CN111763320A - Optical resin monomer and preparation method thereof, optical resin and preparation method thereof - Google Patents
Optical resin monomer and preparation method thereof, optical resin and preparation method thereof Download PDFInfo
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- CN111763320A CN111763320A CN202010698197.6A CN202010698197A CN111763320A CN 111763320 A CN111763320 A CN 111763320A CN 202010698197 A CN202010698197 A CN 202010698197A CN 111763320 A CN111763320 A CN 111763320A
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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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/16—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of hydrogen sulfide or its salts to unsaturated compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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Abstract
The invention provides an optical resin, which is prepared from the following components; the components comprise: 70-80 parts by weight of an episulfide compound; 20-30 parts by weight of an optical resin monomer; 0.1-1 part by weight of a catalyst; the optical resin monomer is obtained by reacting one or more compounds shown in formulas (I) to (IV) with isocyanate alkyl acrylate. Compared with the prior art, the compound with isocyanate functional groups and cyano functional groups is introduced into the optical resin, free isocyanate can be effectively eliminated along with the ring-opening reaction of polythiol, the reaction degree of the monomer is improved, and the toughness and the mechanical property of the optical resin are further improved.
Description
Technical Field
The invention belongs to the technical field of optical resin materials, and particularly relates to an optical resin monomer and a preparation method thereof, and an optical resin and a preparation method thereof.
Background
With the development of polythiourethane optical resin materials in recent years, optical lenses with refractive indexes of 1.60 and 1.67 have been popular in domestic markets, and the characteristics of high refractive index, high abbe number, high light transmittance and high impact toughness are widely evaluated. However, with the exponential increase of myopia proportion of teenagers and the increasing of myopia degrees, the refractive indexes of 1.60 and 1.67 cannot meet the application requirements of high-degree people. The main reason is that the polythiourethane optical resin material is polymerized by polythiol and isocyanate, the polythiol generally accounts for about 50%, the sulfur content basically reaches the upper limit, the refractive index is further improved by increasing sulfur element, and other types of resin materials are needed to realize the polythioether material, namely, the polythioether material, the consumption of episulfide used as a raw material of the polythioether material can reach more than 70%, the sulfur content is greatly improved, and therefore, the refractive index can reach more than 1.70.
However, at present, three components, namely cyclic thioether, polythiol and isocyanate, are adopted as main raw materials of polythioether materials with refractive indexes of more than 1.70, and the reaction mechanism is as follows: under the action of a cationic initiator, the mercapto group of the polythiol attacks the episulfide to open the ring, form new mercapto group, further perform ring-opening self-polymerization with other episulfide, and finally terminate the reaction by isocyanate and block the end. The three-component reaction system has the following problems which cannot be solved: (1) the polythiol is micromolecule, has large pungent smell, can cause the smell of the product to be larger after being cured after a small amount of monomer residues, and the prior art has a general solution mode of secondary curing high-temperature treatment; (2) the isocyanate has low reactivity, and under the production conditions of the prior art, more unreacted isocyanate monomers remain, so that the texture reject ratio of the optical product is high; (3) the residual micromolecule polythiol and isocyanate monomer can directly cause the reduction of the mechanical property of the optical material and the aging resistance of the product, the burning probability is greatly increased in the processes of cleaning and hard coating of the optical lens, and the yield is reduced.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an optical resin monomer, a preparation method thereof, an optical resin and a preparation method thereof, wherein the optical resin has a high degree of monomer reaction.
The invention provides an optical resin, which is prepared from the following components; the components comprise:
70-80 parts by weight of an episulfide compound;
20-30 parts by weight of an optical resin monomer;
0.1-1 part by weight of a catalyst;
the optical resin monomer is obtained by reacting one or more compounds shown in formulas (I) to (IV) with isocyanate alkyl acrylate;
preferably, the ultraviolet light-absorbing material also comprises 0.1-1 part by weight of an ultraviolet absorbent; the ultraviolet absorbent is selected from one or more of UV326, UV327, UV329, UV-531, UV-9 and UV-234.
Preferably, the coating also comprises 0.05-0.1 weight part of phosphate ester release agent.
