CN109825034B - Method for realizing mercapto-epoxy deep photocuring and composition thereof - Google Patents
Method for realizing mercapto-epoxy deep photocuring and composition thereof Download PDFInfo
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- CN109825034B CN109825034B CN201910052139.3A CN201910052139A CN109825034B CN 109825034 B CN109825034 B CN 109825034B CN 201910052139 A CN201910052139 A CN 201910052139A CN 109825034 B CN109825034 B CN 109825034B
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The invention discloses a method for realizing mercapto-epoxy deep layer photocuring and a composition thereof, wherein a point light source with the wavelength range of 220-400nm is used for irradiating a photocuring composition to generate active species, the photocuring composition is uniformly dispersed in the irradiation process, and the irradiated composition is heated and then dried to realize mercapto-epoxy deep layer photocuring; the light-cured composition comprises light-cured epoxy resin, light-cured mercapto monomer, photosensitizer and photobase generator. The invention enables the photo-curing composition to be uniformly dispersed in the ultraviolet irradiation process, thus being beneficial to the generation of active species, and enables the active species to be uniformly dispersed in the system, thereby being capable of avoiding the problem that the curing process is difficult to realize due to the fact that the unirradiated area has no active species, and further leading to the incapability of realizing deep curing. The invention can obtain the needed sulfydryl-epoxy deep light curing material according to the actual requirement and the physical model design, breaks through the difficult problem that the traditional sulfydryl-epoxy is difficult to be cured by deep light, and widens the application field of the photopolymerization technology.
Description
Technical Field
The invention belongs to the field of photopolymerization materials, and particularly relates to a method for realizing mercapto-epoxy deep photocuring and a composition thereof.
Technical Field
The sulfydryl-epoxy photocuring reaction is taken as a typical 'click chemistry' reaction, has the advantages of high regioselectivity, mild reaction conditions, small system shrinkage, no oxygen inhibition, excellent thermal property and mechanical property and the like, and is widely applied to the fields of preparation and modification of coatings, adhesives and high polymer materials, preparation of bioresponse materials and the like. However, due to the limited penetrability of the traditional ultraviolet light in a resin system and the internal shielding, absorption and reflection effects caused by an initiator, a pigment, a filler and the like in the system, the curing process of a non-irradiated area of the system is difficult to realize, so that deep curing cannot be realized.
Patent documents CN105348414A and CN105330790A disclose methods of deep cationic photopolymerization and deep radical photopolymerization, respectively, in which upconverters are added to a cationic system and a radical system, respectively, to obtain cured samples having polymerization depths of 5cm or more and 10 cm or more, respectively, but this method only solves the problem of deep photopolymerization of the cationic system and the radical system. The patent document with publication number CN105199643A provides a method for preparing a cationic ultraviolet and thermal dual deep-curing adhesive, in which a photoinitiator and a thermal initiator are added into a resin system to improve the curing depth of the adhesive, but the addition of the thermal initiator can also cause uncontrollable polymerization of the system.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a method for deep photocuring of mercapto-epoxy and a composition thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for realizing mercapto-epoxy deep layer photocuring, said method uses the point light source irradiation light-cured composition of wavelength range 220-400nm to produce the active species, make the light-cured composition disperse evenly in the course of irradiation, the composition after irradiation is heated and baked, can realize mercapto-epoxy deep layer photocuring; the photocurable composition comprises a photocurable epoxy resin, a photocurable mercapto monomer, a photosensitizer, a photobase generator and a pigment/filler.
The invention enables the photo-curing composition to be uniformly dispersed in the ultraviolet irradiation process, thus being beneficial to the generation of active species, and enables the active species to be uniformly dispersed in the system, thereby being capable of avoiding the problem that the curing process is difficult to realize due to the fact that the unirradiated area has no active species, and further leading to the incapability of realizing deep curing.
Preferably, the temperature of the post-heating baking is 70-100 ℃.
Preferably, the time of heating and post-baking is 5-60 min.
Preferably, the photocurable composition is dispersed uniformly during irradiation by stirring or sonication.
The composition for realizing mercapto-epoxy deep photocuring provided by the invention comprises the following components in parts by mass: 40-80 parts of light-curable epoxy resin, 20-60 parts of light-curable mercapto monomer, 0.1-40 parts of photosensitizer and 0.2-8 parts of photobase generator.
Preferably, the photocurable epoxy resin is one or more of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, an alicyclic epoxy resin, or a linear aliphatic epoxy resin.
