CN113461658B - High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof - Google Patents
High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-refraction high-temperature-resistant optical monomer, optical resin and a preparation method thereof, wherein the high-refraction high-temperature-resistant optical monomer comprises a high-refraction acrylate monomer and a high-refraction mercaptan monomer, the structural formula of the high-refraction acrylate monomer is shown as a formula (1), and the structural formula of the high-refraction mercaptan monomer is shown as a formula (2). The optical resin is obtained by adopting a high-refraction acrylate monomer and a high-refraction mercaptan monomer through a click chemical reaction. By adopting the technical scheme of the invention, the obtained optical resin contains a large amount of S elements and cardo structures, the optical refractive index is greatly improved, and the optical resin has the characteristics of high glass transition temperature, low shrinkage rate, colorless transparency and low water absorption rate. The optical resin obtained by the further reaction can be used as an optical adhesive, an optical lens, an optical plastic part and the like. The optical lens or the adhesive prepared from the optical resin can be applied to vehicles and has good high-temperature resistance and reliability.
Description
Technical Field
The invention belongs to the technical field of optical materials, and particularly relates to a high-refraction high-temperature-resistant optical monomer, optical resin and preparation methods thereof.
Background
Optical resins have wide applications, such as being used as lenses on personal consumer product eyeglasses or lenses of electronic consumer product cameras, and also being used as optical adhesives in optical devices. In the above applications, the properties of the material, such as refractive index, transmittance, and yellowness, are very important, and it is required that the higher the refractive index and the transmittance, the better the yellowness, and the smaller the yellowness, the better the yellowness.
Currently, high refractive optical materials are mainly formed by curing acrylate compounds, and commonly used optical monomers include monomers with a fluorene structure, such as 9, 9-bis (4- (2-acryloyloxyethoxy) phenyl) fluorene, and the refractive index of a cured product of the optical monomers is 1.62. In patent CN109053998A, an epoxy resin containing a sulfur binaphthyl structure is synthesized and cured to prepare a high refractive index resin with a refractive index of about 1.68, however, the binaphthyl structure is easy to crystallize in the epoxy resin group resin adopted in the system, and the epoxy group is mainly thermally cured and cannot be photo-cured, so the processing process is complicated.
At present, most of vehicle-mounted cameras are more than 4. In recent years, with the development of intelligent automobiles, more and more cameras are required, and high-refraction optical lens materials and optical adhesives are required in the cameras. At present, the camera head on the automobile is mainly a glass lens, but the optical glass is difficult to process and form, and the cost is high, so that the industry expects to replace the glass lens with a plastic lens, but the glass transition temperature of the current plastic optical material or adhesive is generally lower than 150 ℃, and the glass transition temperature of the optical material on the automobile is generally required to be more than 160 ℃. Many of the materials reported today have difficulty meeting the above requirements in terms of both mechanical and thermal properties.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a high-refraction high-temperature-resistant optical monomer, an optical resin and a preparation method thereof, wherein the optical resin obtained by reacting a high-refraction acrylate monomer with a high-refraction thiol monomer has the glass transition temperature of over 160 ℃, the refractive index of over 1.7 and good mechanical and thermal properties.
In contrast, the technical scheme adopted by the invention is as follows:
a high-refraction high-temperature-resistant optical monomer comprises a high-refraction acrylate monomer and a high-refraction mercaptan monomer, wherein the structural formula of the high-refraction acrylate monomer is shown as a formula (1):
the structural formula of the high-refraction thiol monomer is shown as a formula (2):
by adopting the technical scheme, the high-refraction acrylate monomer and the high-refraction mercaptan monomer both contain the main skeleton of dibenzothiophene 5-oxide, the obtained monomer not only contains a high-refraction cardo (cardo) structure, but also contains an S element, so that the refractive index of the resin obtained by adopting the monomer reaction is improved, and the two monomers both contain the cardo structure and the benzene ring, so that the glass transition temperature of the resin obtained by the monomer reaction is improved.
The invention also discloses a preparation method of the high-refraction high-temperature-resistant optical monomer, and the high-refraction acrylate monomer is prepared by the following steps:
adding a phenyl methacrylate monomer and a dibenzothiophene 5-oxide monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 20-80 ℃ for 30-120 hours, wherein the reaction formula is shown as a formula (3):
as a further improvement of the invention, the mass ratio of the phenyl methacrylate monomer to the dibenzothiophene 5-oxide is 1: 0.6 to 2.
