CN112300367A - Photo-thermal dual-curing epoxy resin - Google Patents
Photo-thermal dual-curing epoxy resin Download PDFInfo
- Publication number
- CN112300367A CN112300367A CN202011137322.2A CN202011137322A CN112300367A CN 112300367 A CN112300367 A CN 112300367A CN 202011137322 A CN202011137322 A CN 202011137322A CN 112300367 A CN112300367 A CN 112300367A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- curing
- photo
- dual
- thermal
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The photo-thermal dual-curing epoxy resin is prepared by one-step reaction of bio-based itaconic acid and epoxy resin, epoxy groups are arranged at two ends of the photo-thermal dual-curing epoxy resin, and a double bond is arranged on a middle main chain, so that the photo-thermal dual-curing epoxy resin can participate in thermal curing and photo-curing reactions at the same time. The synthetic reaction raw materials are green and environment-friendly, the synthetic process is simple and efficient, the synthetic method is suitable for industrial large-scale production, the glass transition temperature of the cured material is high, the energy storage modulus is high, the strength is high, and the synthetic method is suitable for the application fields of photo-thermal dual curing, such as coatings, 3D printing, adhesives and the like.
Description
Technical Field
The invention relates to aSynthesis ofTechnique ofRadiation curable materialThe technical field is as follows.
Background
The photo-thermal dual curing means that the photo-curing is performed to partially crosslink the system, so that the material has certain properties, and then the thermal curing is performed to completely react the thermal crosslinking groups in the material to form the cured material. In photo-thermal dual curing, a double bond, an epoxy group, and the like are common groups that can be photo-cured. Groups capable of undergoing thermal curing such as carboxyl groups, hydroxyl groups, isocyanate groups, epoxy groups, and the like. The photo-thermal dual curing has the following advantages: curing of adhesives among complex parts, reduction of shrinkage of a photocuring system, pre-shaping of materials, improvement of material performance and the like. Widely used in 3D printing and adhesive industry. At present, a plurality of methods are used for preparing a photo-thermal dual-curing system, for example, a reactive diluent or oligomer for photo-curing, an epoxy resin or polyurethane resin for thermal curing and a corresponding curing agent are added into the system, but the reaction is only simple raw material blending, the material performance is unstable, and the preparation process error is large. And the other method is that acrylic acid consumes part of epoxy groups in the epoxy resin to synthesize the resin containing double bonds and epoxy groups, and then corresponding initiator and epoxy group curing agent are added. But the raw material acrylic acid used by the method is a volatile carcinogen, does not meet the requirements of the existing green production process, and has brittle material performance and narrow application range. This patent introduces double bonds with bio-based itaconic acid, and the synthesized resin molecule has both epoxy groups and double bonds. The prepared material has stable and reliable performance and is suitable for large-scale production.
For example, in patent CN 110791196 a, epoxy resin E51 and terminal hydroxypropyl polydimethylsiloxane are used to synthesize a first component matrix resin with polyhydroxy main chain belt, isophorone diisocyanate, trimethylolpropane, hydroxyethyl acrylate and hexamethylene diisocyanate trimer are used to synthesize a second component curing agent, and then a photo-thermal dual curing system is prepared. And isophorone diisocyanate and organotin catalysts used in the synthesis process are toxic substances.
For example, in patent CN 110643318A, several acrylate reactive diluents are used, and then the method of adding thermal initiator and photoinitiator in the formulation cannot control how many proportion of groups in the system to perform photocuring and thermocuring, the properties of the pre-cured material cannot be accurately controlled, and the prepared material has low modulus and narrow application range.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a photo-thermal dual-curing epoxy resin, which has the following structure:
wherein M represents
wherein R1 and R2 represent hydrogen atom or methyl, R3 represents hydrogen atom or glycidyl, R4 represents benzene ring or cyclohexane structure, and the symbol is the position of the connecting point of the groups.
In one embodiment, the resin structure is as follows:
the second purpose of the invention is to provide a preparation method of the photo-thermal dual-curing epoxy resin, which comprises the following steps: fully mixing difunctional epoxy oligomer or epoxy resin, itaconic acid, a catalyst and a polymerization inhibitor to obtain the photo-thermal dual-curing epoxy resin under high-temperature reaction;
in one embodiment, the epoxy resin comprises a material having the structure
Wherein R1 represents a benzene ring or cyclohexane structure, R2 represents a hydrogen atom or a methyl group, and n represents an integer of 1-3.
