CN103709365A - High refractive resin containing silicon and preparation method of resin - Google Patents
High refractive resin containing silicon and preparation method of resin Download PDFInfo
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- CN103709365A CN103709365A CN201310689416.4A CN201310689416A CN103709365A CN 103709365 A CN103709365 A CN 103709365A CN 201310689416 A CN201310689416 A CN 201310689416A CN 103709365 A CN103709365 A CN 103709365A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/61—Polysiloxanes
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Abstract
The invention discloses a high refractive resin containing silicon and a preparation method of the resin. The high refractive dual curing resin containing silicon comprises a sulfur epoxy acrylate chain segment and a silicon urethane acrylate chain segment. The preparation method comprises the following steps: firstly, reacting ethanedithiol with epichlorohydrin to generate epoxy sulfur, and then reacting epoxy sulfur with crylic acid to generate sulfur epoxy acrylate double ester or sulfur epoxy acrylic acid ester; grafting a silicon urethane acrylate prepolymer with an NCO functional group at the side chain, wherein the obtained resin comprises two structures: one structure contains three acrylate double bonds and can be solidified by ultraviolet light free radicals, and the other structure contains two acrylate double bonds (solidified by ultraviolet light free radicals) and an epoxy group (solidified by ultraviolet light cations or hotly cured), and can be dually solidified by ultraviolet light. The resin has high refractive index, and good adhesive performance and heat resistance after being cured, and can be used in ultraviolet-curable adhesives and coatings.
Description
Technical field
The invention belongs to organic polymer synthesis technical field, relate in particular to a kind of siliceous high refractive power resin and preparation method thereof.
Background technology
Optical material is divided into inorganic optical material and the large class of organic polymer optical material two conventionally.Polymeric optical material has light weight, shock resistance, easily machine-shaping, has the excellent advantages such as optical property, greatly widened the application of optical material, on the products such as CD, optical fiber, resin lens, accurate lens, liquid-crystal display, photodiode, be with a wide range of applications, at a lot of fields polymeric optical material, have the trend that progressively replaces inorganic optical material at present.
Compare with inorganic optical material, polymeric optical material is limited to the chemical structure of polymkeric substance self, have that refractive index is not high, hardness is low, thermotolerance, weathering resistance, wear resistance, solvent resistance, resistance to water soak are poor, the shortcomings such as anti-chemical is poor, limit its development in more profound wider field and application.But polymeric optical material also has the place of its uniqueness, different with object according to use occasion, can design targetedly, the optical resin of preparing high refractive index, obtain novel applicable actual production and the material of use, also have by structurally-modified, obtain the optical material of specific function, this is also the developing direction of optical material.
At present, obtain furtheing investigate also the several frequently seen optical resin of widespread use and comprise polymethylmethacrylate, polystyrene, polycarbonate, poly-diallyl glycol ether two carbonic ethers etc.This class material is when making optics as body material, generally exist the shortcomings such as wear resistance, solvent resistance, resistance to water soak be poor, use properties is not good separately, must just have using value filming of the various specific functions of its surface-coated, and matching used filming also should have high refractive index with it.But, at present specially for this class, there is filming of the specific functions such as high refractive power or gluing with the research of resin seldom.
In organic polymer molecular structure, introduce the refractive index that following functional group contributes to improve organic polymer optical material: haloid element (defluorination), heavy metal ion, phenyl ring and condensed ring, sulphur, phosphorus atom.In these elements and group, to introduce element sulphur in polymkeric substance, be the effective means that improves specific refractory power.This resinoid not only refractive index is higher, and dispersion is less, and density is lower, and easy to prepare, and environmental stability is good.
Summary of the invention
The object of the invention is to introduce element sulphur in the resin of ultraviolet light polymerization or UV-light dual cure, to improve the refractive index of resin, and at the siliceous urethane acrylate segment of resin side chain graft.Because siliceous segment has very low temperature coefficient of viscosity, excellent interface performance, flexibility, good oilness, chemical stability and the outstanding performances such as weathering resistance preferably, the introducing of siliceous segment, can improve the snappiness of resin of the present invention, also can improve its performance such as heat-resisting, weather-proof.
