CN103289049A - Preparation method for dual-curing group-containing high-refraction resin - Google Patents
Preparation method for dual-curing group-containing high-refraction resin Download PDFInfo
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Abstract
The invention discloses a preparation method for dual-curing group-containing high-refraction resin. The dual-curing group-containing high-refraction resin comprises a sulfur-containing epoxy acrylic acid monoester chain segment and a sulfur-containing polyurethane acrylate ester chain segment, as well as two functional groups: acrylate double bonds (ultraviolet light free radical curing) and an epoxy group (ultraviolet light cation curing or thermocuring). The cured resin has higher refractive index, lower curing volume shrinkage and good gluing property, and can be used in adhesive and coating which can be subjected to ultraviolet light double curing and is required for higher refractive index.
Description
Technical field
The invention belongs to the organic polymer synthesis technical field, relate in particular to a kind of preparation method who contains the high refractive power resin of double curing groups, but but this resin has the epoxide group of the radical-cured acrylic double bond group of UV-light and UV-light cationic curing or thermofixation, can be applied to the fields such as sizing agent, coating of UV-light dual cure.
Background technology
Ultraviolet light polymerization comes branch to mainly contain radically curing and cationic curing two big classes according to mechanism.The radical photoinitiator initiator system is ultraviolet light polymerization application form the earliest, and at present, products such as ultraviolet-curing paint, tackiness agent are mainly based on the radically curing system.Advantages such as the radical photoinitiator curing system has that curing speed is fast, performance is easy to regulate, moisture resistance is wet, resin and thinner and initiator type are many, resin and thinner that this class system is used are mainly esters of acrylic acid, and resin commonly used has epoxy acrylate, urethane acrylate, polyester acrylate etc.But the radical photoinitiator curing system also exist and be difficult for that surface drying, polymerization volumetric shrinkage are big, poor adhesive force, problem such as solidification without male offspring.
In order to overcome the problem of radical photoinitiator curing system, positively charged ion initiation photocuring system grew up in late 1970s, compare with the radical photoinitiator curing system, it is not subjected to the inhibition of oxygen in the air when solidifying, it is little to solidify volumetric shrinkage, formed cured film sticking power is stronger, curing reaction is not easy to stop, after fixing is arranged, be adapted to prepare the photocuring product of thick film and colored paint, the resin that cation photocuring system is commonly used mainly contains the epoxidation bisphenol a resin, the epoxidation silicone resin, also has epoxidized polybutadiene, epoxy natural rubber, vinyl ether series etc.Shortcomings such as but the cationic curing system has also that curing speed is slow, oligopolymer and reactive thinner kind are few and cation photocuring require to carry out under low-temperature anhydrous condition usually, and condition is relatively harsher, has hindered its development and application.
Now, in order to bring into play the advantage of various curing systems, avoid its shortcoming, the research of various dual ultraviolet light polymerization systems has obtained attention more and more widely, develop and various forms of dual ultraviolet light polymerization systems, it has broad application prospects at aspects such as speciality coating, tackiness agent, printing ink.
The research of dual ultraviolet light polymerization system mainly contains following a few class: UV-light free radical-positively charged ion dual cure system, UV-light radically curing-thermofixation dual cure system, UV-light-air dual cure, UV-light-moisture dual cure, ultraviolet-anaerobic dual curing etc.In these dual cure systems, with UV-light free radical-positively charged ion dual cure system and UV-light radically curing-thermofixation dual cure system in actual applications solidification process control easily, excellent performance, have a good application prospect, other dual cure system solidification process is influenced greatly by extraneous factor, and applicability is also not strong.
In the various dual ultraviolet light polymerization systems, most of investigator all adopts the mixing of several resins with different curing groups, and mixed system also exists between local solidification inequality or the resin problems such as consistency is bad like this.The research that has two kinds of different curing groups a resinous molecular structure simultaneously is then less, and the segment that will have a high refractive power is introduced then relevant reporting for work not of the research have in the UV-light dual cure group resin.