In one embodiment, the epoxy resin comprises a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a difunctional novolac epoxy resin, a difunctional glycidyl ether, or a difunctional epoxy oligomer; the difunctional epoxy oligomer includes diglycidyl ether, bisphenol a diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, and polydiglycidyl ether.
The epoxy group of the difunctional epoxy oligomer or epoxy resin can react with the carboxyl group of itaconic acid to generate the photothermal dual curing epoxy resin.
In one embodiment of the method of the present invention,
40 to 99 parts by weight of a difunctional epoxy oligomer or epoxy resin;
0.2-30 parts by weight of itaconic acid;
0.5-1.5 parts by weight of catalyst;
0.05 to 0.2 portion of polymerization inhibitor.
In one embodiment, the specific method is as follows: fully mixing difunctional epoxy oligomer or epoxy resin, itaconic acid, a catalyst and a polymerization inhibitor, wherein the reaction starting temperature is 95-105 ℃, heating to 105-120 ℃ after reacting for 0.5 hour, titrating the acid value at an interval of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g to obtain the photo-thermal dual-curing epoxy resin.
In one embodiment, the catalyst includes triphenylphosphine, triethylamine, tetrabutylammonium bromide, acetylacetonato metal complexes, phosphorus pentoxide, aluminum oxide, phosphines, amine catalysts, and the like; the polymerization inhibitor comprises p-methoxyphenol, hydroquinone and phenols.
The third purpose of the invention is to provide an application of the photo-thermal dual-curing epoxy resin, wherein the application comprises the following steps: as a photo-thermal dual-cure coating composition, the composition comprising: photo-thermal dual-curing epoxy resin, a photo-curing reactive diluent, an epoxy resin curing agent, a thermal curing initiator and a photo-curing initiator.
In one embodiment, the photocurable reactive diluent comprises tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), 1, 6-hexanediol diacrylate (HDDA); the epoxy resin curing agent comprises methyl hexahydrophthalic anhydride (MHHPA), polyetheramine (D230) and polyetheramine (D400); catalysts for the thermal curing reaction include 1, 8-diazabicycloundecen-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN); the photo-curing initiator includes 1173, 819, TPO, 184, etc.
In one embodiment, the coating composition is coated on a steel plate, and is cured under an ultraviolet lamp to form a partially cross-linked coating film, and then the coating film is placed in an oven at a temperature of 130-150 ℃ for curing for 4-6 hours to obtain a completely cured coating film.
In one embodiment, the irradiation wavelength range is 250nm to 600nm, and the light intensity is 400 to 1200mJ/cm2。
Has the advantages that:
according to the invention, bio-based itaconic acid and epoxy resin are reacted in one step to prepare photo-thermal dual-curing epoxy resin, epoxy groups are arranged at two ends of the resin, a photo-curable double bond is arranged on the middle main chain, and then succinic acid and the modified epoxy resin prepared by the epoxy resin through the one-step reaction are used for comparison to show that the introduction of a double bond group can improve the crosslinking density of the material, so that the modulus, the glass transition temperature, the hardness of a coating film and the like of the material are improved. The synthetic reaction is simple and efficient, the raw materials are green and environment-friendly, and the material obtained after the synthetic resin is cured has high glass transition temperature, high energy storage modulus and excellent performance. The epoxy resin synthesized from itaconic acid has both epoxy group and double bond on the molecule, thus avoiding the defect of unstable material performance caused by simple blending of raw materials. The double bond of the patent refers to and uses bio-based itaconic acid, has no toxicity and volatility, the generated resin molecules have double bonds and epoxy groups, and the prepared formula is uniform and stable, so that the prepared material has uniform and stable performance, and is suitable for large-scale industrial production.
Drawings
Description of the meanings indicated in the figures
FIG. 1: synthetic schemes for E51-Ita in examples 1-3
FIG. 2: synthetic schemes for E51-Sua in examples 1-3
FIG. 3: resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and the resins are characterized by an infrared spectrum and compared with a raw material E51 to illustrate the successful synthesis of the resins.
FIG. 4: resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and nuclear magnetic spectrum representation is carried out on the resins to be compared with a raw material E51 to illustrate successful synthesis of the resins.
FIG. 5: characterization of DMA phase angle for resin synthesized in example 2 specimens cured according to the formulation of table 4.
FIG. 6: characterization of DMA storage modulus for the resin synthesized in example 2 specimens cured according to the formulation of table 4.
