CN111518504A - High-refraction high-transparency light path glue special for optical communication device - Google Patents
High-refraction high-transparency light path glue special for optical communication device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a special high-refraction high-transparency optical path adhesive for an optical communication device, which is characterized by comprising the following components: fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polyether polyol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer. It has very high refracting index, simultaneously because main part structure naphthyl fluorene structure gives high modulus and rigidity to glue among this resin, polyether polyol gives the resin compliance to guaranteed that this glue possesses good rigidity and compliance, can use in optical device links and bonds in the optical communication.
Description
Technical Field
The invention belongs to the field of optical path glue, and particularly relates to a special high-refraction high-transparency optical path glue for an optical communication device, which can be applied to the optical communication industry.
Background
In the optical communication industry, optical glue with high refraction, high bonding strength and certain buffering performance is required, the glue not only plays a role in bonding and fixing, but also needs to play an optical signal transmission function in an optical device, and therefore the glue needs excellent optical performance, such as refractive index, transmittance, Abbe index and the like.
At present, the most studied high refractive index glues in the industry are organic silicon glues, for example, the invention patents in China, namely patent number ZL201210004141.1, entitled "high refractive index and high transparency organic silicon electronic potting adhesive, and preparation method and application thereof", are that olefinic silane and silanol compounds react with mercaptosilane oligomer precursors to obtain high refractive organic silicon gel. Chinese patent No. ZL200710001733.7 entitled "curable silicone rubber composition and cured product thereof" provides a curable silicone rubber composition that can form a cured product having improved hardness, no surface tackiness, a high refractive index, and rubber-like properties such as elongation without any loss, useful for electric, electronic or optoelectronic parts. The invention relates to a Chinese invention patent with the patent number of 201210307502.X and the name of high-refraction and high-adhesion high-power LED packaging organic silicon material and a chemical synthesis method thereof, which is prepared by using vinylphenyl polysiloxane, vinylphenyl silicone oil, a polysiloxane catalyst containing platinum and a tackifier; the component B comprises: the hydrogen-containing phenyl polysiloxane, the dihydro-terminated phenyl polysiloxane, the ethylene phenyl polysiloxane and the inhibitor effectively solve the contradiction between the strength and the cracking of the cured colloid. The invention can obtain refraction 1.54, is suitable for industrialization, and completely meets the requirements of high-power LED packaging. The invention also discloses a polyurethane and epoxy resin type high-refraction pouring sealant, for example, the invention patent of China with the patent number of ZL201610244889.7 and the name of ultraviolet light curing optical adhesive for glass optical devices and a preparation method thereof, wherein the high-refraction optical adhesive is prepared from sulfur-containing polyurethane, can be rapidly cured under ultraviolet light irradiation, has stronger bonding strength to glass base materials, and simultaneously has high refractive index which is more than or equal to 1.50, can meet the bonding and fixing requirements of the glass optical devices, and solves the defects of low refractive index and the like of the adhesive for the existing glass optical devices. The invention is a Chinese patent application with the patent application number of 201910255007.0 and the name of 'high-refractive index LED epoxy pouring sealant and a preparation method thereof', and the epoxy pouring sealant prepared by mixing low-halogen bisphenol A epoxy resin, a monomer containing sulfydryl or hydroxyl, a toughening agent, a diluent, methyl hexahydrophthalic anhydride, polyhydric alcohol, a curing accelerator and the like has high refractive index, transparency, low halogen, high temperature resistance, corrosion resistance and excellent mechanical properties in LED application.
The high refractive optical cement or potting adhesive mentioned in the above patent is mainly used in the LED packaging industry, and has no high requirements for purity, refractive index and reliability in the optical communication industry.
The optical path glue used in the current optical communication industry is mainly mastered by enterprises in the United states and Japan, and domestic optical path glue cannot be replaced for a while. The optical path glue is relatively less in use amount, but is very important in the field of optical devices, and the price of the optical path glue is comparable to that of gold. The optical path glue not only requires very high transparency, but also requires the refractive index to be more than 1.5, requires the refractive index to be more than 1.65 for part of special optical devices, and simultaneously requires the glue to be capable of being quickly cured, high in bonding strength and certain in buffering performance.