Preferably, the photocurable mercapto monomer is one or more of trimethylolpropane tris (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), 1, 4-butanediol bis (mercaptoacetate), tetraethyleneglycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-butanediol bis (3-mercaptobutyrate) or tris (3-mercaptobutoxyethyl) isocyanurate.
Preferably, the photosensitizer is thioxanthone or a derivative thereof.
Preferably, the photobase generator is one or more of tetraphenyl borate photobase generators, thioxanthone photobase generators or azacyclic amidine photobase generators.
Preferably, the paint also comprises a pigment/filler, and the pigment/filler is one or more of organic pigment, inorganic pigment, glass fiber, carbon nano tube or carbon fiber. The pigment/filler can be 0-4 parts.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention generates active species by point light source irradiation in the wavelength range of 200-400nm at room temperature or lower temperature, the components of the system are uniformly dispersed in the irradiation process by stirring or ultrasonic, the generation of the active species is facilitated, the active species are uniformly diffused to the non-irradiation area, and deep curing can be realized by heating and baking; the active species has no initiation capability or low initiation efficiency to the system at room temperature or lower temperature, the system is stable and can keep fluidity for a long time, and an effective time window is provided for the molding processing of the material; after the temperature is raised, the initiation efficiency of the active species of the system is improved, and the curing and forming can be carried out in a short time, so that the uniform and efficient deep curing of the mercapto-epoxy is realized.
(2) The method has the advantages of low postbaking temperature, short curing reaction time, efficient and simple process, easy operation and wide applicability, can be used in the fields of photocuring composite materials, photocuring thick coatings and the like, can realize deep curing of most of photocuring sulfydryl-epoxy systems, and can obtain deep curing materials with good uniformity and controllable reaction time and space of deep curing, and can customize different body types according to actual requirements.
Drawings
FIG. 1 is a schematic diagram of the photocuring reaction of the composition of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific examples.
The method for realizing the mercapto-epoxy deep photocuring uses a point light source with the wavelength range of 200-400nm to irradiate the photocuring composition to generate active species, the photocuring composition is uniformly dispersed in the irradiation process, and the irradiated composition is heated and then dried to realize the mercapto-epoxy deep photocuring; the photocurable composition comprises a photocurable epoxy resin, a photocurable mercapto monomer, a photosensitizer and a photobase generator.
Wherein, the irradiation of the light curing composition by using a point light source with a wavelength range of 200-400nm can be performed at room temperature or lower, such as 5-30 ℃, and the irradiated composition can be injected into molds with different shapes and depths according to requirements and then heated for curing and molding.
As shown in fig. 1, the photo-curable epoxy resin, the photo-curable mercapto monomer, the photosensitizer and the photobase generator (which may also include pigment/filler) are uniformly mixed and then injected into a culture dish, the mixture is mechanically stirred at room temperature in the irradiation process of a point light source to induce the excited state photosensitizer and the photobase generator to generate energy transfer to generate alkali active species, the alkali active species are uniformly diffused to the whole system under the stirring action, and the photo-crosslinked cured product is obtained after heating and baking.
Wherein the stirring time can be 5-30min, such as 10min, 15min, 20min, 25min, etc.; stirring may be replaced by other dispersion methods such as ultrasonic.
The baking temperature after heating can be 70-100 ℃, such as 80 ℃, 85 ℃, 90 ℃, 95 ℃ and the like; the heating time may be 5-60 min, such as 10min, 15min, 20min, 25min, 30min, 40min, 50min, etc.
The present invention provides a photocurable composition comprising: 40-80 parts of light-curable epoxy resin, 20-60 parts of light-curable mercapto monomer, 0.1-4 parts of photosensitizer and 0.2-8 parts of photobase generator; preferably, 0-4 parts of pigment/filler can also be included.
Wherein the light-curable epoxy resin can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts and the like; the photocurable mercapto monomer can be 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, etc.; 0.1-4 parts of photosensitizer can be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts and the like; the photobase generator can be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts and the like; the pigment/filler may be 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, etc.
Example 1
This example implements a mercapto-epoxy deep photocuring composition comprising:
the composition is uniformly mixed and then injected into a culture dish, at room temperature, a 385nm point light source is utilized to irradiate and mechanically stir for 15min, then the mixture is transferred into a cylindrical tetrafluoroethylene mold with the diameter of 30mm and the depth of 20mm and a rectangular mold with the length, width and thickness of 60mm, 12mm and 3.6mm respectively, and the mold is postbaked for 45min in a 90 ℃ oven, so that a completely cured cylindrical body sample with the size of 30mm multiplied by 20mm and a completely cured rectangular body sample with the size of 60mm multiplied by 12mm multiplied by 3.6mm can be obtained.
