is maintained at 90 ℃, 25.0g of refined maleic anhydride is added into the reaction system, and the reaction is carried out for 1 hour to test the acid value. When the difference of the acid value is less than 5mgKOH/g, 0.1g of p-hydroxyanisole and 1.0g of tetrabutylammonium bromide are added into the system, 36.2g of Glycidyl Methacrylate (GMA) is added dropwise, the reaction is carried out at a constant temperature of 105 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out.
Example 6
Epoxy resin E51100g was weighed into a three-necked flask, 36g of oleic acid was added, and 1.0g of tetrabutylammonium bromide was added. General formula (N)2And the temperature is raised to 120 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 110 ℃. After the temperature was stabilized, 27.6g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved was added dropwise. Reacting until the acid value of the system is less than 10 mgKOH/g. Maintaining the temperature at 100 ℃, adding 20.0g of refined maleic anhydride into the reaction system, and reacting for 1 hour to test the acid value. When the difference of the acid value is less than 5mgKOH/g, 0.02g of p-hydroxyanisole and 1.0g of tetrabutylammonium bromide are added into the system, then 28.9g of Glycidyl Methacrylate (GMA) is added dropwise, the reaction is carried out at the constant temperature of 110 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out.
Example 7
Epoxy resin E51100g was weighed into a three-necked flask, 36g of linoleic acid and 36g of oleic acid were added, and 1.0g of tetrabutylammonium bromide was added. General formula (N)2And the temperature is raised to 100 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 90 ℃. After the temperature was stabilized, 18.4g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved was added dropwise. Reacting until the acid value of the system is less than 10 mgKOH/g. Maintaining the temperature at 95 ℃, adding the purified maleic anhydride 1 into the reaction system5.0g, reacted for 1h to test the acid number. When the difference of the acid value is less than 5mgKOH/g, 0.05g of p-hydroxyanisole, 2.0g of tetrabutylammonium bromide and tetramethylammonium chloride are added into the system, then 21.7g of Glycidyl Methacrylate (GMA) is dripped, the reaction is carried out at the constant temperature of 110 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out.
Example 8
Epoxy resin E51100g was weighed into a three-necked flask, 24g of linoleic acid and 48g of dehydrated ricinoleic acid were added, and 1.0g of tetrabutylammonium bromide was added. General formula (N)2And the temperature is raised to 100 ℃ by stirring. After reacting for 2h, testing the acid value, and when the acid value is less than 10mgKOH/g, cooling to 90 ℃. After the temperature was stabilized, 18.4g of acrylic acid in which 500ppm of p-hydroxyanisole was dissolved was added dropwise. Reacting until the acid value of the system is less than 10 mgKOH/g. Maintaining the temperature at 90 ℃, adding 15.0g of refined maleic anhydride into the reaction system, and reacting for 1 hour to test the acid value. When the difference of the acid value is less than 5mgKOH/g, 0.02g of p-hydroxyanisole and 1.0g of triphenylphosphine are added into the system, then 21.7g of Glycidyl Methacrylate (GMA) is added dropwise, the reaction is carried out at constant temperature of 100 ℃ until the acid value is less than 10mgKOH/g, and the heating is stopped. When the temperature cooled to 80 ℃, the resin was poured out.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The vegetable oleic acid modified epoxy acrylate light-cured resin is characterized by having the following chemical structural general formula:
wherein R1 is a fatty acid ester or acrylate structure;
r2 is-H or
2. The preparation method of the vegetable oleic acid modified epoxy acrylate photocureable resin is characterized by comprising the following steps:
1) weighing epoxy resin in a three-neck flask, adding vegetable oleic acid-based unsaturated fatty acid, adding 1-3 wt% of tetrabutylammonium bromide catalyst, stirring, introducing N2Heating to 100-120 ℃, reacting at constant temperature for 2h, testing the acid value, cooling to 90-110 ℃ when the acid value is less than 10mgKOH/g, dropwise adding acrylic acid for dissolving 500ppm of p-hydroxyanisole, and reacting at constant temperature after dropwise adding until the acid value of the system is reduced to 10 mgKOH/g;
2) adding maleic anhydride into the reaction system in the step 1), reacting at 90-100 ℃, testing the acid value every 1h, adding glycidyl methacrylate into the reaction system when the acid value difference measured in two consecutive times is less than 5mgKOH/g, adding a polymerization inhibitor and a catalyst, reacting at 100-115 ℃ until the acid value of the system is less than 10mgKOH/g, stopping the reaction, and discharging when the temperature is cooled to 80 ℃.