The shading index can be greatly improved to more than 1.7 at most according to Lorentz-Lorenz equation, benzene ring structure, biphenyl structure, naphthalene structure, S element and the like in the communication industry, and the shading index is close to optical glass. Although there are documents of high refractive optical materials reported in the industry, for example, chinese patent application No. 201410164091.2 entitled "composition for high refractive index and high strength optical material" uses an electrodeless compound of sulfur atom, and an episulfide compound and a xylylene sulfide compound react to prepare an optical lens material with a shading index of 1.73. The present invention is a chinese patent application No. 2014800443845 entitled "polymerizable composition for high refractive index optical material and method for producing high refractive index optical material", which uses acrylic resin of fluorene structure to prepare high refractive index lens material by free radical reaction.
Although the refractive index of the material is higher, the lens is mainly prepared by adopting an injection molding process, and the material is not light path glue suitable for being used in an optical device, and the existing light path glue has a space for further improvement and optimization along with the development of the optical device.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the high-refraction high-transparency light path adhesive, which ensures that the resin has a very high refractive index of more than 1.7, has good structural strength and flexibility, has high bonding strength and high reliability after being cured, and can be subjected to UV curing, heating curing and UV + heat dual curing.
In order to achieve the purpose, the technical scheme of the invention is realized by the following steps of: fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene naphthalene polyether polyol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer, wherein the mass ratio of fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer is: 1: 0.1-0.5: 0.8-1.2: 0.005-0.01: 0.1-0.5: 0.1-0.3: 0.001-0.005.
In this technical solution, the method for synthesizing fluorene polyether polyol is: mixing 9,9-Bis (6-hydroxy-2-naphthyl) fluorene (CAS number: 934557-66-1), thiirane, an alkaline catalyst and a solvent A, and reacting at the temperature of 60-120 ℃ for 2-5 hours to obtain the naphthyl fluorene polyether polyol, wherein the mass ratio of the 9,9-Bis (6-hydroxy-2-naphthyl) fluorene to the thiirane to the alkaline catalyst to the solvent A is 1: 0.2-10: 0.01-0.05: 10-50 parts of; the chemical reaction equation is shown as the following formula:
wherein m + n =4-20;
the fluorene naphthalene polyether polyol with end epoxy group is synthesized by dissolving fluorene naphthalene polyether polyol in solvent A, adding epichlorohydrin and sodium hydroxide, reacting at 60-120 deg.C for 1-3 hr, washing with water, and purifying by reduced pressure distillation to obtain fluorene naphthalene polyether polyol with epoxy group; wherein the mass ratio of naphthyl fluorene polyether polyol to epichlorohydrin to sodium hydroxide to solvent A is 1: 0.5-5: 0.1-0.5: 10-20 parts of; the chemical reaction equation is shown as the following formula:
wherein m + n =4-20;
the alkaline catalyst is one or a mixture of more of triethylamine, ammonium carbonate, sodium carbonate, potassium carbonate and sodium hydroxide, and the solvent A is one or a mixture of more of formamide, N-methyl pyrrolidone, dimethyl sulfoxide, cyclohexanone, tetramethyl ethylenediamine or dioxane.
In the technical scheme, the alicyclic epoxy resin is one or a mixture of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate (CAS: 2386-87-0), tetrahydrophthalic acid diglycidyl ester (CAS: 21544-03-6), bis ((3, 4-epoxycyclohexyl) methyl) adipate (CAS: 3130-19-6), poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1) (CAS: 244772-00-7) or cyclohexane-1, 2-dicarboxylic acid diglycidyl ester (CAS: 5493-45-8).
In the technical scheme, the latent amine catalyst is one or a mixture of more of 1, 8-diazabicyclo (5.4.0), undec-7-ene (DBU), 1, 4-diazabicyclo (2, 2, 2) octane (DABCO), triethylamine, Tetramethylguanidine (TMG), dimethyl-p-toluidine (DMPT), dimethylaniline, dihydroxyethylaniline, ethyl-p-toluidine or dialkylaniline.
In the technical scheme, the mercaptan diluent is one or a mixture of trimethylolpropane tris (3-mercaptopropionate) (CAS: 33007-83-9), pentaerythritol tetrakis (3-mercaptopropionate) (CAS: 7575-23-7) or isooctyl 3-mercaptopropionate (CAS: 30374-01-7).
In the technical scheme, the stabilizer is one or a mixture of more of barbituric acid, triphenyl phosphate, salicylic acid, tartaric acid, citric acid, ascorbic acid, trihydroxybenzoic acid or parabanic acid.
