CN114773985B - Low-refractive-index optical fiber coating - Google Patents

Low-refractive-index optical fiber coating Download PDF

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CN114773985B
CN114773985B CN202210485756.4A CN202210485756A CN114773985B CN 114773985 B CN114773985 B CN 114773985B CN 202210485756 A CN202210485756 A CN 202210485756A CN 114773985 B CN114773985 B CN 114773985B
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CN114773985A (en
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袁泉
姜胜斌
曹亮
陈奇
陈迪伟
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Yangtze Optical Fibre and Cable Co Ltd
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

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Abstract

The invention provides a low-refractive-index optical fiber coating, which comprises the following components: fluorine-containing oligomer, fluorine-containing reactive monomer diluent, photoinitiator polymerization inhibitor, fluorine-containing adhesion promoter and auxiliary agent; the fluorine-containing oligomer is fluorine-containing epoxy urethane acrylate oligomer, and the fluorine-containing epoxy urethane acrylate oligomer is obtained by blending fluorine-containing urethane acrylate and fluorine-containing epoxy acrylate; the fluorine-containing reactive monomer diluent is fluorine-containing monoacrylate and fluorine-containing polyacrylate; the fluorine-containing adhesion promoter is a fluorine-containing silane coupling agent containing a photocurable group. The refractive index of the coating is low and is between 1.35 and 1.36, the adhesion promoting effect between the coating and the glass fiber is obvious, in addition, the curing speed of the coating is high, and the manufacturing efficiency of the optical fiber is high.

Description

Low-refractive-index optical fiber coating
Technical Field
The invention relates to the field of optical fiber coatings, in particular to a light-cured low-refractive-index optical fiber coating resin for an optical fiber laser.
Background
Optical fiber coatings are coatings used to protect optical fibers from the environment while maintaining sufficient mechanical strength and optical properties, and are multilayer protective systems that are a combination of a soft buffer layer applied during fiber draw molding and a harder protective layer of toughness, abrasion resistance, chemical resistance, etc. applied later.
The optical fiber laser is a laser using rare earth element doped glass optical fiber as a gain medium, and has wide application in the fields of marking, material processing, material bending, laser cutting and the like. In order to restrict the transmission of pump light in the optical fiber quartz cladding, the refractive index of the inner coating of the optical fiber for the optical fiber laser is required to be low, and the refractive index of the inner coating is generally 1.35-1.37 according to the requirement of the numerical aperture of the optical fiber.
The low-refractive-index optical fiber coating is generally fluorine-containing or silicon-containing photocuring acrylic resin, but the refractive index of the silicon-containing acrylic resin is generally more than 1.41, so that the low-refractive-index optical fiber coating for the optical fiber laser is generally made of fluorine-containing acrylic resin, and the higher the fluorine content of the resin is, the lower the refractive index of the resin is. However, the synthetic fluorine-containing acrylic resin has few fluorine-containing raw materials, is expensive, and has poor compatibility with fluorine-free raw materials, so that the synthetic technology threshold is high. Besides the requirement of refractive index, the low-refractive-index optical fiber coating for the optical fiber laser also needs to have stronger interface bonding force with glass fiber, and the bonding force is not weakened in the high-temperature and high-humidity environment, so that the use scene requirement of the optical fiber laser is met. The optical fiber for the current optical fiber laser is influenced by the structure of an optical fiber preform, the curing speed of a coating and the bonding force of the coating and a glass fiber interface, the drawing speed is slower than that of the common optical fiber, the production efficiency is low, but the research report of a coating supplier on the drawing speed is rare.