As a further improvement of the invention, the mass ratio of the phenyl methacrylate monomer, the dibenzothiophene 5-oxide, the concentrated sulfuric acid, the 3-hydroxypropionic acid and the solvent A is 1: 0.6-2: 0.001-0.01: 0.005-0.01: 10 to 40.
As a further improvement of the invention, the high refractive thiol monomer is prepared by the following steps:
adding a thiophenol monomer and a dibenzothiophene 5-oxide monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting for 30-120 hours at the temperature of 20-80 ℃, wherein the reaction formula is shown as a formula (4):
as a further improvement of the invention, the mass ratio of the thiophenol monomer to the dibenzothiophene 5-oxide monomer is 1: 0.5 to 1.8.
As a further improvement of the invention, the mass ratio of the thiophenol monomer, the dibenzothiophene 5-oxide monomer, the concentrated sulfuric acid, the 3-hydroxypropionic acid and the solvent A is 1: 0.5-1.8: 0.002 to 0.01: 0.003 to 0.02: 20 to 50.
As a further improvement of the invention, the solvent A is one or a mixture of more than two of dichloromethane, trichloromethane, cyclohexanone, dioxane, p-xylene, toluene, acetonitrile and ethyl acetate.
The invention also discloses an optical resin which is obtained by adopting the high-refraction acrylate monomer and the high-refraction thiol monomer in the high-refraction high-temperature-resistant optical monomer through a click chemical reaction.
The invention also discloses a preparation method of the optical resin, which comprises the following steps: and uniformly mixing the high-refraction acrylate monomer, the high-refraction thiol monomer, the diluent and the photoinitiator, and then reacting under the irradiation of ultraviolet rays to obtain the optical resin. Further, the mass ratio of the high-refraction acrylate monomer to the high-refraction thiol monomer is 1: 0.5 to 3.
By adopting the technical scheme, the click chemical reaction is carried out between thiol and double bonds of the high-refraction acrylate monomer and the high-refraction thiol monomer, the obtained resin contains a large amount of S and a high-refraction cardo structure, so that the refractive index of the optical resin is over 1.7, the optical resin has a high refractive index, and simultaneously contains a large amount of benzene rings, the glass transition temperature of the obtained optical resin is over 160 ℃, and the optical resin has good heat resistance, small shrinkage and low water absorption rate.
As a further improvement of the invention, after being uniformly mixed, the mixture has the wavelength of 365nm and the energy of 2000-5000 mw/cm2And irradiating UV 50-500S to obtain the high-refraction optical resin.
As a further improvement of the invention, the diluent comprises a compound containing a benzene ring structure.
As a further improvement of the invention, the diluent comprises a diluent A and a diluent B, the diluent A is one or a mixture of more than two of 1, 4-butanediol bis (mercaptoacetate), 4, 5-bis (mercaptomethyl) o-xylene, 4 '-biphenyldithiol, bis (2-mercaptoethyl) sulfide, 4' -thiobisthiophenol, 1, 5-dimercapto-3-thiapentane, 4-mercapto-1, 8-dimercapto-3, 6-dithiooctane, 4, 8-bis (mercaptomethyl) -1, 11-dithio-3, 6, 9-trithiaundecane and 5, 7-bis (mercaptomethyl) -1, 11-dimercapto-3, 6, 9-trithiaundecane; the diluent B is one or a mixture of more than two of diallyl phthalate, diallyl isophthalate, diallyl terephthalate, 2-phenoxyethyl methacrylate, o-phenylphenol methacrylate, phenyl methacrylate, benzyl methacrylate, o-phenylphenol methacrylate, 2- (benzyloxy) ethyl methacrylate, N-vinyl pyrrolidone, dimethylaminoethylacrylamide, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate and isobornyl (meth) acrylate.