Detailed Description
Illustrating according to what is contained in the claims
Example 1:
weighing the epoxy resin E51: 26g, itaconic acid (Ita): 1g, Triphenylphosphine (TPP): 0.2g, p-Methoxyphenol (MEHQ): adding 0.03g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath kettle, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Ita-1, and the synthetic route is shown in figure 1.
In addition, for comparison, the double bond-free modified epoxy resin was synthesized from the double bond-free succinic acid by the following synthetic process: weighing the epoxy resin E51: 26g, succinic acid (Sua): 1g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Sua-1, and the synthetic route is shown in figure 2.
The synthesized resin was formulated according to the following table
Table 1: example 1 formulation scale units: g
The two formulations were cured under an F300 UVA ultraviolet lamp (total light intensity 1600 mJ/cm)2) The track speed of the ultraviolet exposure machine is 4.5m min-1The cured samples were designated E51-Sua-1-F-UV and E51-Ita-1-F-UV. Similarly, the above formulation is added after UV exposureHeat was applied for 4.5 hours at 130 ℃. The cured samples were designated E51-Sua-1-F-UV-Heat and E51-Ita-1-F-UV-Heat.
Characterization was performed:
1. tensile test
Table 2: tensile Properties of the samples of example 1
From the above results, it can be seen that the epoxy resin modified with itaconic acid (Ita) has a higher crosslinking density than the epoxy resin modified with succinic acid (Sua), and therefore, the tensile strength and Young's modulus are significantly improved, and the elongation at break of the itaconic acid group is higher than that of the succinic acid group when only photocuring is performed, but the elongation at break of the itaconic acid group after thermal curing is lower than that of the succinic acid group.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 3: film coating Properties of example 1 sample
As can be seen from table 3, the epoxy resin modified with itaconic acid has more excellent coating properties than the succinic acid-modified epoxy resin because the introduction of itaconic acid provides more crosslinking sites, thereby increasing the crosslinking density.
Example 2:
weighing the epoxy resin E51: 26g, itaconic acid (Ita): 3g, Triphenylphosphine (TPP): 0.2g of p-Methoxyphenol (MEHQ) and 0.03g of p-Methoxyphenol (MEHQ) are added into a three-neck flask, a mechanical stirring paddle and a hollow glass plug are additionally arranged, the three-neck flask is fixed in an oil bath pot, the initial temperature is 95 ℃, the temperature is increased to 105 ℃ after reaction for half an hour, the acid value is titrated at intervals of half an hour, the reaction is stopped until the acid value is less than 1mgKOH/g, the synthesized resin is E51-Ita-3, and the synthetic route is shown in figure 1.
For comparison, a modified epoxy resin containing no double bond was synthesized from succinic acid by the following procedure: weighing the epoxy resin E51: 26g, succinic acid (Sua): 3g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting the temperature to be 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Sua-3.
Resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and the resins are characterized by an infrared spectrum and compared with a raw material E51 to illustrate the successful synthesis of the resins, and the figure is shown in FIG. 3.
Resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and nuclear magnetic spectrum characterization is carried out on the resins to compare with a raw material E51 to illustrate successful synthesis of the resins, and the figure is shown in FIG. 4.
The synthesized resin was formulated according to the following table
Table 4: example 2 formulation scale units: g
The two formulations were cured under an F300 UVA ultraviolet lamp (total light intensity 1600 mJ/cm)2) The track speed of the ultraviolet exposure machine is 4.5m min-1The cured samples were designated E51-Sua-3-F-UV and E51-Ita-3-F-UV. Again, the above formulation was heated for an additional 4.5 hours after UV exposure at 130 ℃. The cured samples were designated E51-Sua-3-F-UV-Heat and E51-Ita-3-F-UV-Heat.
Characterization was performed:
1. tensile test
Table 5: tensile Properties of the samples of example 2
From the above results, it can be seen that the epoxy resin modified with itaconic acid (Ita) has a higher crosslinking density than the epoxy resin modified with succinic acid (Sua), and therefore, the tensile strength and Young's modulus are significantly improved, and the elongation at break of the itaconic acid group, which is only photo-cured, is improved, but the elongation at break after thermal curing is reduced.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 6: example 2 film coating Properties of samples
As can be seen from table 7, the epoxy resin modified with itaconic acid has more excellent coating properties than the succinic acid-modified epoxy resin because the introduction of itaconic acid provides more crosslinking sites, thereby increasing the crosslinking density.