In the technical scheme, the photoinitiator is one or a mixture of 2,2' -bis (2-bromo-5-methoxyphenyl) -4,4' -5,5' -tetraphenyl-diimidazole (M-HABI) or 2-hydroxy-methylphenyl propane-1-ketone.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the present invention develops a fluorene naphthalene polythiol and fluorene naphthalene polyether polyol which contains a large amount of high refractive sulfur element, benzene rings (each molecule contains 6 benzene rings), naphthalene group, etc. to ensure that the resin has an extremely high refractive index of more than 1.7;
2. fluorene naphthalene polyether polyol and fluorene naphthalene polythiol monomer is developed, wherein fluorene naphthalene has rigid structure and polyether polyol and fluorene naphthalene polythiol have flexible structure, therefore the adhesive based on this resin system has good structural strength and flexibility at the same time.
3. The fluorene naphthalene polythiol and fluorene end ring polyether polyol are subjected to a cross-linking curing reaction by using a chemical reaction between mercaptan and epoxy under the catalysis of an amino catalyst, so that the curing and cross-linking are finally realized, and the high bonding strength and the high reliability of glue after curing are ensured.
4. The high-refractive-index high-light-transmittance road adhesive can be cured by UV, can be cured by heating, and can be cured by UV and heat. The glue can be fully cured under various complex conditions and various application conditions.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example one
(1) Synthesis of fluorene naphthalene polyether polyol:
adding 9,9-Bis (6-hydroxy-2-naphthyl) fluorene (CAS number: 934557-66-1), thiirane, an alkaline catalyst and a solvent A together, reacting at 60 ℃ for 2 hours to obtain the naphthyl fluorene polyether polyol, wherein the mass ratio of the 9,9-Bis (6-hydroxy-2-naphthyl) fluorene to the thiirane to the alkaline catalyst to the solvent A is 1: 0.2: 0.01: 10; the chemical reaction equation is shown as the following formula:
wherein m + n = 4;
wherein the basic catalyst is triethylamine, and the solvent A is formamide.
(2) Synthesis of fluorene polyether polyol terminated with epoxy group
Dissolving fluorene naphthyl polyether polyol in a solvent A, adding epichlorohydrin and sodium hydroxide, raising the reaction temperature to 60 ℃, reacting for 1 hour, washing with water, and carrying out reduced pressure distillation and purification to obtain fluorene naphthyl polyether polyol with epoxy group; wherein the mass ratio of naphthyl fluorene polyether polyol to epichlorohydrin to sodium hydroxide to solvent A is 1: 0.5: 0.1: 10; the chemical reaction equation is shown as the following formula:
wherein m + n = 4;
(3) preparation of high-refraction high-transparency light path adhesive
And mixing the fluorene end ring polyether polyol, the alicyclic epoxy resin, fluorene polythiol, the latent amine catalyst, the thiol diluent, the photoinitiator and the stabilizer to obtain the high-refraction high-transparency optical path adhesive. Wherein the weight ratio of fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer is as follows: 1: 0.1: 0.8: 0.005: 0.1: 0.1: 0.001;
the alicyclic epoxy resin is 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, and the type of the alicyclic epoxy resin is CAS: 2386-87-0; the latent amine catalyst is 1, 8-diazabicyclo (5.4.0); the mercaptan diluent is trimethylolpropane tri (3-mercaptopropionate) with the model of CAS: 33007-83-9; the stabilizer is barbituric acid; the photoinitiator is 2,2' -bis (2-bromo-5-methoxyphenyl) -4,4' -5,5' -tetraphenyl-diimidazole (M-HABI).
Example two
(1) Synthesis of fluorene naphthalene polyether polyol:
adding 9,9-Bis (6-hydroxy-2-naphthyl) fluorene (CAS number: 934557-66-1), thiirane, an alkaline catalyst and a solvent A together, reacting at 120 ℃ for 5 hours to obtain the naphthyl fluorene polyether polyol, wherein the mass ratio of the 9,9-Bis (6-hydroxy-2-naphthyl) fluorene to the thiirane to the alkaline catalyst to the solvent A is 1: 10: 0.05: 50; the chemical reaction equation is shown as the following formula:
wherein m + n = 20;
the alkaline catalyst is sodium hydroxide. The solvent A is dioxane.