The invention provides a kind of preparation method simultaneously with the high refractive power resin of sulfur-bearing epoxy acrylate and silicon-based polyurethane acrylate segment, gained resin has two kinds of structures: a kind of three acrylic double bonds, energy UV-light radically curing of containing; Another kind of containing two acrylic double bonds (UV-light radically curing) and an epoxide group (UV-light cationic curing or thermofixation) Liang Zhong functional group, can UV-light dual cure.After this resin solidification, there is higher refractive index, good gluing performance and resistance toheat, can be applicable to require in the product such as ultraviolet-curing paint, sizing agent of high refractive power.
Synthetic technology route of the present invention is as follows:
(1) preparation of sulfur-bearing epoxy acrylate segment:
In 1000ml there-necked flask, add a certain amount of epoxy chloropropane, be heated with stirring to 50～100 ℃, then two mercaptan that add metering, the mol ratio that the add-on of two mercaptan meets two mercaptan and epoxy chloropropane is 1:5～10,20% sodium hydroxide solution that adds again same volume, stirring reaction 0.5～2h, after cooling, add the ether of 2～5 times of volumes and the distilled water of 2～5 times of volumes, separate organic layer, be washed to neutrality, with anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains sulfur-bearing epoxy; The sulfur-bearing epoxy of gained is added in there-necked flask, be heated with stirring to 90～130 ℃, then add that to account for massfraction be 0.1～1.0% catalyzer and 0.1～1.0% stopper MEHQ; Add a certain amount of acrylic or methacrylic acid, the add-on of described acrylic or methacrylic acid meets epoxide group and acrylic acid mol ratio is 1:1 or 2:1 again; Continue reaction 2～6h, by alkalimetric titration, during to the acid number≤3mgKOH/g of system, obtain sulfur-bearing epoxy acrylate segment.Described sulfur-bearing epoxy acrylate segment has following two kinds of structures:
Two described mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,6-ethanthiol, 2,5-dimercaptothiodiazole, 1, pungent two mercaptan of 8-, 1，2-ethandithiol, 1,3-dimercaptopropane, 1,9-mercaptan in the ninth of the ten Heavenly Stems two, 1,7-mercaptan in heptan two, 3,6-dioxy-1, a kind of in pungent two mercaptan of 8-.
Described catalyzer is N, N-diethyl benzylamine, N, N-dimethyl benzylamine, four butyl bromation amine, triethyl benzyl ammonia chloride, triethylamine, trolamine, chromium trichloride, triphenylphosphine, tri acetylacetonato network aluminium (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), tri acetylacetonato network iron (III), two (methyl ethyl diketone) network copper (II), two (methyl ethyl diketone) network cobalt (II), dichloride two (methyl ethyl diketone) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network vanadium (III), two (methyl ethyl diketone) network beryllium (II), a kind of in two (methyl ethyl diketone) network zinc (II).
(2) preparation of silicon-based polyurethane acrylate segment:
In 1000ml there-necked flask, add a certain amount of vulcabond, be heated to 50～80 ℃; The hydroxy silicon oil of metering is added in vulcabond, and the mol ratio that described hydroxy silicon oil add-on meets vulcabond and hydroxyl is 1:1; Described hydroxy silicon oil is added with the dibutyl tin dilaurate that accounts for total mass 0.1～1.0%; After reaction 2～5h, in reaction system, add hydroxy acrylate, the mol ratio that the add-on of described hydroxy acrylate meets hydroxy acrylate and vulcabond is 1～1.1:2, and described hydroxy acrylate is added with 0.1～1.0% MEHQ; Reaction system is warming up to 65～100 ℃, continues reaction 2～5h, must arrive the silicon-based polyurethane acrylate segment of one end have-NCO group, described urethane acrylate segment has following structure:
Described vulcabond is a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), PPDI (PPDI).
Described hydroxy silicon oil is any hydroxy silicon oil in hydroxy radical content 0.5-10%.
Described hydroxy acrylate is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester.