Summary of the invention
The invention provides a kind of preparation method who contains the high refractive power resin of double curing groups who has sulfur-bearing propylene oxide acid monoester and sulfur-containing polyurethane acrylate segment simultaneously, the gained resin contains the radical-cured acrylic double bond of energy UV-light, also containing can the UV-light positively charged ion or the epoxide group of thermofixation, can be applicable to require in the products such as coating, sizing agent of the UV-light dual cure of high refractive power.
Synthetic technology route of the present invention is as follows:
(1) preparation of sulfur-bearing propylene oxide acid monoester segment:
In the 1000ml there-necked flask, add epoxy chloropropane, be heated with stirring to 50～90 ℃, two mercaptan that add metering then, the mol ratio that the add-on of two mercaptan satisfies two mercaptan and epoxy chloropropane is 1:5～10, the 15%-20% sodium hydroxide solution that adds equal volume then, stirring reaction 0.5～2h, after the cooling, add the ether of 2～5 times of volumes and the distilled water of 2～5 times of volumes, tell organic layer, be washed to neutrality, use anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains the sulfur-bearing epoxy; The sulfur-bearing epoxy of gained is added in the reaction vessel, be heated with stirring to 90～130 ℃, add then that to account for massfraction be 0.1～1.0% catalyzer and 0.1～1.0% stopper MEHQ; Add the acrylic or methacrylic acid of metering again, the add-on of described acrylic or methacrylic acid satisfies epoxide group and acrylic acid mol ratio is 2:1; Continue reaction 2～6h, during to the acid number of system≤3mgKOH/g, obtain sulfur-bearing propylene oxide acid monoester segment by alkalimetric titration, described acrylic acid epoxy monoesters segment has an acrylic double bond group and an epoxide group.
Described two mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,6-ethanthiol, 2,5-dimercaptothiodiazole, 1, hot two mercaptan of 8-, 1,1,3-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 hot two mercaptan of 8-.
Described catalyzer is N, the N-diethyl benzylamine, N, the 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) the network zinc (II).
(2) preparation of sulfur-containing polyurethane acrylate segment:
In the 1000ml there-necked flask, add vulcabond, be heated with stirring to 50～90 ℃, then two mercaptan are added dropwise in the vulcabond, the mol ratio that the add-on of two mercaptan satisfies vulcabond and two mercaptan is 2:1, is added with the dibutyl tin dilaurate that accounts for total mass 0.1～1.0% in two mercaptan; Behind reaction 2～6h, add hydroxy acrylate in reaction system, the mol ratio that the add-on of hydroxy acrylate satisfies hydroxy acrylate and vulcabond is 1～1.1:2, and hydroxy acrylate is added with 0.1～1.0% MEHQ; Reaction system is heated to 60～100 ℃, continues reaction 2～5h, obtaining an end has-and NCO group and the other end are the sulfur-containing polyurethane acrylate segment of acrylic double bond.
Described vulcabond is a kind of in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), the PPDI (PPDI).
Described two mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,6-ethanthiol, 2,5-dimercaptothiodiazole, 1, hot two mercaptan of 8-, 1,1,3-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 hot two mercaptan of 8-.
Described hydroxy acrylate is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester.
(3) contain the preparation of the high refractive power resin of double curing groups:
In reaction vessel, add the synthetic sulfur-bearing propylene oxide acid monoester segment of step (1) and the synthetic sulfur-containing polyurethane acrylate segment of step (2), and add the dibutyl tin dilaurate account for total mass 0.1～0.5%, the add-on of sulfur-bearing propylene oxide acid monoester segment and sulfur-containing polyurethane acrylate segment satisfy the sulfur-bearing epoxy acrylate with-the NCO group molar ratio is 1:0.8～1; React 3～6h down at 60～100 ℃, obtain the acrylate modified sulfur-bearing propylene oxide of sulfur-containing polyurethane acid monoester resin (namely containing the high refractive power resin of double curing groups), the acrylate modified sulfur-bearing propylene oxide of resulting sulfur-containing polyurethane acid monoester resin contains two acrylic double bond groups and an epoxide group.