(2) Synthesis of fluorene polyether polyol terminated with epoxy group
Dissolving fluorene naphthyl polyether polyol in a solvent A, adding epichlorohydrin and sodium hydroxide, raising the reaction temperature to 120 ℃, reacting for 3 hours, washing with water, and carrying out reduced pressure distillation and purification to obtain fluorene naphthyl polyether polyol with epoxy group; wherein the mass ratio of naphthyl fluorene polyether polyol to epichlorohydrin to sodium hydroxide to solvent A is 1: 5: 0.5: 20; the chemical reaction equation is shown as the following formula:
wherein m + n = 20.
(3) Preparation of high-refraction high-transparency light path adhesive
Fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer are mixed to obtain the high-refraction high-transparency optical path adhesive, wherein the mass ratio of fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer is as follows: 1: 0.5: 1.2: 0.01: 0.5: 0.3: 0.005.
the alicyclic epoxy resin is diglycidyl tetrahydrophthalate, and the type of the alicyclic epoxy resin is CAS: 21544-03-6; the latent amine catalyst is dimethylaniline; the mercaptan diluent is isooctyl 3-mercaptopropionate, and the model is CAS: 30374-01-7; the stabilizer is parabanic acid; the photoinitiator is 2-hydroxy-methyl phenyl propane-1-ketone.
EXAMPLE III
(1) Synthesis of fluorene naphthalene polyether polyol:
adding 9,9-Bis (6-hydroxy-2-naphthyl) fluorene (CAS number: 934557-66-1), thiirane, alkaline catalyst and solvent A together, reacting at 100 deg.C for 3 hr to obtain fluorene naphthalene polyether polyol; wherein the mass ratio of the 9,9-Bis (6-hydroxy-2-naphthyl) fluorene to the thiirane to the alkaline catalyst to the solvent A is 1: 10: 0.05: 50; the chemical reaction equation is shown as the following formula:
wherein m + n = 10;
the alkaline catalyst is sodium carbonate and the solvent A is cyclohexanone.
(2) Synthesis of fluorene polyether polyol terminated with epoxy group
Dissolving fluorene naphthyl polyether polyol in a solvent A, adding epichlorohydrin and sodium hydroxide, raising the reaction temperature to 100 ℃, reacting for 2 hours, washing with water, and carrying out reduced pressure distillation and purification to obtain fluorene naphthyl polyether polyol with epoxy group; wherein the mass ratio of naphthyl fluorene polyether polyol to epichlorohydrin to sodium hydroxide to solvent A is 1: 3: 0.3: 12; the chemical reaction equation is shown as the following formula:
wherein m + n = 10.
(3) Preparation of high-refraction high-transparency light path adhesive
Mixing end-ring fluorene polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer to obtain high-refraction high-transparency optical path adhesive; wherein fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent and photoinitiator; the mass ratio of the stabilizer is as follows: 1: 0.4: 1: 0.008: 0.3: 0.2: 0.004;
the cycloaliphatic epoxy resin is poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1) with the type CAS: 244772-00-7; the latent amine catalyst is triethylamine; the mercaptan diluent is isooctyl 3-mercaptopropionate, and the model is CAS: 30374-01-7; the stabilizer is trihydroxybenzoic acid; the photoinitiator is 2-hydroxy-methyl phenyl propane-1-ketone.
Example four
(1) Synthesis of fluorene naphthalene polyether polyol:
adding 9,9-Bis (6-hydroxy-2-naphthyl) fluorene (CAS number: 934557-66-1), thiirane, an alkaline catalyst and a solvent A together, wherein the reaction temperature is 80 ℃, and obtaining the naphthyl fluorene polyether polyol after 4 hours of reaction, wherein the mass ratio of the 9,9-Bis (6-hydroxy-2-naphthyl) fluorene to the thiirane to the alkaline catalyst is 1: 5: 0.03: 25; the chemical reaction equation is shown as the following formula:
wherein m + n = 18;
the alkaline catalyst is potassium carbonate, and the solvent A is dimethyl sulfoxide.
(2) Synthesis of fluorene polyether polyol terminated with epoxy group
Dissolving fluorene naphthalene polyether polyol in a solvent A, adding epichlorohydrin and sodium hydroxide, raising the reaction temperature to 100 ℃, reacting for 2.5 hours, washing with water, and carrying out reduced pressure distillation and purification to obtain fluorene naphthalene polyether polyol with epoxy groups; wherein the mass ratio of naphthyl fluorene polyether polyol to epichlorohydrin to sodium hydroxide to solvent A is 1: 3: 0.35: 15; the chemical reaction equation is shown as the following formula:
wherein m + n = 18.