(3) preparation of siliceous high refractive power resin:
In 1000ml there-necked flask, add the synthetic sulfur-bearing epoxy acrylate segment of a certain amount of step (1) and the synthetic silicon-based polyurethane acrylate segment of step (2), and add the dibutyl tin dilaurate that accounts for total mass 0.1～0.5%, the add-on of described sulfur-bearing epoxy acrylate segment and silicon-based polyurethane acrylate segment meet sulfur-bearing epoxy acrylate with-NCO group molar ratio is 1:0.8～1; At 60～100 ℃, react 3～5h, obtain the acrylate modified sulfur-bearing Epocryl of silicon-based polyurethane, the acrylate modified sulfur-bearing Epocryl of described silicon-based polyurethane has following two kinds of structures:
The features such as quick, solvent-free, applicable streamline production that UV-light (UV) curing technology has, were rapidly developed in recent years.It can be used as the coating for surface protection of plastics, metal, timber, paper, optical fiber etc., industrial, be expected to replace solvent based coating and be used widely.The present invention is the feature based on ultraviolet light polymerization, the synthetic siliceous new type resin with high refractive property of sulfur-bearing, and this resin can be realized ultraviolet light polymerization or UV-light dual cure, is expected to apply in some extraordinary coating and sizing agent.
Resin of the present invention has the sulfur-bearing epoxy acrylate segment of high refractive power and heat-resisting silicon-based polyurethane acrylate segment, can be applicable to the fields such as the agent of photocuring gluing, coating.
Embodiment
Embodiment 1:
The first step adds the epoxy chloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 65 ℃, add again 1 of 0.6mol, pungent two mercaptan of 8-, then add the 20%NaOH solution of about 300mL, stirring reaction 1h, is cooled to room temperature, adds the ether of 5 times of volumes and the distilled water of 5 times of volumes, separate organic layer, be washed to neutrality, with anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains sulfur-bearing epoxy; Take the above-mentioned synthetic sulfur-bearing epoxy of 0.4mol and add in 500mL there-necked flask, be heated with stirring to 120 ℃, then add that to account for massfraction be 0.5% catalyzer triethyl benzyl ammonia chloride and 1.0% stopper MEHQ; The vinylformic acid that adds again 0.8mol, continues reaction 3.5h, obtains sulfur-bearing epoxy acrylate 1.; Second step, the tolylene diisocyanate (TDI) that adds 2.0mol in the there-necked flask of 1000mL, be heated to 65 ℃, dibutyl tin dilaurate joins in the hydroxy silicon oil (hydroxy radical content 10%) containing 2.0mol hydroxyl by 0.8% of total mass, be added dropwise in tolylene diisocyanate (TDI) solution, drip off rear continuation reaction 4h, in the Hydroxyethyl acrylate of 1.0mol, add 0.6% MEHQ, add above-mentioned reaction system, be warming up to 75 ℃ of reaction 4h, obtain the urethane acrylate of one end band-NCO group 2.; The 3rd step, in the there-necked flask of 500mL, add the sulfur-bearing epoxy acrylate of 0.3mol 1., add the urethane acrylate of 0.3mol 2., add the dibutyl tin dilaurate that accounts for total mass 0.5%, be heated to react 4h at 80 ℃ and obtain the acrylate modified sulfur-bearing Epocryl of silicon-based polyurethane.
Embodiment 2:
The first step adds the epoxy chloropropane of 2mol in 1000mL there-necked flask, is heated with stirring to 75 ℃, add again 2 of 0.3mol, 4-dimercapto pyrimidine, then add the 20%NaOH solution of about 200mL, stirring reaction 1h, is cooled to room temperature, adds the ether of 3 times of volumes and the distilled water of 4 times of volumes, separate organic layer, be washed to neutrality, with anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains sulfur-bearing epoxy; Take the above-mentioned synthetic sulfur-bearing epoxy of 0.2mol and add in 250mL there-necked flask, be heated with stirring to 110 ℃, then add that to account for massfraction be 1.0% catalyzer tri acetylacetonato network cobalt (III) and 0.8% stopper MEHQ; The methacrylic acid that adds again 0.4mol, continues reaction 4.5h, obtains sulfur-bearing epoxy acrylate 1.; Second step, the diphenylmethanediisocyanate (MDI) that adds 1.0mol in the there-necked flask of 500mL, be heated to 50 ℃, dibutyl tin dilaurate joins in the hydroxy silicon oil (hydroxy radical content 8%) containing 1.0mol hydroxyl by 1.0% of total mass, be added dropwise in diphenylmethanediisocyanate (MDI) solution, drip off rear continuation reaction 5h, in the Propylene glycol monoacrylate of 0.5mol, add 0.4% MEHQ, add above-mentioned reaction system, be warming up to 80 ℃ of reaction 3h, obtain the urethane acrylate of one end band-NCO group 2.; The 3rd step, in the there-necked flask of 250mL, add the sulfur-bearing epoxy acrylate of 0.2mol 1., add the urethane acrylate of 0.19mol 2., add the dibutyl tin dilaurate that accounts for total mass 0.2%, be heated to react 3h at 100 ℃ and obtain the acrylate modified sulfur-bearing Epocryl of silicon-based polyurethane.