When a cylindrical sample was cut into a series of 9 portions of different depths (h 0cm, h 0.5cm, h 1cm, h 1.5cm and h 2cm) and different radii (r 0cm, r 0.5cm, r 1cm and r 1.5cm), the epoxy conversion of the different portions was found to be around 80%, and the uniformity of the degree of curing reaction was found to be good. By bending the rectangular sample, the flexural modulus was found to be 7.0 GPa.
Example 2
The components and parts of the photocurable composition in this example are the same as those in example 1, except that in this example, the 385nm point light source was irradiated while stirring for 20min, the sample after irradiation was injected into a cylindrical tetrafluoroethylene mold having a diameter of 3cm and a depth of 2cm and a rectangular mold having a length, width and thickness of 60mm, 12mm and 3.6mm, respectively, and the mold was postbaked in an oven at 90 ℃ for 35min, and the other conditions were the same.
This example obtained cured cylindrical and rectangular bulk samples of dimensions 30mm x 20mm and 60mm x 12mm x 3.6mm, respectively, and the cylindrical samples were cut as in example 1 to determine a conversion of epoxy groups of about 89% at different radii and depths of the cured samples, and the rectangular samples were subjected to a bending test to find a flexural modulus of 7.9 GPa.
Example 3
The difference between this example and example 2 is that 1 part of filler is added, the filler is glass fiber powder, after 20min of mechanical stirring while irradiation is carried out by using a 385nm point light source, a sample is injected into a cylindrical tetrafluoroethylene mold with the diameter of 3cm and the depth of 2cm and a rectangular mold with the length, width and thickness of 60mm, 12mm and 3.6mm respectively, the mold is baked for 35min in an oven at 90 ℃, and other conditions are consistent.
This example obtained fully cured cylindrical and rectangular bulk samples which were treated as in example 1 and found that the cured samples had approximately 87% conversion of epoxy groups at different radii and depths and increased flexural modulus to 12 GPa.
Example 4
The difference between this example and example 1 is that 0.5 part of a filler, which is carbon nanotubes, is added, and after mechanical stirring for 30min while irradiation is performed with a 385nm point light source, the sample is injected into a cylindrical tetrafluoroethylene mold having a diameter of 3cm and a depth of 2cm and a rectangular mold having a length, a width and a thickness of 60mm, 12mm and 3.6mm, respectively, and the molds are post-baked for 45min in an oven at 90 ℃ and the other conditions are the same.
This example obtained a fully cured cylindrical bulk sample of dimensions 3cm x 2cm, treated as in example 1, and found a conversion of epoxy groups at different radii and depths of the cured sample of approximately 82% and an increase in flexural modulus to 12.8 GPa.
Example 5
This example implements a mercapto-epoxy deep photocuring composition comprising:
the composition is uniformly mixed and then injected into a culture dish, at room temperature, a 365nm point light source is utilized to irradiate and mechanically stir for 20min, then the sample is transferred into a cylindrical tetrafluoroethylene mold with the length of 3cm multiplied by 2cm and a rectangular mold with the length, width and thickness of 60mm, 12mm and 3.6mm respectively, the mold is placed in an oven with the temperature of 90 ℃ for post-baking for 30min, a colorless cylindrical composite material sample and a rectangular sample which are completely cured can be obtained, the sample is treated according to the example 1, the epoxy conversion rate of the cured sample at different radiuses and depths is about 91%, and the flexural modulus is 11.3 GPa.
Example 6
This example implements a mercapto-epoxy deep photocuring composition comprising:
the above composition was mixed well and poured into a petri dish, at room temperature, using a 385nm point light source to irradiate while mechanically stirring for 20min, then pouring the sample into a standard dumbbell-type tetrafluoroethylene mold (75 mm by 12.5mm by 2mm in length and width), then placing the sample into an oven at 95 ℃ and post-baking for 20min, a completely cured black dumbbell-type composite sample could be obtained, the surface epoxy conversion of the cured sample was 89%, and the tensile test found to have a tensile modulus of 2805 MPa.