As a further improvement of the present invention, the initiator is methyl benzoylformate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene, benzoin dimethyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, methyl benzoylformate, ethyl benzoylformate, methyl-1-propanone, methyl-2, methyl-1-propanone, methyl-1-propanone, methyl-1-propanone, methyl-1-methyl-1-propanone, methyl-phenyl-1-methyl-1-propanone, and methyl-1-propanone, 4-phenyl benzophenone, ethyl 4-dimethylaminobenzoate, 2, 4-diethyl thioxanthone and isopropyl thioxanthone (2,4 isomeric mixture).
As a further improvement of the invention, the mass ratio of the high-refraction acrylate monomer, the high-refraction thiol monomer, the diluent A, the diluent B and the photoinitiator is 1: 0.5-3: 0.2-5: 0.1-4: 0.001 to 0.005.
Compared with the prior art, the invention has the beneficial effects that:
according to the technical scheme, dibenzothiophene 5-oxide is used as a main skeleton and reacts with phenyl methacrylate and thiophenol respectively to obtain a high-refraction acrylate monomer and a high-refraction dithiol monomer, the two monomers are compared with a traditional high-refraction fluorene structure, the high-refraction dithiol monomer and the high-refraction dithiol monomer not only contain a high-refraction cardo structure, but also contain S elements, so that the refractive index is greatly improved, the finally obtained optical resin is obtained by adopting click chemical reaction between thiol and double bonds, the S elements can be reserved on a main chain after the reaction is finished, the content of the S elements in the finally obtained optical resin is high, the S elements contain the high-refraction cardo structure, and the refractive index of the obtained optical resin is high and exceeds 1.7.
Secondly, the obtained thiol monomer and the acrylate monomer both contain cardo structures, have high glass transition temperature, and also have the characteristics of low shrinkage, colorless transparency and low water absorption. The optical resin obtained by the further reaction can be used as an optical adhesive, an optical lens, an optical plastic part and the like.
Finally, the cardo structure in the monomer and the optical resin in the technical scheme of the invention contains a large number of benzene rings, and further the thinner is mainly a benzene ring structure monomer, so that the resin obtained after the reaction contains a large number of rigid benzene ring structures, therefore, the obtained optical resin has good heat resistance, the glass transition temperature of the optical resin is above 160 ℃, and the optical lens or the adhesive prepared by the material can be applied to vehicles and has good high-temperature resistance and reliability.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
A high-refraction high-temperature-resistant optical monomer comprises a high-refraction acrylate monomer and a high-refraction thiol monomer, wherein the structural formula of the high-refraction acrylate monomer is shown as a formula (1):
the structural formula of the high-refraction thiol monomer is shown as a formula (2):
the synthesis method of the high-refraction optical acrylate monomer comprises the following steps: adding a phenyl methacrylate (CAS:2177-70-0) monomer and a dibenzothiophene 5-oxide (CAS:1013-23-6) monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 20-80 ℃ for 30-120 hours; wherein the mass ratio of phenyl methacrylate (CAS:2177-70-0) monomer, dibenzothiophene 5-oxide (CAS:1013-23-6), concentrated sulfuric acid, 3-hydracrylic acid and solvent A is 1: 0.6-2: 0.001-0.01: 0.005-0.01: 10 to 40.
The synthesis method of the high-refraction mercaptan monomer comprises the following steps: adding a thiophenol monomer (CAS number: 108-98-5) and a dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 20-80 ℃ for 30-120 hours; wherein, the mass ratio of thiophenol monomer (CAS number: 108-98-5), dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer, concentrated sulfuric acid, 3-hydracrylic acid and solvent A is 1: 0.5-1.8: 0.002 to 0.01: 0.003 to 0.02: 20 to 50.
The solvent A is one or a mixture of more of dichloromethane, trichloromethane, cyclohexanone, dioxane, p-xylene, toluene, acetonitrile and ethyl acetate.
A high-refraction optical resin is prepared through mixing high-refraction optical acrylic monomer with high-refraction thiol monomer, adding diluent A, diluent B and photoinitiator, stirring, and adding energy 2000-5000 mw/cm at 365nm2Irradiating UV 50-500S to obtain high-refraction optical resin; wherein the mass ratio of the high-refraction acrylate monomer, the high-refraction mercaptan monomer, the diluent A, the diluent B and the photoinitiator is 1: 0.5-3: 0.2-5: 0.1-4: 0.001 to 0.005.