3. The method for preparing the vegetable oil acid modified epoxy acrylate light-cured resin according to claim 2, wherein the epoxy resin in the step 1) is bisphenol A epoxy resin E51.
4. The method for preparing the vegetable oleic acid-modified epoxy acrylate photocurable resin according to claim 2, wherein the vegetable oleic acid-based unsaturated fatty acid in the step 1) is one or more of oleic acid, linoleic acid, linolenic acid and dehydrated ricinoleic acid.
5. The method for preparing the vegetable oleic acid-modified epoxy acrylate photocurable resin according to claim 2, wherein the molar ratio of the vegetable oleic acid-based unsaturated fatty acid to the acrylic acid in the step 1) is 1: 0.5-1, wherein the molar ratio of the total carboxyl of the epoxy resin to the added vegetable oleic acid-based unsaturated fatty acid and acrylic acid is 1: 1-1.05.
6. The method for preparing the vegetable oleic acid-modified epoxy acrylate photocurable resin according to claim 2, wherein maleic anhydride is added in step 2) in an amount of 30 to 50% of the total molar number of the vegetable oleic acid-based unsaturated fatty acid and acrylic acid added in step 1); glycidyl methacrylate was added equimolar to the measured acid number.
7. The method for preparing the vegetable oil acid modified epoxy acrylate photocuring resin as claimed in claim 2, wherein the polymerization inhibitor in the step 2) is p-hydroxyanisole, and the addition amount of the polymerization inhibitor is 0.1-0.5 wt% of glycidyl methacrylate.
8. The method for preparing the vegetable oil acid modified epoxy acrylate photocuring resin according to claim 2, wherein the catalyst in the step 2) is one or a mixture of tetrabutylammonium bromide, tetramethylammonium chloride or triphenylphosphine, and the addition amount of the catalyst is 1-3 wt% of the total mass of the reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010675200.2A CN111777742A (en) | 2020-07-14 | 2020-07-14 | Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010675200.2A CN111777742A (en) | 2020-07-14 | 2020-07-14 | Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111777742A true CN111777742A (en) | 2020-10-16 |
Family
ID=72767591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010675200.2A Pending CN111777742A (en) | 2020-07-14 | 2020-07-14 | Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111777742A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112335687A (en) * | 2020-10-22 | 2021-02-09 | 广东京兴航天农业技术开发有限公司 | Long-acting antibacterial disinfectant |
| CN112538310A (en) * | 2020-12-10 | 2021-03-23 | 中电保力（北京）科技有限公司 | Flexible epoxy acrylate UV curing coating and application thereof in cable joint |
| CN112939831A (en) * | 2021-01-22 | 2021-06-11 | 华南农业大学 | Multifunctional bio-based epoxy acrylate prepolymer and preparation method and application thereof |
| CN113637146A (en) * | 2021-07-30 | 2021-11-12 | 华南农业大学 | Tung oil acid maleic anhydride modified vinyl ester resin and preparation method and application thereof |
| CN113980234A (en) * | 2021-11-30 | 2022-01-28 | 江苏三木化工股份有限公司 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
| CN115386053A (en) * | 2022-09-26 | 2022-11-25 | 浙江传化涂料有限公司 | Modified epoxy resin and preparation method and application thereof |
| CN115717047A (en) * | 2021-08-24 | 2023-02-28 | 深圳飞世尔新材料股份有限公司 | Photo-thermal dual-curing sealant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247649A (en) * | 1999-12-28 | 2001-09-11 | Dainippon Ink & Chem Inc | Photosensitive resin, process for preparation thereof, and solder-resist ink composition |
| CN109734885A (en) * | 2019-01-23 | 2019-05-10 | 安庆北化大科技园有限公司 | A kind of cation-type water-thinned polyester acrylate light-cured resin and preparation method thereof |
-
2020
- 2020-07-14 CN CN202010675200.2A patent/CN111777742A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247649A (en) * | 1999-12-28 | 2001-09-11 | Dainippon Ink & Chem Inc | Photosensitive resin, process for preparation thereof, and solder-resist ink composition |