Preferably, further comprises a toner; the concentration of the toner in the optical resin is 10-20 ppm; the toner is one or more selected from 1-hydroxy-4- (p-toluidino) -anthraquinone, 1, 4-bis [ (2,4, 6-trimethylphenyl) amino ] -9, 10-anthracenedione, 1, 4-bis [ (2-methylphenyl) amino ] anthraquinone, 1, 4-bis (ethylamino) -9, 10-anthracenedione and N- [4- [ (4-hydroxyanthradin-1-yl) amino ] phenyl ] acetamide.
Preferably, the episulfide compound is selected from one or more of bis (β -epithiopropyl) sulfide, bis (β -epithiopropyl) disulfide, bis (β -epithiopropyl) trisulfide, bis (β -epithiopropyl sulfide) methane, 1, 2-bis (β -epithiopropyl sulfide) ethane, 1, 3-bis (β -epithiopropyl sulfide) propane, 1, 4-bis (β -epithiopropyl sulfide) butane, bis (β -epithiopropyl thioethyl) sulfide;
the catalyst is selected from one or more of tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide and triphenylphosphine.
Preferably, the alkyl group of the isocyanate alkyl acrylate has 1 to 3 carbon atoms.
The invention also provides a preparation method of the optical resin, which comprises the following steps:
s1) mixing an optical resin monomer with a catalyst, and then mixing and reacting with an episulfide compound to obtain a prepolymerization feed liquid;
s2) carrying out gradient temperature rise solidification on the prepolymerization feed liquid to obtain the optical resin.
Preferably, the procedure of the gradient temperature-rising curing is as follows: the initial temperature is 15-25 ℃, the temperature is kept for 1.5-3.5 h, the temperature is raised to 45-55 ℃ for 10-15 h, the temperature is raised to 75-85 ℃ for 2.5-3.5 h, and finally the temperature is lowered to 65-75 ℃ for 0.5-2.5 h.
The invention also provides an optical resin monomer, which is obtained by reacting one or more compounds shown in the formulas (I) to (IV) with isocyanate alkyl acrylate;
the invention also provides a preparation method of the optical resin monomer, which comprises the following steps:
mixing one or more compounds shown in formulas (I) to (IV), isocyanate alkyl acrylate and a photoinitiator, and obtaining an optical resin monomer after light-induced reaction;
the invention provides an optical resin, which is prepared from the following components; the components comprise: 70-80 parts by weight of an episulfide compound; 20-30 parts by weight of an optical resin monomer; 0.1-1 part by weight of a catalyst; the optical resin monomer is obtained by reacting one or more compounds shown in formulas (I) to (IV) with isocyanate alkyl acrylate. Compared with the prior art, the compound with isocyanate functional groups and cyano functional groups is introduced into the optical resin, free isocyanate can be effectively eliminated along with the ring-opening reaction of polythiol, the reaction degree of the monomer is improved, and the toughness and the mechanical property of the optical resin are further improved.
Drawings
FIG. 1 is an infrared spectrum of an optical resin monomer NCO-S3SH2 obtained in example 1 of the present invention;
FIG. 2 is an infrared spectrum of an optical resin monomer NCO-S6SH3 obtained in example 2 of the present invention;
FIG. 3 is an infrared spectrum of an optical resin monomer NCO-S2SH1 obtained in example 3 of the present invention;
FIG. 4 is an infrared spectrum of NCO-S4SH3 as an optical resin monomer obtained in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an optical resin monomer, which is characterized in that the optical resin monomer is obtained by reacting one or more compounds shown in formulas (I) to (IV) with isocyanate alkyl acrylate;
the carbon number of the alkyl group in the isocyanate alkyl acrylate is preferably 1-3, more preferably 2-3, and even more preferably 2, namely, the isocyanate alkyl acrylate is most preferably isocyanate ethyl acrylate in the invention.
In the present invention, the optical resin monomer is most preferably represented by the following formula:
wherein n is an integer of 1-3, and R is a group of the compounds represented by the formulas (I) to (IV) except for a mercapto group.