The diluent A is one or a mixture of more than two of 1, 4-butanediol bis (mercaptoacetate), 4, 5-bis (mercaptomethyl) o-xylene, 4 '-biphenyldithiol, bis (2-mercaptoethyl) sulfide, 4' -thiobisthiophenol, 1, 5-dimercapto-3-thiapentane, 4-mercapto-1, 8-dimercapto-3, 6-dithiooctane, 4, 8-bis (mercaptomethyl) -1, 11-dithio-3, 6, 9-trithiaundecane and 5, 7-bis (mercaptomethyl) -1, 11-dimercapto-3, 6, 9-trithiaundecane.
The diluent B is one or a mixture of more than two of diallyl phthalate, diallyl isophthalate, diallyl terephthalate, 2-phenoxyethyl methacrylate, o-phenylphenol methacrylate, phenyl methacrylate, benzyl methacrylate, o-phenylphenol methacrylate, 2- (benzyloxy) ethyl methacrylate, N-vinyl pyrrolidone, dimethylaminoethylacrylamide, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate and isobornyl (meth) acrylate.
The initiator is methyl benzoylformate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene, benzoin dimethyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, or, 4-phenyl benzophenone, ethyl 4-dimethylaminobenzoate, 2, 4-diethyl thioxanthone and isopropyl thioxanthone (2,4 isomeric mixture).
The following description will be given with reference to specific examples.
Example 1
(1) The synthesis of the high-refraction acrylate monomer comprises the following steps:
adding a phenyl methacrylate (CAS:2177-70-0) monomer and a dibenzothiophene 5-oxide (CAS:1013-23-6) monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 20 ℃ for 30 hours; wherein the mass ratio of phenyl methacrylate (CAS:2177-70-0) monomer, dibenzothiophene 5-oxide (CAS:1013-23-6), concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 0.6: 0.001: 0.005: 10; the solvent A is dichloromethane.
(2) The synthesis of the high refractive thiol monomer comprises the following steps:
adding thiophenol monomer (CAS number: 108-98-5) and dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer into solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at 20 deg.C for 30 hr; wherein the mass ratio of thiophenol monomer (CAS number: 108-98-5), dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer, concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 0.5: 0.002: 0.003: 20; the solvent A is acetonitrile.
(3) The synthesis of the high-refraction optical resin comprises the following steps:
mixing newly synthesized high-refraction optical acrylic monomer and high-refraction mercaptan monomer together, adding diluent A, diluent B and photoinitiator, stirring uniformly, and obtaining the product with the wavelength of 365nm and the energy of 2000mw/cm2Irradiating UV50S to obtain high refractive optical resin; wherein the mass ratio of the high-refraction acrylate monomer, the high-refraction mercaptan monomer, the diluent A, the diluent B and the photoinitiator is 1: 0.5: 0.2: 0.1: 0.001. the diluent A is 4, 5-bis (mercaptomethyl) o-xylene, the diluent B is diallyl phthalate, and the initiator is methyl benzoylformate.
Example 2
(1) The synthesis of the high-refraction acrylate monomer comprises the following steps:
adding a phenyl methacrylate (CAS:2177-70-0) monomer and a dibenzothiophene 5-oxide (CAS:1013-23-6) monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 80 ℃ for 120 hours; wherein the mass ratio of phenyl methacrylate (CAS:2177-70-0) monomer, dibenzothiophene 5-oxide (CAS:1013-23-6), concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 2: 0.01: 0.01: 40; the solvent A is cyclohexanone.
(2) The synthesis of the high refractive thiol monomer comprises the following steps:
adding thiophenol monomer (CAS number: 108-98-5) and dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer into solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at 80 deg.C for 120 hr; wherein the mass ratio of thiophenol monomer (CAS number: 108-98-5), dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer, concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 1.8: 0.01: 0.02: 50; the solvent A is trichloromethane.