| CN109734885A (en) * | 2019-01-23 | 2019-05-10 | 安庆北化大科技园有限公司 | A kind of cation-type water-thinned polyester acrylate light-cured resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴卫东: ""脂肪酸改性环氧丙烯酸酯性能的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 李东兵等: ""高活性丙烯酸酯单体的合成及其光聚合性能研究"", 《涂料工业》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112335687A (en) * | 2020-10-22 | 2021-02-09 | 广东京兴航天农业技术开发有限公司 | Long-acting antibacterial disinfectant |
| CN112538310A (en) * | 2020-12-10 | 2021-03-23 | 中电保力（北京）科技有限公司 | Flexible epoxy acrylate UV curing coating and application thereof in cable joint |
| CN112538310B (en) * | 2020-12-10 | 2022-03-15 | 中电保力（北京）科技有限公司 | Flexible epoxy acrylate UV curing coating and application thereof in cable joint |
| CN112939831A (en) * | 2021-01-22 | 2021-06-11 | 华南农业大学 | Multifunctional bio-based epoxy acrylate prepolymer and preparation method and application thereof |
| CN112939831B (en) * | 2021-01-22 | 2022-12-23 | 华南农业大学 | Multifunctional bio-based epoxy acrylate prepolymer and preparation method and application thereof |
| CN113637146A (en) * | 2021-07-30 | 2021-11-12 | 华南农业大学 | Tung oil acid maleic anhydride modified vinyl ester resin and preparation method and application thereof |
| CN115717047A (en) * | 2021-08-24 | 2023-02-28 | 深圳飞世尔新材料股份有限公司 | Photo-thermal dual-curing sealant |
| CN115717047B (en) * | 2021-08-24 | 2023-08-18 | 深圳飞世尔新材料股份有限公司 | Photo-thermal dual-curing sealant |
| CN113980234A (en) * | 2021-11-30 | 2022-01-28 | 江苏三木化工股份有限公司 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
| CN115386053A (en) * | 2022-09-26 | 2022-11-25 | 浙江传化涂料有限公司 | Modified epoxy resin and preparation method and application thereof |
| CN115386053B (en) * | 2022-09-26 | 2024-06-04 | 浙江传化涂料有限公司 | Modified epoxy resin and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111777742A (en) | Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof | |
| US4126527A (en) | Radiation curable coatings containing hydroxy functional polyethers and polyesters of monoethylenic acids or hydroxy esters thereof | |
| US8084545B2 (en) | Photo- and/or thermo-curable copolymer, curable resin compositions, and cured articles | |
| GB2068384A (en) | Coatings of acrylic-fatty acid drying oil resins | |
| CN106519182A (en) | Organic silicon modified polyurethane acrylate oligomer, and preparation method thereof | |
| Yan et al. | Thiourethane thermoset coatings from bio‐based thiols | |
| CN112300367A (en) | Photo-thermal dual-curing epoxy resin | |
| CN107384109B (en) | High-reliability UV (ultraviolet) curing conformal coating and preparation method thereof | |
| US3991024A (en) | Novel curable resin and preparation thereof | |
| CN111825847A (en) | Branched modified multifunctional epoxy acrylate light-cured resin and preparation method thereof | |
| CN108047854A (en) | A kind of UV-curable waterborne BMC high-temperature resistant coatings | |
| JPS6152185B2 (en) | ||
| US4064199A (en) | Curable coating compositions | |
| CA2286676A1 (en) | Modified epoxy resin and its use as a formulating component for heat-curable compositions, especially for powder coatings | |
| JP2000504362A (en) | Low release binder for coatings | |
| JP4880249B2 (en) | Photoradical crosslinking polymer and photocurable resin composition | |
| JPS6145648B2 (en) | ||
| US6255444B1 (en) | Aromatic ester (meth)acrylate dendrimers and curable resin composition | |
| US4140606A (en) | Process for preparing a polymerizable (meth) acrylate oligomer | |
| CA1334462C (en) | Water-dilutable, crosslinkable binder resin | |
| US4973624A (en) | Coating resin composition | |
| JPS6029753B2 (en) | UV curable resin composition | |
| US20030158282A1 (en) | Radio hardenable powder paints | |
| KR101400120B1 (en) | A photo-curable composition for coating | |
| EP0483796B1 (en) | A composition comprising polyether compounds, a process for the preparation thereof and a photocurable resin composition |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201016 |