Embodiment 3:
The first step adds the epoxy chloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 50 ℃, add again 3 of 0.3mol, 6-dioxy-1, pungent two mercaptan of 8-, the 20%NaOH solution that adds again about 300mL, stirring reaction 2h, is cooled to room temperature, add the ether of 2 times of volumes and the distilled water of 2 times of volumes, separate organic layer, be washed to neutrality, with anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains sulfur-bearing epoxy; Take the above-mentioned synthetic sulfur-bearing epoxy of 0.2mol and add in 250mL there-necked flask, be heated with stirring to 100 ℃, then add that to account for massfraction be 0.8% catalyst n, N-dimethyl benzylamine and 0.5% stopper MEHQ; The methacrylic acid that adds again 0.4mol, continues reaction 5h, obtains sulfur-bearing epoxy acrylate 1.; Second step, the hexamethylene diisocyanate (HDI) that adds 1.0mol in the there-necked flask of 500mL, be heated to 70 ℃, dibutyl tin dilaurate joins in the hydroxy silicon oil (hydroxy radical content 6%) containing 1.0mol hydroxyl by 0.7% of total mass, be added dropwise in hexamethylene diisocyanate (HDI) solution, drip off rear continuation reaction 3h, in the hydroxyethyl methylacrylate of 0.5mol, add 0.5% MEHQ, add above-mentioned reaction system, be warming up to 75 ℃ of reaction 3.5h, obtain the urethane acrylate of one end band-NCO group 2.; The 3rd step, in the there-necked flask of 250mL, add the sulfur-bearing epoxy acrylate of 0.2mol 1., add the urethane acrylate of 0.2mol 2., add the dibutyl tin dilaurate that accounts for total mass 0.4%, be heated to react 4h at 75 ℃ and obtain the acrylate modified sulfur-bearing Epocryl of silicon-based polyurethane.
Embodiment 4:
The first step adds the epoxy chloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 80 ℃, add again 4 of 0.5mol, 4'-dimercapto diphenyl sulfide, then add the 20%NaOH solution of about 300mL, stirring reaction 0.5h, is cooled to room temperature, adds the ether of 3 times of volumes and the distilled water of 3 times of volumes, separate organic layer, be washed to neutrality, with anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains sulfur-bearing epoxy; Take the above-mentioned synthetic sulfur-bearing epoxy of 0.4mol and add in 250mL there-necked flask, be heated with stirring to 90 ℃, then add that to account for massfraction be 0.9% catalyzer tri acetylacetonato network lanthanum (III) and 0.4% stopper MEHQ; The vinylformic acid that adds again 0.4mol, continues reaction 6h, obtains sulfur-bearing epoxy acrylate 1.; Second step, the isophorone diisocyanate (IPDI) that adds 1.0mol in the there-necked flask of 500mL, be heated to 80 ℃, dibutyl tin dilaurate joins in the hydroxy silicon oil (hydroxy radical content 4%) containing 1.0mol hydroxyl by 0.5% of total mass, be added dropwise in isophorone diisocyanate (IPDI) solution, drip off rear continuation reaction 2h, in the Rocryl 410 of 0.5mol, add 0.4% MEHQ, add above-mentioned reaction system, be warming up to 85 ℃ of reaction 3h, obtain the urethane acrylate of one end band-NCO group 2.; The 3rd step, in the there-necked flask of 250mL, add the sulfur-bearing epoxy acrylate of 0.3mol 1., add the urethane acrylate of 0.28mol 2., add the dibutyl tin dilaurate that accounts for total mass 0.2%, be heated to react 3.5h at 85 ℃ and obtain the acrylate modified sulfur-bearing Epocryl of silicon-based polyurethane.