At present, there are reports related to obtaining a low refractive index optical fiber coating by introducing fluorine atoms into raw materials, for example, patent CN202010121219.2 discloses a low refractive index optical fiber inner layer coating, which uses fluorine-containing urethane acrylate oligomer, bifunctional fluorine-containing acrylate monomer, long-chain monofunctional fluorine-containing acrylate monomer, initiator, leveling agent, and silane coupling agent, and maintains higher mechanical strength and excellent glass adhesion while ensuring low refractive index of the coating, wherein the bifunctional fluorine-containing acrylate monomer can significantly improve the film forming modulus of the formula. However, fluorine-free silane coupling agents are poorly compatible with fluorine-containing coating systems, resulting in coatings with too short a shelf life and adversely affecting their peel force. For example, the properties of a commercially available low index optical fiber coating are as follows: the low-refractive-index optical fiber coating has the problems of 1.369 refractive index, 2500 mPas viscosity, 5.2MPa tensile strength, 22.35 percent elongation at break, 45.46MPa tensile modulus at 2.5 percent strain, 2.4N glass adhesion and 220m/min maximum optical fiber drawing speed, and is slow in curing speed and low in optical fiber manufacturing efficiency.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the low-refractive-index optical fiber coating which has the advantages of low refractive index of 1.35-1.36, obvious adhesion promoting effect with glass fibers, high curing speed and high manufacturing efficiency of optical fibers.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
the low-refractive-index optical fiber coating comprises the following components in percentage by weight: 20 to 70 weight percent of fluorine-containing oligomer, 10 to 70 weight percent of fluorine-containing active monomer diluent, 1 to 10 weight percent of photoinitiator, 0.1 to 2 weight percent of polymerization inhibitor, 0.5 to 5 weight percent of fluorine-containing adhesion promoter and 0 to 5 weight percent of auxiliary agent;
wherein the fluorine-containing oligomer is a fluorine-containing epoxy urethane acrylate oligomer, and the fluorine-containing epoxy urethane acrylate oligomer is obtained by blending fluorine-containing urethane acrylate and fluorine-containing epoxy acrylate, wherein the mass ratio of the fluorine-containing urethane acrylate to the fluorine-containing epoxy acrylate is (2);
the preparation method of the fluorine-containing epoxy polyurethane acrylate oligomer comprises the following steps: (1) preparation of fluorine-containing epoxy acrylate: sequentially adding fluorine-containing epoxy resin and a polymerization inhibitor into a three-neck flask provided with a mechanical stirrer, a thermometer and a constant-pressure funnel, controlling the reaction temperature to be 100 +/-5 ℃, dropwise adding a mixture of acrylic acid and a catalyst through the constant-pressure funnel, wherein the molar ratio of epoxy groups in the fluorine-containing epoxy resin to the acrylic acid is 1-1: 1.05, the dosage of the catalyst is 0.1-1% of the total mass of reactants, the dosage of the polymerization inhibitor is 0.1-1% of the total mass of the reactants, after the dropwise addition is finished, carrying out heat preservation reaction for 3-4 h, carrying out interval sampling to measure the acid value, and stopping the reaction when the interval acid value is not changed to obtain the fluorine-containing epoxy acrylate for later use;
(2) Sequentially adding fluorine-containing polyol, isocyanate and a catalyst into a three-neck flask provided with a mechanical stirrer and a thermometer, heating to 60-70 ℃, and reacting for 2-2.5 hours in a heat preservation manner; and (2) adding hydroxyl (meth) acrylate and a polymerization inhibitor, continuing to react for 2-3 hours at 60-70 ℃, sampling to determine the content of isocyanate, after the content is zero, adding the fluorine-containing epoxy acrylate prepared in the step (1), continuing to stir for 0.5-1 hour, and cooling to room temperature to obtain the fluorine-containing epoxy urethane acrylate oligomer, wherein the dosage of the catalyst is 0.1-1% of the total mass of the reactants, and the dosage of the polymerization inhibitor is 0.1-1% of the total mass of the reactants.
The fluorine-containing epoxy resin is 2, 2-bisphenol hexafluoropropane diglycidyl ether, octafluorobiphenyl diglycidyl ether, 1,3- (bis hexafluoro light propyl) benzene diglycidyl ether, 1, 4-bis (hexafluoro antelope inner group) benzene diglycidyl ether and has a structural general formula of epoxy-CF 2 O-(CF 2 CF 2 O) m -(CF 2 O) n -CF 2 -one or a mixture of two or more epoxy oligomers, wherein m is from 1 to 20 and n is from 1 to 20.
