CN116496463B - Optical resin material with high refractive index and high Abbe number and curing process thereof - Google Patents

Optical resin material with high refractive index and high Abbe number and curing process thereof Download PDF

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Publication number
CN116496463B
CN116496463B CN202310350974.1A CN202310350974A CN116496463B CN 116496463 B CN116496463 B CN 116496463B CN 202310350974 A CN202310350974 A CN 202310350974A CN 116496463 B CN116496463 B CN 116496463B
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curing
refractive index
abbe number
resin material
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CN116496463A (en
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梁万根
崔卫华
孔凡波
张建林
曹飞羽
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Yifeng New Material Co ltd
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Yifeng New Material Co ltd
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/52—Polythioethers
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

The application belongs to the technical field of optical resin, and particularly relates to an optical resin material with high refractive index and high Abbe number and a curing process thereof.

Description

Optical resin material with high refractive index and high Abbe number and curing process thereof
Technical Field
The application belongs to the technical field of optical resin, and particularly relates to an optical resin material with high refractive index and high Abbe number and a curing process thereof.
Technical Field
Compared with glass materials, the optical resin material has the advantages of low specific gravity, high impact toughness, difficult breakage, comfortable wearing, convenient processing, rich product series, easy dyeing and the like, and is increasingly widely applied to the optical lens market.
Under the same photometric lens, the high refractive index resin can greatly reduce the thickness of the lens and meet the comfort level of wearing by people. The abbe number, also known as the dispersion coefficient, of a lens is an important parameter for measuring the dispersion phenomenon generated by a resin lens, and the higher the abbe number of the resin lens, the lower the dispersion, and the clearer the lens.
In the optical resin technology, the technology is still in reference to the foreign technology and is produced according to experience, so that the quality of the product is far from foreign. Particularly, the research on the episulfide compound in China is less, the episulfide compound is started late, and the production raw material is monopoly of foreign enterprises; the technology for producing optical resins of episulfide compounds is thus far lower than foreign levels.
Generally, the higher the refractive index of the resin material, the more chromatic dispersion and the lower the definition of the image. There has been a great interest in reducing the dispersion while pursuing a high refractive index, i.e., a resin lens having a high refractive index and a high abbe number. At present, in CN105254907B, by accurately determining the curing temperature rising gradient of polyurethane optical resin, the method can greatly improve the curing efficiency and the resin performance in the primary and secondary curing stages for polyurethane optical resins with different refractive index series and same series and different formulas, so that the mechanical property, the thermal property and other properties of the finally obtained resin are optimal. The technology has better use effect on a polyurethane material system which is polymerized step by step, but is not applicable to an anionic ring-opening polymerized polythioether material system with insignificant heat release, and does not play a role in Abbe number promotion in the technology. CN114605639a, by designing the composition, achieves an optimized improvement in storage stability, polymerization rate during the reaction, and heat resistance of the optical material, while controlling the rate of temperature rise in the curing procedure of its embodiment, but does not play a role in improving abbe number.
Disclosure of Invention
Aiming at the defects in the production technology, the application aims to provide an optical resin material with high refractive index and high Abbe number and a curing process thereof.
The technical scheme of the application is as follows:
an optical resin material with high refractive index and high Abbe number is prepared from episulfide compound, polythiol and isocyanate, wherein the chlorine content of polythiol is less than or equal to 500ppm, and the chlorine content of isocyanate is less than or equal to 1000ppm.
Preferably, the polythiol has a chlorine content of 400ppm or less and the isocyanate has a chlorine content of 300ppm or less.
Preferably, the episulfide compound is 70-80 parts, polythiol is 8-20 parts, and isocyanate is 5-15 parts by weight.
Preferably, the episulfide compound is one or more of bis (β -episulfide propyl) sulfide, bis (β -episulfide propyl) disulfide, bis (β -episulfide propyl) trisulfide, bis (β -episulfide propyl sulfide) methane, 1, 2-bis (β -episulfide propyl sulfide) ethane, 1, 3-bis (β -episulfide propyl sulfide) propane, 1, 4-bis (β -episulfide propyl sulfide) butane, bis (β -episulfide propyl sulfide).
Preferably, the polythiol is one or more of thiobis Gan Liuchun, 2, 3-dithio (2-mercapto) -1-propanethiol, 1,5,9, 13-tetramercapto-3, 7, 11-tritridecane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, tetrakis (mercaptomethyl) methane, pentaerythritol tetrakis (3-mercaptopropionic) ester, pentaerythritol tris (3-mercaptopropionic) ester, 1, 2-tetrakis (mercaptomethylthiothio) ethane, dipentaerythritol hexa (3-mercaptopropionic) ester, pentaerythritol tetrakis (3-mercaptobutyric acid) ester.