(3) The synthesis of the high-refraction optical resin comprises the following steps:
mixing newly synthesized high-refraction optical acrylic monomer and high-refraction mercaptan monomer together, adding diluent A, diluent B and photoinitiator, stirring uniformly, and obtaining the product with the wavelength of 365nm and the energy of 5000mw/cm2Irradiating UV500S to obtain high refractive optical resin; wherein the mass ratio of the high-refraction acrylate monomer, the high-refraction mercaptan monomer, the diluent A, the diluent B and the photoinitiator is 1: 3: 5: 4: 0.005.
the diluent A is 11-dithiol-3, 6, 9-trithiaundecane, the diluent B is o-phenylphenol methacrylate, and the initiator is 1-hydroxycyclohexyl phenyl ketone.
Example 3
(1) The synthesis of the high-refraction acrylate monomer comprises the following steps:
adding a phenyl methacrylate (CAS:2177-70-0) monomer and a dibenzothiophene 5-oxide (CAS:1013-23-6) monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 70 ℃ for 100 hours; wherein the mass ratio of phenyl methacrylate (CAS:2177-70-0) monomer, dibenzothiophene 5-oxide (CAS:1013-23-6), concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 1: 0.005: 0.008: 30, of a nitrogen-containing gas; the solvent A is toluene.
(2) The synthesis of the high refractive thiol monomer comprises the following steps:
adding thiophenol monomer (CAS number: 108-98-5) and dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer into solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at 70 ℃ for 90 hours; wherein the mass ratio of thiophenol monomer (CAS number: 108-98-5), dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer, concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 1: 0.008: 0.01: 30, of a nitrogen-containing gas; the solvent A is p-xylene.
(3) The synthesis of the high-refraction optical resin comprises the following steps:
mixing newly synthesized high-refraction optical acrylic monomer and high-refraction mercaptan monomer together, adding diluent A, diluent B and photoinitiator, stirring uniformly, and obtaining the product with the wavelength of 365nm and the energy of 4000mw/cm2Irradiating UV100S to obtain high refractive optical resin; wherein the mass ratio of the high-refraction acrylate monomer, the high-refraction mercaptan monomer, the diluent A, the diluent B and the photoinitiator is 1: 2: 2: 2: 0.0022.
the diluent A is 4,4' -thiobisthiophenol, the diluent B is 2-phenoxyethyl methacrylate, and the initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Example 4
(1) The synthesis of the high-refraction acrylate monomer comprises the following steps:
adding a phenyl methacrylate (CAS:2177-70-0) monomer and a dibenzothiophene 5-oxide (CAS:1013-23-6) monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 60 ℃ for 70 hours; wherein the mass ratio of phenyl methacrylate (CAS:2177-70-0) monomer, dibenzothiophene 5-oxide (CAS:1013-23-6), concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 1.5: 0.009: 0.009: 35; the solvent A is cyclohexanone.
(2) The synthesis of the high refractive thiol monomer comprises the following steps:
adding a thiophenol monomer (CAS number: 108-98-5) and a dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 20-80 ℃ for 30-120 hours; wherein the mass ratio of thiophenol monomer (CAS number: 108-98-5), dibenzothiophene 5-oxide (CAS number: 1013-23-6) monomer, concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 1.5: 0.0018: 0.0028: 45, a first step of; the solvent A is cyclohexanone.
(3) The synthesis of the high-refraction optical resin comprises the following steps:
mixing newly synthesized high-refraction optical acrylic monomer and high-refraction mercaptan monomer, adding diluent A and diluent B, and photoinitiatingThe agent is evenly stirred, and the wavelength is 365nm, and the energy is 3000mw/cm2Irradiating UV300S to obtain high refractive optical resin; wherein the mass ratio of the high-refraction acrylate monomer, the high-refraction mercaptan monomer, the diluent A, the diluent B and the photoinitiator is 1: 2.5: 3.5: 3: 0.0035. the diluent A is 4, 8-bis (mercaptomethyl) -1, 11-dithio-3, 6, 9-trithiaundecane, the diluent B is 2-phenoxyethyl (meth) acrylate, and the initiator is 2, 4-diethylthioxanthone.
Comparative example
The resin prepared according to example 4 of the publication of chinese patent CN109053998A was used as a comparative example.
The examples 1 to 4 and the comparative example were subjected to performance tests, and the results are shown in table 1.