DMA characterization
The samples were subjected to DMA characterization for glass transition temperature and storage modulus. The results are shown in FIGS. 5 and 6
The result shows that the glass transition temperature and the storage modulus of the itaconic acid modified epoxy resin E51-Ita-3-F-UV are higher than those of the succinic acid modified epoxy resin E51-Sua-3-F-UV when only the photocuring is carried out. The glass transition temperature and the storage modulus of the E51-Ita-3-F-UV-Heat after photo-curing and thermal curing are higher than those of the E51-Sua-3-F-UV-Heat, and the results also show that the itaconic acid can improve the crosslinking density.
Example 3:
weighing the epoxy resin E51: 26g, itaconic acid (Ita): 5g, Triphenylphosphine (TPP): 0.2g of p-Methoxyphenol (MEHQ) and 0.03g of p-Methoxyphenol (MEHQ) are added into a three-neck flask, a mechanical stirring paddle and a hollow glass plug are additionally arranged, the three-neck flask is fixed in an oil bath pot, the initial temperature is 95 ℃, the temperature is increased to 105 ℃ after reaction for half an hour, the acid value is titrated at intervals of half an hour, the reaction is stopped until the acid value is less than 1mgKOH/g, the synthesized resin is E51-Ita-5, and the synthetic route is shown in figure 1.
For comparison, a modified epoxy resin containing no double bond was synthesized from succinic acid by the following procedure: weighing the epoxy resin E51: 26g, succinic acid (Sua): 5g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Sua-5.
The synthesized resin was formulated according to the following table
Table 7: example 3 formulation scale units: g
Characterization was performed:
1. tensile test
Table 8: tensile Properties of the samples of example 3
From the above results, it can be seen that the epoxy resin modified with itaconic acid (Ita) has a higher crosslinking density than the epoxy resin modified with succinic acid (Sua), and therefore, the tensile strength and Young's modulus are significantly improved, and the elongation at break of the itaconic acid group is higher than that of the succinic acid group when only photocuring is performed, but the elongation at break after thermal curing is lower than that of the succinic acid group.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 9: example 3 film coating Properties of samples
As can be seen from table 9, the epoxy resin modified with itaconic acid has more excellent coating properties than the succinic acid-modified epoxy resin because the introduction of itaconic acid provides more crosslinking sites, thereby increasing the crosslinking density.
Example 4:
weighing 1, 4-butanediol diglycidyl ether (DDE): 26g, itaconic acid (Ita): 5g, Triphenylphosphine (TPP): 0.2g of p-Methoxyphenol (MEHQ) and 0.03g of p-Methoxyphenol (MEHQ) are added into a three-neck flask, a mechanical stirring paddle and a hollow glass plug are additionally arranged, the three-neck flask is fixed in an oil bath pot, the initial temperature is 95 ℃, the temperature is increased to 105 ℃ after reaction for half an hour, the acid value is titrated at intervals of half an hour, the reaction is stopped until the acid value is less than 1mgKOH/g, and the synthesized resin is DDE-Ita-7.
For additional comparison, a modified epoxy resin was synthesized using 1, 4-butanediol diglycidyl ether (DDE) by the following procedure: weighing diglycidyl ether (DDE): 12g, tetronic acid (Sua): 5g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is DDE-Sua-7.
The synthesized resin was formulated according to the following table
Table 10: example 4 formulation scale units: g
Characterization was performed:
1. tensile test
Table 11: tensile Properties of the samples of example 3
From the above results, it can be seen that, compared with the epoxy resin modified with itaconic acid and 1, 4-butanediol diglycidyl ether (DDE), the diglycidyl ether (DDE) and the succinic acid-modified epoxy resin have a high tensile elongation at break and excellent flexibility due to an increase in the crosslinking density of the material.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 12: example 3 film coating Properties of samples
As can be seen from Table 12, compared with the epoxy resin modified with 1, 4-butanediol diglycidyl ether (DDE), the epoxy resin modified with succinic acid and diglycidyl ether (DDE) has excellent flexibility of the material, the adhesion of the coating film is 5B, and the impact resistance is excellent.
Claims (10)
1. The photo-thermal dual-curing epoxy resin is characterized by having the following structure:
wherein M represents
wherein R1 and R2 represent hydrogen atom or methyl, R3 represents hydrogen atom or glycidyl, R4 represents benzene ring or cyclohexane structure, and the symbol is the position of the connecting point of the groups.
2. The photo-thermal dual-curing epoxy resin as claimed in claim 1, wherein the resin has the following structure:
3. the method of claim 1, wherein the epoxy resin is obtained by mixing the difunctional epoxy oligomer or epoxy resin with itaconic acid, a catalyst and a polymerization inhibitor, and reacting at a high temperature.