The invention combines polythiol and isocyanate monomer into one to form a sulfhydryl and isocyanate-terminated compound (two functional groups can stably exist without Lewis base initiator), and free isocyanate can be effectively eliminated along with the ring-opening reaction of polythiol, thereby improving the monomer reaction degree to the maximum extent, and solving the problems of poor texture, mechanical property, temperature and ageing resistance of optical resin, large smell and the like fundamentally.
The invention also provides a preparation method of the optical resin monomer, which is characterized by comprising the following steps: mixing one or more compounds shown in formulas (I) to (IV), isocyanate alkyl acrylate and a photoinitiator, and obtaining an optical resin monomer after light-induced reaction;
in the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Mixing one or more compounds shown in formulas (I) to (IV) and isocyanate alkyl acrylate with a photoinitiator; the isocyanate alkyl acrylate is the same as that described above and is not described in detail herein; the molar ratio of one or more of the compounds of formulae (I) to (IV) to the isocyanate alkyl acrylate is preferably 1: (1 to 1.5), more preferably 1: (1.1 to 1.4), and more preferably 1: (1.1-1.2); the photoinitiator is preferably a free radical photoinitiator, more preferably one or more of a free radical photoinitiator 1173, 184, 907, TPO and TPO-L; the mass of the photoinitiator is preferably 1 to 5 percent, more preferably 25 to 4 percent, and even more preferably 2 to 3 percent of the total mass of one or more compounds shown in formulas (I) to (IV) and the isocyanate alkyl acrylate.
After mixing, the mixture is irradiated by light to initiate reaction, and preferably placed under an ultraviolet lamp for photoreaction; the reaction time is preferably 10-60 s, more preferably 30-60 s, and still more preferably 50-60 s.
After the reaction, removing unreacted monomers by preferably vacuum degassing to obtain optical resin monomers; the time for vacuum degassing is preferably 10-60 min, more preferably 20-50 min, still more preferably 20-40 min, and most preferably 30 min.
The invention also provides an optical resin comprising the optical resin monomer, which is prepared from the following components; the components comprise:
70-80 parts by weight of an episulfide compound;
20-30 parts by weight of an optical resin monomer;
0.1-1 part by weight of a catalyst;
the optical resin monomer is obtained by reacting one or more compounds shown in formulas (I) to (IV) with isocyanate alkyl acrylate;
in the present invention, the content of the episulfide compound is preferably 72 to 78 parts by weight, more preferably 74 to 76 parts by weight, and still more preferably 75 parts by weight; the episulfide compound is preferably one or more of bis (beta-epithiopropyl) sulfide, bis (beta-epithiopropyl) disulfide, bis (beta-epithiopropyl) trisulfide, bis (beta-epithiopropyl sulfide) methane, 1, 2-bis (beta-epithiopropyl sulfide) ethane, 1, 3-bis (beta-epithiopropyl sulfide) propane, 1, 4-bis (beta-epithiopropyl sulfide) butane and bis (beta-epithiopropyl sulfide) sulfide.
The content of the optical resin monomer is preferably 22 to 28 parts by weight, more preferably 24 to 36 parts by weight, and even more preferably 25 parts by weight; the kind of the optical resin monomer is the same as that described above, and is not described in detail herein.
The content of the catalyst is preferably 0.1 to 0.8 part by weight, more preferably 0.1 to 0.6 part by weight, still more preferably 0.1 to 0.4 part by weight, and most preferably 0.1 to 0.2 part by weight; the catalyst is preferably one or more of tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide and triphenylphosphine.
According to the invention, the optical resin preferably further comprises 0.1-1 part by weight of an ultraviolet absorber, more preferably 0.1-0.6 part by weight, still more preferably 0.1-0.4 part by weight, and most preferably 0.1-0.2 part by weight; the ultraviolet absorbent is preferably one or more of UV326, UV327, UV329, UV-531, UV-9 and UV-234.
According to the invention, the optical resin also comprises 0.05-0.1 weight part of phosphate ester release agent, more preferably 0.08-0.1 weight part; the phosphate ester release agent is preferably one or more of di-n-butyl phosphate, nonylphenol polyoxyethylene ether phosphate, styrylphenol polyoxyethylene ether phosphate, C12 alcohol polyoxyethylene ether phosphate, C12 alcohol phosphate and C12-14 alcohol phosphate.