Preferably, the isocyanate is one or more of 4, 4-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate, hydrogenated xylylene diisocyanate.
The curing process of the optical resin material with high refractive index and high Abbe number comprises primary curing and secondary curing, wherein the curing temperature rise interval of the primary curing is within the range of 20-80 ℃, and the total duration is 11.5-15 h.
Preferably, the curing temperature rise interval comprises 20 ℃ to 55 ℃ and 55 ℃ to 80 ℃, wherein the average temperature rise rate is 5 ℃ to 20 ℃ per hour at 55 ℃ to 80 ℃.
Further preferably, the primary curing comprises in particular five stages, in particular:
the first stage: maintaining at 20deg.C for 2 hr;
and a second stage: raising the temperature to 55 ℃ at 2.50 ℃/h;
and a third stage: raising the temperature to 80 ℃ at a speed of 5-20 ℃/h;
fourth stage: maintaining at 80deg.C for 4 hr;
fifth stage: the temperature was reduced to 60℃at 20℃per hour.
In the polyurethane material system, the aim of high refractive index and Abbe number can not be met at the same time, if Abbe number is more than 35, the refractive index of the polyurethane material is generally less than 1.63, if the refractive index is more than 1.65, the Abbe number is generally lower than 32, and the technology of the polythioether material system is not universal because of the difference between the anionic ring-opening polymerization polythioether material system with insignificant heat release and the polyurethane material system. The inventors have developed studies on a polythioether resin material in order to obtain a resin material having a high refractive index and an Abbe number, specifically as follows: in the polythioether resin material, halogen exists in a form of an end capping group, the existence of the halogen directly influences the crosslinking degree of the material, the lower the crosslinking degree is, the worse the temperature resistance of the material is, the halogen is easy to reduce the weather resistance of the material and easy to yellow; meanwhile, with the improvement of the curing temperature, particularly under the condition of rapid heat release caused by the rapid reaction of the curing rate, the problems of reduced crosslinking degree, reduced temperature resistance and poor weather resistance caused by halogen exist, so that the material is easier to oxidize and break bonds, short-wavelength spectrum absorption is generated, the refractive index nF value is increased, and the Abbe number is reduced. In the same material, the variation fluctuation of Abbe number is mainly influenced by a polymerization process, and aiming at the polythioether resin material, the curing program is usually controlled by adopting temperature programming, mainly because the provided environment temperature is matched with the reaction rate, if the provided temperature is higher than the temperature required by curing, the reaction rate is passively accelerated, rapid heat release and even explosion polymerization are generated, the material is poorly polymerized, and meanwhile, short-wavelength spectrum absorption is generated due to the oxidation of a local overheat molecular chain, the nF value is increased, and the Abbe value is reduced; if the temperature rising rate is too slow, the polymerization reaction proceeds smoothly, but the production efficiency is seriously affected. Meanwhile, according to classical electromagnetic theory, the dispersion of an optical material can be expressed as:
R 1 in 2 in As molecular dispersion, see R 1 in 2 in The polarization ratio of meson at 1 and 2 wavelengths is proportional to the difference of the polarization ratio and the relative molecular mass M, and the polarization ratio is inversely proportional to the density, so that the proper temperature rising rate is selected in the polymer synthesis process, the increase of the M/rho value of the product is ensured, and the corresponding polymer dispersion is relatively reduced, namely the Abbe number is increased. Therefore, the inventors have searched for a polythioether resin material, and have found that an optical resin material having a high refractive index and an Abbe number can be obtained by using an episulfide compound, a polythiol and an isocyanate as raw materials, controlling the chlorine content of the thiol to be 500ppm or less and the chlorine content of the isocyanate to be 1000ppm or less, and matching a specific temperature-increasing program.
The optical resin material with high refractive index and high Abbe number and the curing process thereof provided by the application can be used for preparing the optical resin with lower dispersion and better definition by utilizing the specific raw materials and the specific curing process.
Detailed Description
The technical solutions in the present embodiment will be described in detail below, but the described embodiments are only some embodiments of the present application and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
Example 1
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 1.5h Heating up 16.67℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 20℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Example 2
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 2h Heating up 12.5℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 20℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Example 3