4. The method of claim 3, wherein the epoxy resin comprises a material having the following structure
Wherein R1 represents a benzene ring or cyclohexane structure, R2 represents a hydrogen atom or a methyl group, and n represents an integer of 0-3.
5. The method of claim 3, wherein the epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, difunctional novolac epoxy resin, difunctional glycidyl ether or difunctional epoxy oligomer; the difunctional epoxy oligomer includes diglycidyl ether, bisphenol a diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, and polydiglycidyl ether.
6. The method for preparing a photothermal dual curing epoxy resin according to claim 3,
40 to 99 parts by weight of a difunctional epoxy oligomer or epoxy resin;
0.2-30 parts by weight of itaconic acid;
0.5-1.5 parts by weight of catalyst;
0.05 to 0.2 portion of polymerization inhibitor.
7. The preparation method of the photothermal dual curing epoxy resin according to claim 3, is characterized by comprising the following steps: fully mixing difunctional epoxy oligomer or epoxy resin, itaconic acid, a catalyst and a polymerization inhibitor, wherein the reaction starting temperature is 95-105 ℃, heating to 105-120 ℃ after reacting for 0.5 hour, titrating the acid value at an interval of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g to obtain the photo-thermal dual-curing epoxy resin.
8. The method for preparing a photothermal dual cure epoxy resin according to any one of claims 3 to 7, wherein the catalyst comprises triphenylphosphine, triethylamine, tetrabutylammonium bromide, acetylacetonato-based metal complex, phosphorus pentoxide, aluminum oxide, phosphines, amine-based catalysts, etc.; the polymerization inhibitor comprises p-methoxyphenol, hydroquinone and phenols.
9. Use of the photothermal dual curing epoxy resin according to claim 1 or 2 or prepared by the method according to any one of claims 3 to 7, as a photothermal dual curing coating composition comprising: photo-thermal dual-curing epoxy resin, a photo-curing reactive diluent, an epoxy resin curing agent, a thermal curing initiator and a photo-curing initiator.
10. The application of the photo-thermal dual-curing epoxy resin as claimed in claim 9, wherein the coating composition is coated on a steel plate, and is cured under an ultraviolet lamp to form a partially cross-linked coating film, and then the coating film is placed in an oven at a temperature of 130-150 ℃ to be cured for 4-6 hours to obtain a fully cured coating film.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011137322.2A CN112300367A (en) | 2020-10-22 | 2020-10-22 | Photo-thermal dual-curing epoxy resin |
| PCT/CN2021/074149 WO2022083024A1 (en) | 2020-10-22 | 2021-01-28 | Photo-thermal dual-curing epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011137322.2A CN112300367A (en) | 2020-10-22 | 2020-10-22 | Photo-thermal dual-curing epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112300367A true CN112300367A (en) | 2021-02-02 |
Family
ID=74328468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011137322.2A Pending CN112300367A (en) | 2020-10-22 | 2020-10-22 | Photo-thermal dual-curing epoxy resin |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112300367A (en) |
| WO (1) | WO2022083024A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011219B (en) * | 2022-07-07 | 2023-04-07 | 浙江伟星实业发展股份有限公司 | Button coating, preparation method and application thereof |
| CN117430505A (en) * | 2023-10-23 | 2024-01-23 | 广东炎墨方案科技有限公司 | Itaconic acid derived glycidyl ether photo-curing epoxy resin and preparation method and application thereof |
| CN118165195B (en) * | 2024-05-14 | 2024-08-02 | 北京极溯光学科技有限公司 | Dual-cure resin, 3D printing method and 3D printed product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956235A (en) * | 1974-06-24 | 1976-05-11 | Continental Can Company, Inc. | Photopolymerizable compounds stabilized against premature gelation with copper compounds and thiocarbamates |
| CN1425642A (en) * | 2002-12-20 | 2003-06-25 | 中国科学院广州化学研究所 | Method of catalyzing esterification of carboxylic acid and expoxy compound |
| CN102718945A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院宁波材料技术与工程研究所 | Itaconic acid-based epoxy resin composition and method for preparing cured substance |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2514017B2 (en) * | 1987-01-21 | 1996-07-10 | ダイセル化学工業株式会社 | Method for producing unsaturated epoxy ester resin |