According to the summary of experience of former studies, introduce the refractive index that following functional group helps to improve the organic polymer optical material in the organic polymer molecular structure: haloid element (defluorination), heavy metal ion, phenyl ring and condensed ring, sulphur, phosphorus atom.Comprehensive, in these structural units, be the most effectual way that improves specific refractory power in polymkeric substance, to introduce element sulphur.The present invention is that element sulphur is this to have high refractive power unit and introduce first in the resin with UV-light dual cure group with containing, thereby obtains to contain the high refractive power resin of double curing groups, has fine better industrial application prospect.
Specific embodiments
Embodiment 1:
The first step, the epoxy chloropropane of adding 3mol is heated with stirring to 60 ℃ in the 1000mL there-necked flask, add 2 of 0.6mol again, 4-dimercapto pyrimidine, the 15%NaOH solution of the about 300mL of adding again, stirring reaction 1h is cooled to room temperature, adds the ether of 4 times of volumes and the distilled water of 5 times of volumes, tell organic layer, be washed to neutrality, use anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains the sulfur-bearing epoxy; Take by weighing the above-mentioned synthetic sulfur-bearing epoxy of 0.3mol and add in the 500mL there-necked flask, be heated with stirring to 130 ℃, add then that to account for massfraction be 0.4% catalyzer triethyl benzyl ammonia chloride and 1.0% stopper MEHQ; The vinylformic acid that adds 0.3mol again continues reaction 2h, obtains sulfur-bearing propylene oxide acid monoester segment
Second step, the diphenylmethanediisocyanate (MDI) that in the there-necked flask of 1000mL, adds 2.0mol, be heated to 60 ℃, dibutyl tin dilaurate joins 1 of 1mol by 0.8% of total mass, hot two mercaptan of 8-, be added dropwise in diphenylmethanediisocyanate (MDI) solution, drip off the back and continue reaction 4.5h, the MEHQ of adding 0.3% in the Hydroxyethyl acrylate of 1mol, add above-mentioned reaction system, be warming up to 95 ℃ of reaction 2h, namely obtaining an end band NCO group and the other end is the sulfur-containing polyurethane acrylate segment of acrylic double bond
The 3rd step, the sulfur-bearing propylene oxide acid monoester of adding 0.2mol in the there-necked flask of 500mL
, the sulfur-containing polyurethane acrylate of adding 0.2mol
, add the dibutyl tin dilaurate that accounts for total mass 0.1%, be heated to 65 ℃ of following reaction 5h and namely obtain the acrylate modified sulfur-bearing propylene oxide of sulfur-containing polyurethane acid monoester resin.
Embodiment 2:
The first step, the epoxy chloropropane of adding 3mol is heated with stirring to 50 ℃ in the 1000mL there-necked flask, add 1 of 0.3mol again, 6-ethanthiol, the 20%NaOH solution of the about 300mL of adding again, stirring reaction 2h is cooled to room temperature, adds the ether of 3 times of volumes and the distilled water of 4 times of volumes, tell organic layer, be washed to neutrality, use anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains the sulfur-bearing epoxy; Take by weighing the above-mentioned synthetic sulfur-bearing epoxy of 0.2mol and add in the 500mL there-necked flask, be heated with stirring to 110 ℃, add then that to account for massfraction be 0.8% catalyzer four butyl bromation amine and 0.6% stopper MEHQ; The methacrylic acid that adds 0.2mol again continues reaction 4h, obtains sulfur-bearing propylene oxide acid monoester segment
Second step, the tolylene diisocyanate (TDI) that in the there-necked flask of 1000mL, adds 1.0mol, be heated to 50 ℃, dibutyl tin dilaurate joins 3 of 0.5mol by 1.0% of total mass, 6-dioxy-1, hot two mercaptan of 8-, be added dropwise in tolylene diisocyanate (TDI) solution, drip off the back and continue reaction 6h, the MEHQ of adding 0.6% in the Propylene glycol monoacrylate of 0.5mol, add above-mentioned reaction system, be warming up to 90 ℃ of reaction 2.5h, namely obtaining an end band NCO group and the other end is the sulfur-containing polyurethane acrylate segment of acrylic double bond
The 3rd step, the sulfur-bearing propylene oxide acid monoester of adding 0.2mol in the there-necked flask of 500mL
, the sulfur-containing polyurethane acrylate of adding 0.18mol
, add the dibutyl tin dilaurate that accounts for total mass 0.1%, be heated to 80 ℃ of following reaction 3h and namely obtain the acrylate modified sulfur-bearing propylene oxide of sulfur-containing polyurethane acid monoester resin.