The fluorine-containing polyol is one or a mixture of more than two of fluorine-containing polyether monol, fluorine-containing polyether diol, fluorine-containing polyester monol and fluorine-containing polyester diol.
The isocyanate is any one or a mixture of more than two of toluene diisocyanate, 4' -diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate, trans-butadiene diacid diethyl diisocyanate, methyl cyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and tetramethyl xylylene diisocyanate.
The hydroxyl (meth) acrylate is one or a mixture of two or more of hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolethane di (meth) acrylate.
The fluorine-containing active monomer diluent is fluorine-containing monoacrylate, fluorine-containing diacrylate and fluorine-containing polyacrylate, wherein the fluorine-containing polyacrylate accounts for 10-45% by mass;
wherein the structural formula of the fluorine-containing monoacrylate is as follows:
CH 2 ＝CR 2 COO(CH 2 ) c (CF 2 ) d X
wherein R is 2 Is a hydrogen atom or a methyl group, X is a hydrogen atom or a fluorine atom; c is 1 to 5, d is 1 to 10;
the structural formula of the fluorine-containing diacrylate is as follows:
CH 2 ＝CR 3 COOCH 2 CF 2 O-[(CF 2 CF 2 O) e -(CF 2 O) f ]-CF 2 CH 2 OCOCR 3 ＝CH 2
wherein R is 3 Is hydrogen atom or methyl, e is 1 to 15, f is 1 to 15;
the fluorine-containing polyacrylate is fluorine-containing tetraacrylate, and the structural formula of the fluorine-containing tetraacrylate is as follows:
(CH 2 ＝CR 5 COOCH 2 ) 2 CFO-[(CF 2 CF 2 O) j -(CF 2 O) k ]-CF(CH 2 OCOCR 5 ＝CH 2 ) 2 wherein R is 5 Is hydrogen atom or methyl, j is 1 to 15, k is 1 to 15.
The fluorine-containing adhesion promoter is a fluorine-containing silane coupling agent containing a light-curable group, and the molecular formula of the fluorine-containing adhesion promoter is as follows:
CH 2 ＝CR 1 COOCH 2 CF 2 O-[(CF 2 CF 2 O) a -(CF 2 O) b ]-CF 2 CH 2 -Si(OEt) 3
wherein R is 1 Is hydrogen atom or methyl, a is 1 to 30, b is 1 to 30.
The polymerization inhibitor is one of hydroquinone and p-hydroxyanisole; the catalyst is one or a mixture of more than two of dibutyl tin dilaurate, bismuth carboxylate, bismuth isooctanoate, N, N-dimethyl cyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethyl alkylene diamine, triethylamine, N, N-dimethyl benzylamine, solid amine, N-ethyl morpholine, N, N '-diethyl piperazine, triethanolamine, dimethyl amino ethanol, pyridine and N, N' -dimethyl pyridine.
The photoinitiator is one or a mixture of more than two of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone.
The auxiliary agent comprises a defoaming agent, a leveling agent, an antioxidant and a stabilizing agent.
Compared with the prior art, the low-refractive-index optical fiber coating provided by the invention has the following advantages:
(1) The components in the low-refractive-index coating provided by the invention are matched with each other to obtain the low-refractive-index optical fiber coating suitable for an optical fiber laser, the refractive index of the low-refractive-index optical fiber coating is 1.35-1.36, and the low-refractive-index optical fiber coating has good stripping force performance and high curing speed.
(2) The fluorine-containing oligomer is fluorine-containing epoxy urethane acrylate oligomer, fluorine-containing urethane acrylate is generated by reacting fluorine-containing polyol, isocyanate and (methyl) acrylic hydroxyl ester, and then fluorine-containing epoxy acrylate is added into the fluorine-containing urethane acrylate for blending. The introduction of the fluorine-containing epoxy acrylate can improve the modulus of the coating after curing and increase the adhesion between the coating and glass, but when the fluorine-containing epoxy acrylate is excessive, the adhesion and the wire drawing speed are reduced on the contrary although the modulus is higher.