According to the present invention, the optical resin preferably further includes a toner; the concentration of the toner in the optical resin is preferably 10-20 ppm, more preferably 12-18 ppm, still more preferably 14-16 ppm, and most preferably 15 ppm; the toner is preferably one or more of 1-hydroxy-4- (p-toluidino) -anthraquinone, 1, 4-bis [ (2,4, 6-trimethylphenyl) amino ] -9, 10-anthracenedione, 1, 4-bis [ (2-methylphenyl) amino ] anthraquinone, 1, 4-bis (ethylamino) -9, 10-anthracenedione, and N- [4- [ (4-hydroxyanthradin-1-yl) amino ] phenyl ] acetamide.
According to the invention, the compound with isocyanate functional groups and cyano functional groups is introduced into the optical resin, so that free isocyanate can be effectively eliminated along with the ring-opening reaction of polythiol, the reaction degree of monomers is improved, and the toughness and mechanical properties of the optical resin are further improved.
The invention also provides a preparation method of the optical resin, which comprises the following steps: s1) mixing an optical resin monomer with a catalyst, and then mixing and reacting with an episulfide compound to obtain a prepolymerization feed liquid; s2) carrying out gradient temperature rise solidification on the prepolymerization feed liquid to obtain the optical resin.
Mixing an optical resin monomer with a catalyst; the optical resin monomer and the catalyst are the same as those described above, and are not described in detail herein; according to the present invention, this step is preferably further added with one or more of an ultraviolet absorber, a forest acid ester type release agent and a toner; the ultraviolet absorber, the phosphate releasing agent and the toner are the same as those described above, and are not described herein again.
Then mixing the prepolymer with an episulfide compound for reaction to obtain prepolymerization feed liquid; the reaction is preferably carried out under stirring; the temperature of the reaction is preferably 20 ℃ or lower; the mixing reaction time is preferably 30-60 min, more preferably 40-60 min, and still more preferably 50 min.
Preferably, the prepolymerization feed liquid is subjected to vacuum degassing, filtering and then gradient heating solidification to obtain optical resin; the vacuum degassing time is preferably 10-60 min, more preferably 20-40 min, and further preferably 30 min; the aperture of the filter membrane used for filtering is preferably 1-5 μm, more preferably 2-4 μm, and further preferably 3 μm; the procedure of gradient temperature rise curing is as follows: the initial temperature is 15-25 ℃, the heat is preserved for 1.5-3.5 h, the temperature is raised to 45-55 ℃ for 10-15 h, the temperature is raised to 75-85 ℃ for 2.5-3.5 h, the heat is preserved for 1-3 h, and finally the temperature is lowered to 65-75 ℃ for 0.5-2.5 h; more preferably: the initial temperature is 18-22 ℃, the heat preservation is carried out for 1.5-3 h, the temperature is raised to 50-55 ℃ for 11-14 h, the temperature is raised to 78-82 ℃ for 2.8-3.2 h, the heat preservation is carried out for 1.5-2.5 h, and finally the temperature is lowered to 68-72 ℃ for 0.8-2 h; further preferably: the initial temperature is 20 ℃, the temperature is kept for 1.5-2.5 h, the temperature is raised to 53-55 ℃ for 12-13 h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 1.8-2.2 h, and finally the temperature is lowered to 68-72 ℃ for 1-1.5 h; most preferably: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, and finally the temperature is lowered to 70 ℃ for 1 h.
In order to further illustrate the present invention, the following describes the optical resin monomer and the preparation method thereof, the optical resin and the preparation method thereof in detail with reference to the examples.
The reagents used in the following examples are all commercially available.