Example 7
This example implements a mercapto-epoxy deep photocuring composition comprising:
the composition is uniformly mixed and then injected into a culture dish, a 365nm point light source is utilized to irradiate and mechanically stir for 10min at room temperature, then a sample is poured into a standard dumbbell type tetrafluoroethylene mold (the length, width and thickness are 75mm, 12.5mm and 2mm), then the sample is placed into a 90 ℃ oven and then is baked for 25min, and a fully cured dumbbell type composite material sample can be obtained, wherein the surface epoxy conversion rate of the cured sample reaches 77%, and the tensile modulus is 1162 MPa.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (1)
1. A method for realizing mercapto-epoxy deep layer photocuring is characterized in that a point light source with the wavelength ranging from 220 nm to 400nm is used for irradiating a photocuring composition to generate active species, all components of a photocuring system are uniformly dispersed by stirring or ultrasound in the irradiation process, and the irradiated system is heated and then dried to realize mercapto-epoxy deep layer photocuring;
the light-cured composition comprises the following components in parts by mass: 40-80 parts of light-curable epoxy resin, 20-60 parts of light-curable mercapto monomer, 1.5-4 parts of photosensitizer and 3-8 parts of photobase generator;
the photosensitizer is thioxanthone or a derivative thereof;
the photobase generator is one or more of tetraphenyl borate photobase generator and azacyclic amidine photobase generator;
the temperature of the heated and dried material is 70-100 ℃;
and the time for heating and baking is 5-60 min.
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| CN201910052139.3A CN109825034B (en) | 2019-01-21 | 2019-01-21 | Method for realizing mercapto-epoxy deep photocuring and composition thereof |
| PCT/CN2020/071868 WO2020151527A1 (en) | 2019-01-21 | 2020-01-14 | Method for implementing mercapto-epoxy deep photocuring and application thereof |
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| CN109825034B (en) * | 2019-01-21 | 2020-10-30 | 江南大学 | Method for realizing mercapto-epoxy deep photocuring and composition thereof |
| CN112080241B (en) * | 2020-09-24 | 2021-12-21 | 广东普赛达密封粘胶有限公司 | Photo-curing adhesive and preparation method and application thereof |
| CN113201203A (en) * | 2021-03-15 | 2021-08-03 | 苏州市汇涌进光电有限公司 | Light-cured transparent epoxy material and application thereof |
| CN116410682B (en) * | 2023-04-14 | 2024-09-13 | 南通康尔乐复合材料有限公司 | Thermosetting UV pressure-sensitive adhesive and preparation method thereof |
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| US20060223978A1 (en) * | 2005-04-04 | 2006-10-05 | Shengqian Kong | Radiation- or thermally-curable oxetane barrier sealants |
| CN101553549B (en) * | 2006-12-14 | 2013-02-20 | 旭化成电子材料株式会社 | Photobase generator and photocurable resin composition |
| PT3256542T (en) * | 2015-02-13 | 2022-07-29 | Chemetall Gmbh | Sealing mass based on mercapto-terminated base polymer/epoxy compound and method for hardening by means of a photolatent catalyst |
| CN104844564A (en) * | 2015-04-15 | 2015-08-19 | 江南大学 | Latent type photoinduced decarboxylation photobase generator and preparation method thereof |
| CN106243251B (en) * | 2016-08-23 | 2018-07-03 | 江南大学 | A kind of one pack system visible light initiator and the application in hybrid UV-curing |
| CN106883210A (en) * | 2017-02-03 | 2017-06-23 | 江南大学 | A kind of carbanion type Photobase generator and preparation method thereof |
| CN108659471A (en) * | 2018-05-23 | 2018-10-16 | 北京化工大学 | A kind of light-cured resin and preparation method thereof that polyfunctionality POSS is modified |
| CN109825034B (en) * | 2019-01-21 | 2020-10-30 | 江南大学 | Method for realizing mercapto-epoxy deep photocuring and composition thereof |
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Non-Patent Citations (3)
| Title |
|---|
| "Curing kinetics and characterization of dual-curable thiol-acrylate-epoxy thermosets with latent reactivity";Ali Osman Konuray，et al;《Reactive and Functional Polymers》;20171121;第122卷;第60-67页 * |
| "Thiol–epoxy/thiol–acrylate hybrid materials synthesized by photopolymerization";Yu Jian，et al;《J. Mater. Chem. C》;20130617;第1卷;第4481-4489页 * |
| Ali Osman Konuray，et al."Curing kinetics and characterization of dual-curable thiol-acrylate-epoxy thermosets with latent reactivity".《Reactive and Functional Polymers》.2017,第122卷第60-67页. * |
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