Embodiment 3:
The first step, the epoxy chloropropane of adding 3mol is heated with stirring to 65 ℃ in the 1000mL there-necked flask, add 2 of 0.5mol again, 5-dimercaptothiodiazole, the 18%NaOH solution of the about 300mL of adding again, stirring reaction 1h is cooled to room temperature, adds the ether of 2 times of volumes and the distilled water of 2 times of volumes, tell organic layer, be washed to neutrality, use anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains the sulfur-bearing epoxy; Take by weighing the above-mentioned synthetic sulfur-bearing epoxy of 0.4mol and add in the 500mL there-necked flask, be heated with stirring to 115 ℃, add then that to account for massfraction be 0.6% catalyst n, N-dimethyl benzylamine and 0.8% stopper MEHQ; The vinylformic acid that adds 0.4mol again continues reaction 3.5h, obtains sulfur-bearing propylene oxide acid monoester segment
Second step, the isophorone diisocyanate (IPDI) that in the there-necked flask of 1000mL, adds 2.0mol, be heated to 75 ℃, dibutyl tin dilaurate joins 1 of 1mol by 0.5% of total mass, the 6-ethanthiol, be added dropwise in isophorone diisocyanate (IPDI) solution, drip off the back and continue reaction 4h, the MEHQ of adding 0.4% in the vinylformic acid hydroxy butyl ester of 1mol, add above-mentioned reaction system, be warming up to 85 ℃ of reaction 3h, namely obtaining an end band NCO group and the other end is the sulfur-containing polyurethane acrylate segment of acrylic double bond
The 3rd step, the sulfur-bearing propylene oxide acid monoester of adding 0.4mol in the there-necked flask of 500mL
, the sulfur-containing polyurethane acrylate of adding 0.38mol
, add the dibutyl tin dilaurate that accounts for total mass 0.3%, be heated to 75 ℃ of following reaction 4.5h and namely obtain the acrylate modified sulfur-bearing propylene oxide of sulfur-containing polyurethane acid monoester resin.
Embodiment 4:
The first step, the epoxy chloropropane of adding 3mol is heated with stirring to 70 ℃ in the 1000mL there-necked flask, add 1 of 0.4mol again, hot two mercaptan of 8-, the 20%NaOH solution of the about 300mL of adding again, stirring reaction 1h is cooled to room temperature, adds the ether of 3 times of volumes and the distilled water of 5 times of volumes, tell organic layer, be washed to neutrality, use anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains the sulfur-bearing epoxy; Take by weighing the above-mentioned synthetic sulfur-bearing epoxy of 0.3mol and add in the 500mL there-necked flask, be heated with stirring to 100 ℃, add then that to account for massfraction be 0.9% catalyzer two (methyl ethyl diketone) network cobalt (II) and 0.5% stopper MEHQ; The vinylformic acid that adds 0.3mol again continues reaction 5h, obtains sulfur-bearing propylene oxide acid monoester segment
Second step, the hexamethylene diisocyanate (HDI) that in the there-necked flask of 1000mL, adds 2.0mol, be heated to 65 ℃, dibutyl tin dilaurate joins 1 of 1mol by 0.6% of total mass, 7-mercaptan in heptan two, be added dropwise in hexamethylene diisocyanate (HDI) solution, drip off the back and continue reaction 4.5h, the MEHQ of adding 0.3% in the Rocryl 410 of 1mol, add above-mentioned reaction system, be warming up to 80 ℃ of reaction 3.5h, namely obtaining an end band NCO group and the other end is the sulfur-containing polyurethane acrylate segment of acrylic double bond
The 3rd step, the sulfur-bearing propylene oxide acid monoester of adding 0.3mol in the there-necked flask of 500mL
, the sulfur-containing polyurethane acrylate of adding 0.3mol
, add the dibutyl tin dilaurate that accounts for total mass 0.2%, be heated to 80 ℃ of following reaction 3.5h and namely obtain the acrylate modified sulfur-bearing propylene oxide of sulfur-containing polyurethane acid monoester resin.