Evaluation method
1. Refractive index: measuring the nd value by using a multi-wavelength Abbe refractometer, wherein the instrument manufacturer and the model are Japanese ATAGO, DR-M4;
2. transmittance and yellow index: measuring full-wavelength light transmittance by using a spectrocolorimeter, wherein the manufacturers and models of the instruments are HunterLab and UltraScan;
3. impact resistance: measuring the weight of a steel ball which can be borne by the lens by adopting a ball drop impact tester, and measuring the height of the steel ball by 1.27 m and the weights of the steel ball by 16g, 32g, 50g, 64g, 90g, 110g and 500g according to an FDA standard measuring method; the test object is a 500-degree optical resin lens, and the center thickness is 1.2 mm;
4. glass transition temperature: detecting the Tg point by using a differential scanning calorimeter, wherein the manufacturer and model of the instrument are METTLER-TOLEDO, DSC 1;
5. texture: observing the polymerization poor texture condition in a dark box under strong light;
6. ultraviolet aging resistance: the ultraviolet aging test box has the instrument manufacturer and model of Q-Lab, QUV. Aging conditions are as follows: 340nm, 0.69w/m2，48h。
Example 1
Mixing an S2SH3 compound (a compound shown in a formula (I)) with isocyanate ethyl acrylate according to a molar mass ratio of 1:1.1, adding a photoinitiator 1173, wherein the addition amount of the photoinitiator 1173 accounts for 2% of the total mass of the materials, uniformly stirring at room temperature, placing under an ultraviolet lamp (365nm and 100W) for photoreaction for 60 seconds, and removing unreacted monomers by vacuum degassing for 30min to obtain an optical resin monomer NCO-S3SH 2.
The optical resin monomer NCO-S3SH2 obtained in example 1 was analyzed by infrared spectroscopy to obtain an infrared spectrum thereof, as shown in FIG. 1.
Example 2
Mixing an S5SH4 compound (a compound shown in a formula (II)) with isocyanate ethyl acrylate according to a molar mass ratio of 1:1.1, adding a photoinitiator 1173, wherein the addition amount of the photoinitiator 1173 accounts for 2% of the total mass of the materials, uniformly stirring at room temperature, placing under an ultraviolet lamp (365nm and 100W) for photoreaction for 60 seconds, and removing unreacted monomers by vacuum degassing for 30min to obtain an optical resin monomer NCO-S6SH 3.
The optical resin monomer NCO-S6SH3 obtained in example 2 was analyzed by infrared spectroscopy to obtain an infrared spectrum thereof, as shown in FIG. 2.
Example 3
Mixing an S1SH2 compound (a compound shown in a formula (III)) and isocyanate ethyl acrylate according to a molar mass ratio of 1:1.1, adding a photoinitiator 1173, wherein the addition amount of the photoinitiator 1173 accounts for 2% of the total mass of the materials, uniformly stirring at room temperature, placing the mixture in an ultraviolet lamp (365nm, 100W) for photoreaction for 60 seconds, and then carrying out vacuum degassing for 30min to remove unreacted monomers to obtain an optical resin monomer NCO-S2SH 1.
The optical resin monomer NCO-S2SH1 obtained in example 3 was analyzed by infrared spectroscopy to obtain an infrared spectrum thereof, as shown in FIG. 3.
Example 4
Mixing an S3SH4 compound (a compound shown in a formula (IV)) and isocyanate ethyl acrylate according to a molar mass ratio of 1:1.2, adding a photoinitiator 1173, wherein the addition amount of the photoinitiator 1173 accounts for 2% of the total mass of the materials, uniformly stirring at room temperature, placing under an ultraviolet lamp (365nm and 100W) for photoreaction for 60 seconds, and removing unreacted monomers by vacuum degassing for 30min to obtain an optical resin monomer NCO-S4SH 3.
The optical resin monomer NCO-S4SH3 obtained in example 4 was analyzed by infrared spectroscopy to obtain an infrared spectrum thereof, as shown in FIG. 4.