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 3h Heating up 8.33℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 20℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Example 4
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g of methylene dicyclohexyl diisocyanate (with the chloride ion content of 300 ppm), 77g of bis (beta-cyclopropylsulfanyl) sulfide, 15g of pentaerythritol tri (3-mercaptopropionic acid) ester (with the chloride ion content of 400 ppm) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 2.5h Heating up 10℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 20℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Example 5
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g of methylene dicyclohexyl diisocyanate (with the chloride ion content of 300 ppm), 77g of bis (beta-cyclopropylsulfanyl) sulfide, 15g of pentaerythritol tri (3-mercaptopropionic acid) ester (with the chloride ion content of 400 ppm) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 4h Heating up 6.25℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 20℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Example 6
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g of methylene dicyclohexyl diisocyanate (with the chloride ion content of 300 ppm), 77g of bis (beta-cyclopropylsulfanyl) sulfide, 15g of pentaerythritol tri (3-mercaptopropionic acid) ester (with the chloride ion content of 400 ppm) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 5h Heating up 5℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 20℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Comparative example 1
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (chloride ion content 150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Comparative example 2
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (chloride ion content 150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 90 5h Heating up 7℃/h
4 90 4h Maintenance of /
5 60 1h Cooling down 30℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Comparative example 3
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g (chloride ion content 200 ppm) of 1, 2-tetra (mercapto methylthio) ethane, 77g of bis (beta-cyclopropylthioethyl) sulfide, 15g (chloride ion content 230 ppm) of isophorone diisocyanate and 0.10g of tetrabutyl phosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Comparative example 4
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g (chloride ion content is 450 ppm) of 1, 2-tetra (mercapto methyl thio) ethane, 77g of bis (beta-cyclopropyl thio-ethyl) sulfide, 15g (chloride ion content is 350 ppm) of isophorone diisocyanate and 0.10g of tetrabutyl phosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 16h Heating up 1.56℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 30℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Comparative example 5
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g (chloride ion content 600 ppm) of 1, 2-tetra (mercapto methylthio) ethane, 77g of bis (beta-cyclopropylthioethyl) sulfide, 15g (chloride ion content 1200 ppm) of isophorone diisocyanate and 0.10g of tetrabutyl phosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
Proceduresegment(s) Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 20 2h Maintenance of /
2 55 10h Heating up 2.50℃/h
3 80 10h Heating up 2.50℃/h
4 80 4h Maintenance of /
5 60 1h Cooling down 30℃/h
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
program segment Temperature (. Degree. C.) Time (h) Status of Rate of temperature control
1 100 2h Maintenance of /
2 60 1h Cooling down 40℃/h
Physical properties of the optical resin materials prepared in examples and comparative examples were tested in accordance with the following methods.
Refractive index (ne): the sample was prepared as described above, and data at a wavelength of 546.1nm (mercury green e line) was measured at 20℃using an Abbe refractometer Multi-wave length Abbe Refractometer DR-M4 (ATTGO Co., ltd.).
Abbe number (vd): the sample was prepared in the above manner, and the refractive indices (nd, nF, nC) at a wavelength of 589.3nm (d-line in sodium spectrum), a wavelength of 480.0nm (F-line in hydrogen spectrum), and a wavelength of 656.3nm (C-line in hydrogen spectrum) were measured at 20℃using an Abbe refractometer Multi-wave length Abbe Refractometer DR-M4 (ATTGO Co., ltd.) to obtain Abbe numbers (vd) as follows:
the various physical properties tested on the optical resins obtained in examples 1-6 and comparative examples 1-5 are specifically shown in Table 1:
table 1: test performance of examples 1-6 and comparative examples 1-4
As is evident from the data in Table 1, the refractive index and Abbe number of the optical resin materials in examples 1 to 6 are higher than those of comparative examples 1 to 5, and it is effectively demonstrated that the selection of the raw materials of the specific chlorine content polythioether resin material of the present application in combination with the specific curing process gives a resin material having a high refractive index (. Gtoreq.1.66) and a high Abbe number (. Gtoreq.38), and by the present application, an optical resin having a lower dispersion and a better definition can be produced. The price of the common polythioether resin material (the refractive index is about 1.63, the Abbe number is less than 38) is 10-15 ten thousand yuan, the price of the resin material with high refractive index (more than or equal to 1.66) and high Abbe number (more than or equal to 38) is more than 30 ten thousand yuan, and the application adopts specific raw materials to be matched with a specific curing process, thereby obtaining remarkable progress and having significance and value of industrial production and application.