Embodiment 5:
The first step, the epoxy chloropropane of adding 2mol is heated with stirring to 80 ℃ in the 1000mL there-necked flask, add 3 of 0.4mol again, 6-dioxy-1, hot two mercaptan of 8-, add the 16%NaOH solution of about 200mL again, stirring reaction 0.5h is cooled to room temperature, add the ether of 4 times of volumes and the distilled water of 3 times of volumes, tell organic layer, be washed to neutrality, use anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains the sulfur-bearing epoxy; Take by weighing the above-mentioned synthetic sulfur-bearing epoxy of 0.3mol and add in the 500mL there-necked flask, be heated with stirring to 90 ℃, add then that to account for massfraction be 1.0% catalyzer tri acetylacetonato network lanthanum (III) and 0.4% stopper MEHQ; The vinylformic acid that adds 0.3mol again continues reaction 6h, obtains sulfur-bearing propylene oxide acid monoester segment
Second step, the PPDI (PPDI) that in the there-necked flask of 1000mL, adds 2.0mol, be heated to 70 ℃, dibutyl tin dilaurate joins 1 of 1mol by 0.7% of total mass, the 3-dimercaptopropane, be added dropwise in PPDI (PPDI) solution, drip off the back and continue reaction 4h, the MEHQ of adding 0.6% in the Propylene glycol monoacrylate of 1mol, add above-mentioned reaction system, be warming up to 85 ℃ of reaction 3h, namely obtaining an end band NCO group and the other end is the sulfur-containing polyurethane acrylate segment of acrylic double bond
The 3rd step, the sulfur-bearing propylene oxide acid monoester of adding 0.3mol in the there-necked flask of 500mL
, the sulfur-containing polyurethane acrylate of adding 0.28mol
, add the dibutyl tin dilaurate that accounts for total mass 0.3%, be heated to 70 ℃ of following reaction 4.5h and namely obtain the acrylate modified sulfur-bearing propylene oxide of sulfur-containing polyurethane acid monoester resin.
Claims (6)
1. one kind contains the high refractive power resin of double curing groups, comprises sulfur-bearing propylene oxide acid monoester segment and sulfur-containing polyurethane acrylate segment.