(3) Preparation of high-refraction high-transparency light path adhesive
Mixing the fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene naphthalene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer to obtain the high-refraction high-transparency optical path adhesive, wherein the mass ratio of fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene naphthalene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer is as follows: 1: 0.35: 1.1: 0.009: 0.45: 0.25: 0.004;
the cycloaliphatic epoxy resin is cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, the type of which is CAS: 5493-45-8; the latent amine catalyst is Tetramethylguanidine (TMG); the mercaptan diluent is pentaerythritol tetrakis (3-mercaptopropionate) with the model CAS: 7575-23-7; the stabilizer is triphenyl phosphate; the photoinitiator is 2-hydroxy-methyl phenyl propane-1-ketone.
EXAMPLE five
(1) Synthesis of fluorene naphthalene polyether polyol:
adding 9,9-Bis (6-hydroxy-2-naphthyl) fluorene (CAS number: 934557-66-1), thiirane, alkaline catalyst and solvent A together, reacting at 90 deg.C for 4 hr to obtain fluorene naphthyl polyether polyol; wherein the mass ratio of the 9,9-Bis (6-hydroxy-2-naphthyl) fluorene to the thiirane to the alkaline catalyst to the solvent A is 1: 7: 0.03: 30, of a nitrogen-containing gas; the chemical reaction equation is shown as the following formula:
wherein m + n = 10;
the alkaline catalyst is potassium carbonate, and the solvent A is tetramethylethylenediamine.
(2) Synthesis of fluorene polyether polyol terminated with epoxy group
Dissolving fluorene naphthalene polyether polyol in a solvent A, adding epichlorohydrin and sodium hydroxide, raising the reaction temperature to 100 ℃, reacting for 2.5 hours, washing with water, and carrying out reduced pressure distillation and purification to obtain fluorene naphthalene polyether polyol with epoxy groups; wherein the mass ratio of naphthyl fluorene polyether polyol to epichlorohydrin to sodium hydroxide to solvent A is 1: 3: 0.35: 15; the chemical reaction equation is shown as the following formula:
wherein m + n = 10.
(3) Preparation of high-refraction high-transparency light path adhesive
Fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer are mixed to obtain the high-refraction high-transparency optical path adhesive. Wherein the fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer in the weight ratio: 1: 0.35: 0.9: 0.009: 0.35: 0.25: 0.002;
the alicyclic epoxy resin is cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, and the type of the alicyclic epoxy resin is CAS: 5493-45-8; the latent amine catalyst is dihydroxyethyl aniline; the mercaptan diluent is isooctyl 3-mercaptopropionate, and the model is CAS: 30374-01-7; the stabilizer is ascorbic acid; the photoinitiator is 2-hydroxy-methyl phenyl propane-1-ketone.
The high-refractive index and high-transparency optical path adhesive obtained in the first to fifth embodiments is applied to an optical device for optical communication, and the curing method thereof may be UV curing, or thermal curing or UV reheating first.
The UV light curing conditions are as follows: the LED 365 or 405nm wave band and the power of 200-2Irradiating for 10-40 s; the heat curing conditions were: temperature ofThe temperature is 70-100 ℃, and the time is 30-60 min.
The optical path glues prepared in the first to fifth examples were subjected to application testing, and the performance testing parameters are shown in table 1 below. And (3) viscosity testing: and the viscosity of the glue is tested by a rotary viscometer by referring to GB/T22235-2008.
Tg point test: DMA test is adopted, the frequency is 1Hz, the temperature rising speed is 10 ℃/min, and the temperature rising range is 25-400 ℃.
CTE test: the linear expansion coefficient was measured by TMA test with reference to JIS K7197, 10mm by 25mm test specimen, and heating rate 50 ℃/min.
And (3) testing the refractive index: with reference to GB 7962.11-2010-T, refractive index tests of the hardened coatings were performed.