Claims (6)

1. The optical resin material with high refractive index and high Abbe number is characterized in that the raw materials comprise, by weight, 70-80 parts of an episulfide compound, 8-20 parts of polythiol and 5-15 parts of isocyanate, wherein the chlorine content of the polythiol is less than or equal to 500ppm, and the chlorine content of the isocyanate is less than or equal to 1000ppm;
the curing process of the optical resin material comprises primary curing and secondary curing, wherein the curing temperature rise interval of the primary curing is within the range of 20-80 ℃, and the total duration is 11.5-15 h;
the curing temperature rise interval comprises 20-55 ℃ and 55-80 ℃, wherein the average temperature rise rate is 5-20 ℃/h in the temperature rise interval of 55-80 ℃;
the primary curing specifically comprises five stages, specifically:
the first stage: maintaining at 20deg.C for 2 hr;
and a second stage: raising the temperature to 55 ℃ at 2.50 ℃/h;
and a third stage: heating to 80 ℃ at a speed of 5-20 ℃/h;
fourth stage: maintaining at 80deg.C for 4 hr;
fifth stage: the temperature was reduced to 60℃at 20℃per hour.
2. An optical resin material of high refractive index and high abbe number according to claim 1, wherein the chlorine content of the polythiol is 400ppm or less and the chlorine content of the isocyanate is 300ppm or less.
3. The high refractive index and high abbe number optical resin material according to claim 1, wherein the cyclic sulfur compound is one or more of bis (β -cyclic thiopropyl) sulfide, bis (β -cyclic thiopropyl) disulfide, bis (β -cyclic thiopropyl) trisulfide, bis (β -cyclic thiopropyl) thiophanate, 1, 2-bis (β -cyclic thiopropyl) ethane, 1, 3-bis (β -cyclic thiopropyl) propane, 1, 4-bis (β -cyclic thiopropyl) thiopropane, and bis (β -cyclic thiopropyl) thiophanate-ethyl).
4. The high refractive index and high abbe number optical resin material according to claim 1, wherein the polythiol is one or more of thiobis Gan Liuchun, 2, 3-dithio (2-mercapto) -1-propanethiol, 1,5,9, 13-tetramercapto-3, 7, 11-tritridecane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, tetra (mercaptomethyl) methane, pentaerythritol tetra (3-mercaptopropionic acid) ester, pentaerythritol tri (3-mercaptopropionic acid) ester, 1, 2-tetra (mercaptomethylthio) ethane, dipentaerythritol hexa (3-mercaptopropionic acid) ester, pentaerythritol tetra (3-mercaptobutyric acid) ester.
5. The high refractive index and high abbe number optical resin material according to claim 1, wherein the isocyanate is one or more of 4, 4-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, methylenedicyclohexyl diisocyanate, and hydrogenated xylylene diisocyanate.
6. The high refractive index and high abbe number optical resin material according to claim 1, further comprising a polymerization catalyst, wherein the polymerization catalyst is tetrabutylphosphine bromide.
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