2. a preparation method who contains the high refractive power resin of double curing groups comprises the steps:
A) preparation of sulfur-bearing propylene oxide acid monoester segment:
In reaction vessel, add epoxy chloropropane, be heated with stirring to 50～90 ℃, add two mercaptan then, the mol ratio that the add-on of two mercaptan satisfies two mercaptan and epoxy chloropropane is 1:5～10, adds the 15%-20% sodium hydroxide solution of equal volume then, stirring reaction 0.5～2h, after the cooling, add the ether of 2～5 times of volumes and the distilled water of 2～5 times of volumes, tell organic layer, be washed to neutrality, use anhydrous magnesium sulfate drying, filter, solvent is removed in decompression, obtains the sulfur-bearing epoxy; The sulfur-bearing epoxy of gained is added in the reaction vessel, be heated with stirring to 90～130 ℃, add then that to account for massfraction be 0.1～1.0% catalyzer and 0.1～1.0% stopper MEHQ; Add acrylic or methacrylic acid again, the add-on of described acrylic or methacrylic acid satisfies epoxide group and acrylic acid mol ratio is 2:1; Continue reaction 2～6h, during to the acid number of system≤3mgKOH/g, obtain sulfur-bearing propylene oxide acid monoester segment by alkalimetric titration, described acrylic acid epoxy monoesters segment has an acrylic double bond group and an epoxide group;
B) preparation of sulfur-containing polyurethane acrylate segment:
In reaction vessel, add vulcabond, be heated to 50～90 ℃; Stir, then two mercaptan are added dropwise in the vulcabond, the mol ratio that the add-on of two mercaptan satisfies vulcabond and two mercaptan is 2:1; Be added with the dibutyl tin dilaurate that accounts for total mass 0.1～1.0% in described two mercaptan; Behind reaction 2～6h, in reaction system, add hydroxy acrylate, the mol ratio that the add-on of described hydroxy acrylate satisfies hydroxy acrylate and vulcabond is 1～1.1:2, and described hydroxy acrylate is added with 0.1～1.0% MEHQ; Reaction system is heated to 60～100 ℃, continues reaction 2～5h, obtaining an end has-and NCO group and the other end are the sulfur-containing polyurethane acrylate segment of acrylic double bond;
C) contain the preparation of the high refractive power resin of double curing groups:
In reaction vessel, add steps A) synthetic sulfur-bearing propylene oxide acid monoester segment and step B) synthetic sulfur-containing polyurethane acrylate segment, and add the dibutyl tin dilaurate account for total mass 0.1～0.5%, the add-on of described sulfur-bearing propylene oxide acid monoester segment and sulfur-containing polyurethane acrylate segment satisfy the sulfur-bearing epoxy acrylate with-the NCO group molar ratio is 1:0.8～1; React 3～6h down at 60～100 ℃, obtain the acrylate modified sulfur-bearing propylene oxide of sulfur-containing polyurethane acid monoester resin, namely contain the high refractive power resin of double curing groups, the acrylate modified sulfur-bearing propylene oxide of described sulfur-containing polyurethane acid monoester resin contains two acrylic double bond groups and an epoxide group.
3. the method for preparing the high refractive power resin of sulfur-bearing as claimed in claim 2, it is characterized in that: described two mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,6-ethanthiol, 2,5-dimercaptothiodiazole, 1, hot two mercaptan, 1 of 8-, 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 hot two mercaptan of 8-.
4. the method for preparing the high refractive power resin of sulfur-bearing as claimed in claim 2, it is characterized in that: described catalyzer is N, the N-diethyl benzylamine, N, the 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) the 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), the 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 acrylate is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester.
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| CN104312390A (en) * | 2014-09-28 | 2015-01-28 | 上海维凯光电新材料有限公司 | Brightness-enhancement paint composition with high refraction rate |
| CN104312390B (en) * | 2014-09-28 | 2016-11-23 | 上海维凯光电新材料有限公司 | High refractive index brightness enhancement coating composition |
| CN105175644A (en) * | 2015-09-21 | 2015-12-23 | 中国林业科学研究院林产化学工业研究所 | Preparation method for dual-curing resin monomer based on castor oil |
| 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 |
| CN105713550B (en) * | 2016-04-19 | 2019-04-09 | 深圳职业技术学院 | A kind of ultraviolet light solidification optical cement and preparation method thereof for Glass optical device |
| 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 |
| CN105754545B (en) * | 2016-04-26 | 2019-04-09 | 深圳职业技术学院 | A kind of display ultraviolet light mixing cured adhesive and preparation method thereof |
| CN106590108A (en) * | 2016-12-28 | 2017-04-26 | 广东天安新材料股份有限公司 | Photocuring oligomer solution, preparation method thereof and photopolymerizable membrane |
| CN115010898A (en) * | 2022-05-16 | 2022-09-06 | 江南大学 | Oligomer for improving adhesive force of metal coating and preparation method and application thereof |
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Application publication date: 20130911 |