Embodiment 5:
The first step adds the epoxy chloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 85 ℃, add again 2 of 0.6mol, 5-dimercaptothiodiazole, then add the 20%NaOH solution of about 300mL, stirring reaction 0.5h, is cooled to room temperature, adds the ether of 4 times of volumes and the distilled water of 5 times of volumes, separate organic layer, be washed to neutrality, with anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains sulfur-bearing epoxy; Take the above-mentioned synthetic sulfur-bearing epoxy of 0.5mol and add in 250mL there-necked flask, be heated with stirring to 110 ℃, then add that to account for massfraction be 0.6% catalyzer triphenylphosphine and 0.7% stopper MEHQ; The vinylformic acid that adds again 0.5mol, continues reaction 4h, obtains sulfur-bearing epoxy acrylate 1.; Second step, the dicyclohexyl methane diisocyanate (HMDI) that adds 1.0mol in the there-necked flask of 500mL, be heated to 70 ℃, dibutyl tin dilaurate joins in the hydroxy silicon oil (hydroxy radical content 1%) containing 1.0mol hydroxyl by 0.6% of total mass, be added dropwise in dicyclohexyl methane diisocyanate (HMDI) solution, drip off rear continuation reaction 3.5h, in the Hydroxyethyl acrylate of 0.5mol, add 0.6% MEHQ, add above-mentioned reaction system, be warming up to 80 ℃ of reaction 3h, obtain the urethane acrylate of one end band-NCO group 2.; The 3rd step, in the there-necked flask of 250mL, add the sulfur-bearing epoxy acrylate of 0.5mol 1., add the urethane acrylate of 0.48mol 2., add the dibutyl tin dilaurate that accounts for total mass 0.1%, be heated to react 3h at 100 ℃ and obtain the acrylate modified sulfur-bearing Epocryl of silicon-based polyurethane.
Claims (7)
1. a siliceous high refractive power resin, comprises sulfur-bearing epoxy acrylate segment and silicon-based polyurethane acrylate segment, and described siliceous high refractive power resin has following two kinds of structures:
。
2. a method of preparing siliceous high refractive power resin, comprises the steps:
(1) preparation of sulfur-bearing epoxy acrylate segment:
In reaction vessel, add epoxy chloropropane, be heated with stirring to 50～100 ℃, then add two mercaptan, the mol ratio that the add-on of two mercaptan meets two mercaptan and epoxy chloropropane is 1:5～10, then adds 20% sodium hydroxide solution of same volume, stirring reaction 0.5～2h, after cooling, add the ether of 2～5 times of volumes and the distilled water of 2～5 times of volumes, separate organic layer, be washed to neutrality, with anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains sulfur-bearing epoxy; The sulfur-bearing epoxy of gained is added in reaction vessel, be heated with stirring to 90～130 ℃, then add that to account for massfraction be 0.1～1.0% catalyzer and 0.1～1.0% stopper MEHQ; Add a certain amount of acrylic or methacrylic acid, the add-on of described acrylic or methacrylic acid meets epoxide group and acrylic acid mol ratio is 1:1 or 2:1 again; Continue reaction 2～6h, by alkalimetric titration, during to the acid number≤3mgKOH/g of system, obtain sulfur-bearing epoxy acrylate segment; Described sulfur-bearing epoxy acrylate segment has following two kinds of structures:
(2) preparation of silicon-based polyurethane acrylate segment:
In reaction vessel, add vulcabond, be heated to 50～80 ℃; Hydroxy silicon oil is added in vulcabond, and the mol ratio that described hydroxy silicon oil add-on meets vulcabond and hydroxyl is 1:1; Described hydroxy silicon oil is added with the dibutyl tin dilaurate that accounts for total mass 0.1～1.0%; After reaction 2～5h, in reaction system, add hydroxy acrylate, the mol ratio that the add-on of described hydroxy acrylate meets hydroxy acrylate and vulcabond is 1～1.1:2, and described hydroxy acrylate is added with 0.1～1.0% MEHQ; Reaction system is warming up to 65～100 ℃, continues reaction 2～5h, must arrive the silicon-based polyurethane acrylate segment of one end have-NCO group, described urethane acrylate segment has following structure:
(3) preparation of siliceous high refractive power resin:
In reaction vessel, add the synthetic sulfur-bearing epoxy acrylate segment of step (1) and the synthetic silicon-based polyurethane acrylate segment of step (2), and add the dibutyl tin dilaurate that accounts for total mass 0.1～0.5%, the add-on of described sulfur-bearing epoxy acrylate segment and silicon-based polyurethane acrylate segment meet sulfur-bearing epoxy acrylate with-NCO group molar ratio is 1:0.8～1; At 60～100 ℃, react 3～5h, obtain the acrylate modified sulfur-bearing Epocryl of silicon-based polyurethane, the acrylate modified sulfur-bearing Epocryl of described silicon-based polyurethane has following two kinds of structures:
3. the method for the siliceous high refractive power resin of preparation as claimed in claim 2, is characterized in that: two described mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,6-ethanthiol, 2,5-dimercaptothiodiazole, 1, pungent two mercaptan of 8-, 1,2-dithioglycol, 1,3-dimercaptopropane, 1,9-mercaptan in the ninth of the ten Heavenly Stems two, 1,7-mercaptan in heptan two, 3,6-dioxy-1, a kind of in pungent two mercaptan of 8-.