| JP2007153853A (en) * | 2005-12-08 | 2007-06-21 | Toagosei Co Ltd | Method for producing ester compound |
| CN102382079B (en) * | 2011-08-25 | 2013-09-25 | 中国科学院宁波材料技术与工程研究所 | Itaconic acid glycidyl ester, and preparation method and application thereof |
| CN102964968A (en) * | 2012-11-06 | 2013-03-13 | 广东大盈化工有限公司 | UV (ultraviolet) light dual-curing powder paint and preparation method thereof |
| CN102977335B (en) * | 2012-11-30 | 2015-04-22 | 深圳职业技术学院 | Method for preparing resin containing light-heat dual cured groups from epoxy chloropropane as raw material |
| CN105061727B (en) * | 2015-07-23 | 2017-11-21 | 广州大学 | A kind of UV-curable water-borne epoxy itaconic acid resin and preparation method thereof |
-
2020
- 2020-10-22 CN CN202011137322.2A patent/CN112300367A/en active Pending
-
2021
- 2021-01-28 WO PCT/CN2021/074149 patent/WO2022083024A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956235A (en) * | 1974-06-24 | 1976-05-11 | Continental Can Company, Inc. | Photopolymerizable compounds stabilized against premature gelation with copper compounds and thiocarbamates |
| CN1425642A (en) * | 2002-12-20 | 2003-06-25 | 中国科学院广州化学研究所 | Method of catalyzing esterification of carboxylic acid and expoxy compound |
| CN102718945A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院宁波材料技术与工程研究所 | Itaconic acid-based epoxy resin composition and method for preparing cured substance |
Non-Patent Citations (1)
| Title |
|---|
| 韦星船等: ""UV 固化水性环氧衣康酸树脂的合成及性能研究"", 《涂料工业》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022083024A1 (en) | 2022-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112300367A (en) | Photo-thermal dual-curing epoxy resin | |
| Wu et al. | High-performance soybean-oil-based epoxy acrylate resins:“Green” synthesis and application in UV-curable coatings | |
| Bao et al. | Synthesis and properties of hyperbranched polyurethane acrylate used for UV curing coatings | |
| AU2010230549B2 (en) | Thermosetting compositions containing isocyanurate rings | |
| JPS6049206B2 (en) | Polymerizable prepolymer with excellent adhesion | |
| EP2531543A1 (en) | Highly functional epoxidized resins and coatings | |
| Yin et al. | Synthesis, photopolymerization kinetics, and thermal properties of UV-curable waterborne hyperbranched polyurethane acrylate dispersions | |
| WO2008001637A1 (en) | Amine imide compound to be activated by irradiation of active energy ray, composition using the same, and method for curing the same | |
| CN111777742A (en) | Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof | |
| JP2001240794A (en) | Cellulose-based ultraviolet curable coating composition | |
| Keramatinia et al. | Synthesis and viscoelastic properties of acrylated hyperbranched polyamidoamine UV-curable coatings with variable microstructures | |
| Jian et al. | Preparation and properties of dual-cure polyurethane acrylate | |
| Jiao et al. | UV-curable hyperbranched urethane acrylate oligomers modified with different fatty acids | |
| US20120259044A1 (en) | Hyperbranched polymers for modifying the toughness of anionically cured epoxy resin systems | |
| CN113897082A (en) | All-bio-based photocuring material and preparation method and application thereof | |
| CN111825847A (en) | Branched modified multifunctional epoxy acrylate light-cured resin and preparation method thereof | |
| Cui et al. | Facile method to prepared photoinitiated cationic curable plant oil and its enhancement on the impact strength of cycloaliphatic diepoxide | |
| Meng et al. | Design and Preparation of Tertiary Amine Modified Polyurethane Acrylate Oligomer with Co‐Initiation/Polymerization Bifunctions for Photo‐Curable Inkjet Printing of Textiles | |
| JPS61101518A (en) | Production of vinyl ester resin having air dryability | |
| Deshmukh et al. | Synthesis of urethane acrylate from PENTA based polyol and EB curing with varying ratio of TMTPA | |
| CN118652401A (en) | Self-repairing photo-curing resin based on epoxidized soybean oil and preparation method thereof | |
| JP7555376B2 (en) | Carbonate-containing epoxy resin, method for preparing the same, cured epoxy product prepared therefrom, and method for decomposing the cured epoxy product | |
| Yang et al. | Synthesis of vinyl functionalized polyurethane acrylate oligomers and their photopolymerization via thiol-ene click reaction | |
| KR100193393B1 (en) | Coating composition containing thermosetting modified polyester resin | |
| JPS5974116A (en) | Production of radical-polymerizable prepolymer |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210202 |