TABLE 1 Performance parameters of high refractive optical materials prepared in examples 1-4
As can be seen from the comparison between the examples and the comparative examples, the optical resin obtained by the embodiment of the technical scheme of the invention has the advantages of refractive index of more than 1.7, high transmittance, good optical properties such as Abbe number, haze and the like, high hardness, small yellowness, glass transition temperature of more than 160 ℃ and good mechanical properties.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments and it is not intended to limit the invention to the specific embodiments described. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (5)
1. A preparation method of a high-refraction high-temperature-resistant optical monomer is characterized by comprising the following steps: the high-refraction high-temperature-resistant optical monomer comprises a high-refraction acrylate monomer and a high-refraction mercaptan monomer, wherein the structural formula of the high-refraction acrylate monomer is shown as the formula (1):
the structural formula of the high-refraction thiol monomer is shown as a formula (2):
the high-refraction acrylate monomer is prepared by the following steps:
adding a phenyl methacrylate monomer and a dibenzothiophene 5-oxide monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 20-80 ℃ for 30-120 hours;
the high-refraction mercaptan monomer is prepared by the following steps:
adding a thiophenol monomer and a dibenzothiophene 5-oxide monomer into a solvent A, adding concentrated sulfuric acid and 3-mercaptopropionic acid, and reacting at the temperature of 20-80 ℃ for 30-120 hours.
2. The method for preparing a high refractive index and high temperature resistant optical monomer according to claim 1, wherein: the mass ratio of the phenyl methacrylate monomer, dibenzothiophene 5-oxide, concentrated sulfuric acid, 3-hydroxypropionic acid and solvent A is 1: 0.6-2: 0.001-0.01: 0.005-0.01: 10 to 40.
3. The method for preparing a high refractive index and high temperature resistant optical monomer according to claim 2, wherein: the mass ratio of the thiophenol monomer, the dibenzothiophene 5-oxide monomer, the concentrated sulfuric acid, the 3-hydroxypropionic acid and the solvent A is 1: 0.5-1.8: 0.002 to 0.01: 0.003 to 0.02: 20 to 50.
4. The method for preparing a high refractive index and high temperature resistant optical monomer according to claim 3, wherein: the solvent A is one or a mixture of more than two of dichloromethane, trichloromethane, cyclohexanone, dioxane, p-xylene, toluene, acetonitrile and ethyl acetate.
5. A method for preparing an optical resin, comprising: it comprises the following steps: uniformly mixing the high-refraction acrylate monomer, the high-refraction mercaptan monomer, the diluent and the photoinitiator, and then reacting under the irradiation of ultraviolet rays to obtain optical resin; the high-refraction acrylate monomer and the high-refraction thiol monomer are obtained by the preparation method of the high-refraction high-temperature-resistant optical monomer according to claim 1;
the diluent A is one or a mixture of more than two of 1, 4-butanediol bis (mercaptoacetate), 4, 5-bis (mercaptomethyl) o-xylene, 4 '-biphenylthiol, bis (2-mercaptoethyl) sulfide, 4' -thiobisthiophenol, 1, 5-dimercapto-3-thiapentane, 4-mercapto-1, 8-dimercapto-3, 6-dithiooctane, 4, 8-bis (mercaptomethyl) -1, 11-dithio-3, 6, 9-trithiaundecane and 5, 7-bis (mercaptomethyl) -1, 11-dimercapto-3, 6, 9-trithiaundecane; the diluent B is one or a mixture of more than two of diallyl phthalate, diallyl isophthalate, diallyl terephthalate, 2-phenoxyethyl methacrylate, o-phenylphenol methacrylate, phenyl methacrylate, benzyl methacrylate, o-phenylphenol methacrylate, 2- (benzyloxy) ethyl methacrylate, N-vinyl pyrrolidone, dimethylaminoethylacrylamide, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate and isobornyl (meth) acrylate;
the initiator is methyl benzoylformate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis [2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl ] titanocene, benzoin dimethyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, or, 4-phenyl benzophenone, one or more of ethyl 4-dimethylaminobenzoate, 2, 4-diethyl thioxanthone and isopropyl thioxanthone;
the mass ratio of the high-refraction acrylate monomer to the high-refraction mercaptan monomer to the diluent A to the diluent B to the photoinitiator is 1: 0.5-3: 0.2-5: 0.1-4: 0.001 to 0.005.
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