And (3) transparency test: the transmittance test is carried out by referring to GB T2410-2008;
elongation at break and modulus test: referring to the method for preparing the sample in GB-T30776-. The elongation at break reflects the flexibility of the material to a certain extent, and the modulus reflects the rigidity of the material to a certain extent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A special high-refraction high-transparency optical path adhesive for optical communication devices is characterized by comprising the following components: fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene naphthalene polyether polyol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer, wherein the mass ratio of fluorene end ring polyether polyol, alicyclic epoxy resin, fluorene polythiol, latent amine catalyst, thiol diluent, photoinitiator and stabilizer is: 1: 0.1-0.5: 0.8-1.2: 0.005-0.01: 0.1-0.5: 0.1-0.3: 0.001-0.005.
2. The special high-refraction high-transparency optical path adhesive for optical communication device of claim 1, wherein the fluorene naphthalene polyether polyol is synthesized by: mixing 9,9-Bis (6-hydroxy-2-naphthyl) fluorene (CAS number: 934557-66-1), thiirane, an alkaline catalyst and a solvent A, and reacting at the temperature of 60-120 ℃ for 2-5 hours to obtain the naphthyl fluorene polyether polyol, wherein the mass ratio of the 9,9-Bis (6-hydroxy-2-naphthyl) fluorene to the thiirane to the alkaline catalyst to the solvent A is 1: 0.2-10: 0.01-0.05: 10-50 parts of; the chemical reaction equation is shown as the following formula:
wherein m + n =4-20;
the fluorene naphthalene polyether polyol with end epoxy group is synthesized by dissolving fluorene naphthalene polyether polyol in solvent A, adding epichlorohydrin and sodium hydroxide, reacting at 60-120 deg.C for 1-3 hr, washing with water, and purifying by reduced pressure distillation to obtain fluorene naphthalene polyether polyol with epoxy group; wherein the mass ratio of naphthyl fluorene polyether polyol to epichlorohydrin to sodium hydroxide to solvent A is 1: 0.5-5: 0.1-0.5: 10-20 parts of; the chemical reaction equation is shown as the following formula:
wherein m + n =4-20;
the alkaline catalyst is one or a mixture of more of triethylamine, ammonium carbonate, sodium carbonate, potassium carbonate and sodium hydroxide, and the solvent A is one or a mixture of more of formamide, N-methyl pyrrolidone, dimethyl sulfoxide, cyclohexanone, tetramethylethylenediamine and dioxane.
3. The special high-refraction high-transparency optical path adhesive for optical communication devices according to claim 1, wherein the alicyclic epoxy resin is 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate (CAS: 2386-87-0), tetrahydrophthalic acid diglycidyl ester (CAS: 21544-03-6), bis ((3, 4-epoxycyclohexyl) methyl) adipate (CAS: 3130-19-6), poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1) (CAS: 244772-00-7), cyclohexane-1, 2-dicarboxylic acid diglycidyl ester (CAS: 5493-45-8).
4. The special high-refraction high-transparency optical-path adhesive for optical communication devices according to claim 1, wherein the latent amine catalyst is one or a mixture of 1, 8-diazabicyclo (5.4.0), undec-7-ene (DBU), 1, 4-diazabicyclo (2, 2, 2) octane (DABCO), triethylamine, Tetramethylguanidine (TMG), dimethyl-p-toluidine (DMPT), dimethylaniline, dihydroxyethylaniline, ethyl-p-toluidine, and dialkylaniline.
5. The special high-refraction high-transparency optical path adhesive for optical communication devices as claimed in claim 1, wherein the thiol diluent is one or more of trimethylolpropane tris (3-mercaptopropionate) (CAS: 33007-83-9), pentaerythritol tetrakis (3-mercaptopropionate) (CAS: 7575-23-7), or isooctyl 3-mercaptopropionate (CAS: 30374-01-7).
6. The special high-refraction high-transparency optical path adhesive for optical communication devices as claimed in claim 1, wherein the stabilizer is one or more of barbituric acid, triphenyl phosphate, salicylic acid, tartaric acid, citric acid, ascorbic acid, trihydroxybenzoic acid or parabanic acid.
7. The special high-refraction high-transparency optical path adhesive for optical communication devices as claimed in claim 1, wherein the photoinitiator is one or more of 2,2' -bis (2-bromo-5-methoxyphenyl) -4,4' -5,5' -tetraphenyl-diimidazole (M-HABI) or 2-hydroxy-methylphenylpropane-1-one.
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| CN112961570A (en) * | 2021-02-06 | 2021-06-15 | 杭州每步材料科技有限公司 | Environment-friendly underwater toughening epoxy resin adhesive and preparation method thereof |
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