Example 5
(1) To 25g of NCO-S3SH2 obtained in example 1, 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added at 20 ℃ and, after complete dissolution by stirring, 75g of bis (. beta. -epithiopropyl) sulfide was added and, then, the mixture was stirred at 20 ℃ for 50 minutes to obtain a prepolymerization feed liquid.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Example 6
(1) To 25g of NCO-S6SH3 obtained in example 2, 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added at 20 ℃ and, after complete dissolution by stirring, 75g of bis (. beta. -epithiopropyl) sulfide was added and the mixture was stirred at 20 ℃ for 50 minutes to obtain a prepolymerization liquid.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Example 7
(1) To 25g of NCO-S2SH1 obtained in example 3, 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added at 20 ℃ and, after complete dissolution by stirring, 75g of bis (. beta. -epithiopropyl) sulfide was added and, then, the mixture was stirred at 20 ℃ for 50 minutes to obtain a prepolymerization liquid.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Example 8
(1) To 25g of NCO-S4SH3 obtained in example 4, 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added at 20 ℃ and, after complete dissolution by stirring, 75g of bis (. beta. -epithiopropyl) sulfide was added and, then, the mixture was stirred at 20 ℃ for 50 minutes to obtain a prepolymerization liquid.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Example 9
(1) To 25g of NCO-S3SH2 obtained in example 1, 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added at 20 ℃ and, after completion of stirring and dissolution, 75g of bis (. beta. -epithiopropyl) disulfide was added and stirred at 20 ℃ for 50 minutes to obtain a prepolymerization feed solution.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Example 10
(1) To 25g of NCO-S6SH3 obtained in example 2, 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added at 20 ℃ and, after completion of stirring and dissolution, 75g of bis (. beta. -epithiopropyl) disulfide was added and stirred at 20 ℃ for 50 minutes to obtain a prepolymerization solution.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Example 10
(1) To 25g of NCO-S2SH1 obtained in example 3 were added 0.1g of UV-329 as an ultraviolet absorber, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone at 20 ℃ and, after complete dissolution by stirring, 75g of bis (. beta. -epithiopropyl) disulfide was added and the mixture was stirred at 20 ℃ for 50 minutes to obtain a prepolymerization solution, the results of which are shown in Table 1.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, then the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Example 11
(1) To 25g of NCO-S4SH3 obtained in example 4, 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added at 20 ℃ and, after completion of stirring and dissolution, 75g of bis (. beta. -epithiopropyl) disulfide was added and stirred at 20 ℃ for 50 minutes to obtain a prepolymerization solution.
(2) And (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Comparative example 1
(1) After 12.5g each of S1SH2 (a compound represented by formula III) and isophorone diisocyanate (IPDI) were mixed at 20 ℃ and 0.1g of an ultraviolet absorber UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone were added thereto, followed by stirring and dissolving completely, 75g of bis (. beta. -epithiocyclopropyl) sulfide was added thereto and stirred at 20 ℃ for 50 minutes to obtain a prepolymerization feed solution;
(2) and (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
Comparative example 2
(1) S1SH2 and IPDI (12.5 g each) were mixed at 20 ℃ and then added with 0.1g of UV-329, 0.1g of di-n-butyl phosphate, 0.1g of tetraphenylphosphonium bromide and 15ppm of 1-hydroxy-4- (p-toluidino) -anthraquinone as an ultraviolet absorber, and after complete dissolution by stirring, 75g of bis (. beta. -epithiopropyl) disulfide was added and stirred at 20 ℃ for 50 minutes to obtain a prepolymerization feed solution;
(2) and (2) degassing the prepolymerization feed liquid obtained in the step (1) in vacuum for 30min, filtering the obtained prepolymerization feed liquid by a polytetrafluoroethylene filtering membrane with the aperture of 3 mu m, injecting the obtained product into a glass mold, placing the mold into a temperature programming curing furnace for primary curing to obtain a cured optical resin lens, and performing a curing and temperature programming: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, the temperature is finally lowered to 70 ℃ for 1h, the mold is opened, and the performance of the obtained optical resin lens is detected, and the obtained results are shown in table 1.
TABLE 1 test results of optical resin lenses
As can be seen from table 1, the refractive index, the ultraviolet aging resistance, the odor and the texture of the product obtained in the example are significantly better than those of the comparative example, which shows that after 1 mercapto group in polythiol and C ═ C bond in isocyanate ethyl acrylate are subjected to photo-addition reaction, the material performance and the aging resistance of the obtained novel optical resin monomer are greatly improved and the problems of the texture and the odor of the product are effectively eliminated after the monomolecular polythiol and the isocyanate are replaced by the novel optical resin monomer.