4. the method for the siliceous high refractive power resin of preparation as claimed in claim 2, it is characterized in that: described catalyzer is N, N-diethyl benzylamine, N, N-dimethyl benzylamine, four butyl bromation amine, triethyl benzyl ammonia chloride, triethylamine, trolamine, chromium trichloride, triphenylphosphine, tri acetylacetonato network aluminium (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), tri acetylacetonato network iron (III), two (methyl ethyl diketone) network copper (II), two (methyl ethyl diketone) network cobalt (II), dichloride two (methyl ethyl diketone) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network vanadium (III), two (methyl ethyl diketone) network beryllium (II), a kind of in two (methyl ethyl diketone) network zinc (II).
5. the method for preparing the high refractive power resin of sulfur-bearing as claimed in claim 2, is characterized in that: described vulcabond is a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), PPDI (PPDI).
6. the method for preparing the high refractive power resin of sulfur-bearing as claimed in claim 2, is characterized in that: described hydroxy silicon oil is the hydroxy silicon oil in hydroxy radical content 0.5-10%.
7. the method for preparing the high refractive power resin of sulfur-bearing as claimed in claim 2, is characterized in that: described hydroxy acrylate is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester.
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| CN105713550A (en) * | 2016-04-19 | 2016-06-29 | 深圳职业技术学院 | Ultraviolet-cured optical adhesive for glass optical device and preparation method of adhesive |
| CN105754545A (en) * | 2016-04-26 | 2016-07-13 | 深圳职业技术学院 | Ultraviolet mixing solidifying adhesive for display and preparation method thereof |
| CN105754108A (en) * | 2016-04-26 | 2016-07-13 | 深圳职业技术学院 | Polyurethane acrylate modified ultraviolet light cured water-dilutable resin and preparation method thereof |
| CN108586755A (en) * | 2018-04-12 | 2018-09-28 | 中科广化（重庆）新材料研究院有限公司 | A kind of Photocurable Silicone Material and its preparation method and application |
| CN108727593A (en) * | 2018-06-15 | 2018-11-02 | 张礼国 | A kind of antimicrobial organosilane glue material and preparation method thereof |
| CN110105578A (en) * | 2019-04-26 | 2019-08-09 | 深圳职业技术学院 | A kind of highly-water-soluble UV-Curing Waterborne Resin and preparation method thereof with siliceous segment |
| CN116023813A (en) * | 2022-12-14 | 2023-04-28 | 江苏视科新材料股份有限公司 | Preparation method of high-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter |
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| CN110105578B (en) * | 2019-04-26 | 2021-12-21 | 深圳职业技术学院 | High-water-solubility ultraviolet-curing water-based resin with silicon-containing chain segment and preparation method thereof |
| CN116023813A (en) * | 2022-12-14 | 2023-04-28 | 江苏视科新材料股份有限公司 | Preparation method of high-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter |
| CN116023813B (en) * | 2022-12-14 | 2023-10-31 | 江苏视科新材料股份有限公司 | Preparation method of high-refractive-index blue-light-resistant modified epoxy acrylate material and optical filter |
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