Claims (10)
1. An optical resin is characterized by being prepared from the following components; the components comprise:
70-80 parts by weight of an episulfide compound;
20-30 parts by weight of an optical resin monomer;
0.1-1 part by weight of a catalyst;
the optical resin monomer is obtained by reacting one or more compounds shown in formulas (I) to (IV) with isocyanate alkyl acrylate;
2. the optical resin according to claim 1, further comprising 0.1 to 1 part by weight of an ultraviolet absorber; the ultraviolet absorbent is selected from one or more of UV326, UV327, UV329, UV-531, UV-9 and UV-234.
3. The optical resin according to claim 1, further comprising 0.05 to 0.1 parts by weight of a phosphoric ester-based release agent.
4. An optical resin according to claim 1, further comprising a toner; the concentration of the toner in the optical resin is 10-20 ppm; the toner is one or more selected from 1-hydroxy-4- (p-toluidino) -anthraquinone, 1, 4-bis [ (2,4, 6-trimethylphenyl) amino ] -9, 10-anthracenedione, 1, 4-bis [ (2-methylphenyl) amino ] anthraquinone, 1, 4-bis (ethylamino) -9, 10-anthracenedione and N- [4- [ (4-hydroxyanthradin-1-yl) amino ] phenyl ] acetamide.
5. The optical resin according to claim 1, wherein the episulfide compound is selected from one or more of bis (β -epithiopropyl) sulfide, bis (β -epithiopropyl) disulfide, bis (β -epithiopropyl) trisulfide, bis (β -epithiopropyl) methane, 1, 2-bis (β -epithiopropyl sulfide) ethane, 1, 3-bis (β -epithiopropyl sulfide) propane, 1, 4-bis (β -epithiopropyl sulfide) butane, bis (β -epithiopropyl thioethyl) sulfide;
the catalyst is selected from one or more of tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide and triphenylphosphine.
6. The optical resin according to claim 1, wherein the alkyl group of the isocyanate alkyl acrylate has 1 to 3 carbon atoms.
7. A method for producing an optical resin according to claim 1, comprising:
s1) mixing an optical resin monomer with a catalyst, and then mixing and reacting with an episulfide compound to obtain a prepolymerization feed liquid;
s2) carrying out gradient temperature rise solidification on the prepolymerization feed liquid to obtain the optical resin.
8. The preparation method according to claim 7, wherein the procedure of the gradient temperature-rising curing is as follows: the initial temperature is 15-25 ℃, the temperature is kept for 1.5-3.5 h, the temperature is raised to 45-55 ℃ for 10-15 h, the temperature is raised to 75-85 ℃ for 2.5-3.5 h, and finally the temperature is lowered to 65-75 ℃ for 0.5-2.5 h.
9. An optical resin monomer, which is characterized in that the optical resin monomer is obtained by reacting one or more compounds shown in (I) to (IV) with isocyanate alkyl acrylate;
10. a method for preparing an optical resin monomer, comprising:
mixing one or more compounds shown in formulas (I) to (IV), isocyanate alkyl acrylate and a photoinitiator, and obtaining an optical resin monomer after light-induced reaction;
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| CN113088067A (en) * | 2021-04-30 | 2021-07-09 | 江苏可奥熙光学材料科技有限公司 | High-refraction episulfide modified resin and preparation method thereof |
| CN114736549A (en) * | 2022-03-23 | 2022-07-12 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced Plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
| CN116496463A (en) * | 2023-03-31 | 2023-07-28 | 益丰新材料股份有限公司 | Optical resin material with high refractive index and high Abbe number and curing process thereof |
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| CN114736549A (en) * | 2022-03-23 | 2022-07-12 | 武汉长盈鑫科技有限公司 | FRP (fiber reinforced Plastic) coating resin composition suitable for UV-LED (ultraviolet-light emitting diode) curing and preparation method thereof |
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| CN116496463A (en) * | 2023-03-31 | 2023-07-28 | 益丰新材料股份有限公司 | Optical resin material with high refractive index and high Abbe number and curing process thereof |
| CN116496463B (en) * | 2023-03-31 | 2023-10-17 | 益丰新材料股份有限公司 | Optical resin material with high refractive index and high Abbe number and curing process thereof |
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