(3) The fluorine-containing reactive monomer diluent is fluorine-containing monoacrylate and fluorine-containing polyacrylate, and the viscosity, the refractive index and the mechanical property of the coating can be adjusted by adjusting the adding amount and the proportion of the fluorine-containing reactive monomer diluent and the fluorine-containing polyacrylate in a coating system. The fluorine-containing polyacrylate can greatly improve the curing speed of the coating, further improve the manufacturing efficiency of the optical fiber and solve the problem of low curing speed of the traditional fluorine-containing coating. Especially, the adoption of a proper amount of fluorine-containing tetraacrylate ensures that the coating has good comprehensive performance.
(4) The low-refractive-index coating provided by the invention is added with the fluorine-containing silane coupling agent containing the photocurable group, so that the problems of poor compatibility of a common silane coupling agent and a fluorine-containing coating system and small promotion effect on the adhesive force of the coating are solved, and the adhesive force and the curing speed of the coating and glass are improved by participating in a photocuring reaction and under the combined action of fluorine-containing epoxy acrylate.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples.
Preparation of fluorine-containing epoxy acrylate: sequentially adding fluorine-containing epoxy resin (epoxy-CF) into a three-neck flask provided with a mechanical stirrer, a thermometer and a constant pressure funnel 2 O-(CF 2 CF 2 O) a -(CF 2 O) b -CF 2 Epoxy, M =1100 g/mol) 110g and polymerization inhibitor 1.2g, controlling the reaction temperature to be 100 +/-5 ℃, dropwise adding a mixture of 14.41g of acrylic acid and 3.11g of catalyst triethylamine through a constant-pressure funnel, controlling the dropwise adding speed to ensure that the temperature in the reaction is not too high, keeping the temperature for reaction for 3-4 h after the dropwise adding is finished, sampling to measure the acid value, and stopping the reaction after the reaction is qualified to obtain the fluorine-containing epoxy acrylate for later use.
Example 1
Preparation of fluorine-containing epoxy urethane acrylate oligomer: sequentially adding perfluoropolyether diol (M = 2000), isophorone diisocyanate and a catalyst dibutyltin dilaurate into a three-neck flask provided with a mechanical stirrer and a thermometer, heating to 60-70 ℃, carrying out heat preservation reaction for 2-2.5 hours, adding hydroxyethyl acrylate and a polymerization inhibitor hydroquinone, continuously reacting for 2-3 hours at 60-70 ℃, sampling to determine the content of isocyanate, adding the fluorine-containing epoxy acrylate prepared in the step (1) after the content is zero, continuously stirring to react for 0.5-1 hour, and cooling to room temperature to obtain the fluorine-containing epoxy urethane acrylate oligomer.
Preparing the low-refractive-index optical fiber coating: and (2) directly and uniformly mixing 1.5g of self-made fluorine-containing oligomer, fluorine-containing active monomer diluent, photoinitiator, fluorine-containing adhesion promoter and polymerization inhibitor at 60 ℃ to obtain the low-refractive-index optical fiber coating.
Examples 2 to 6 and comparative examples 1 to 4 were prepared according to the method of example 1, and the formulation compositions and performance tests thereof are shown in the following table. In the table IPDI is isophorone diisocyanate, TPO is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and DAROCURE 1173 is 2-hydroxy-2-methyl-1-phenylacetone.
Figure BDA0003629857280000051
The glass adhesion test method comprises the following steps:
the liquid coating was cured to a cured film thickness of 100 μm on a polished glass plate. Cutting a sample of 150mm multiplied by 25mm, stripping off an adhesive surface of 25mm, freely clamping the sample by a clamp, fixing the other end of the glass plate on furniture of an electronic tensile machine, starting the tensile machine, pulling the cured film at the speed of 100mm/min, carrying out a 180-degree stripping test, slowly and continuously stripping the cured film from the glass plate, and reading the stripping force displayed by the tensile machine, namely the glass adhesive force.
As can be seen from example 1 and comparative example 3, when the fluorine-containing tetraacrylate is added to the low-refractive-index optical fiber coating, the maximum drawing speed of the optical fiber can be increased from 250m/min to 460m/min, and the curing speed of the coating is obviously increased. The fluorine-containing tetraacrylate contains higher-density light-curable acrylate groups, so that the curing speed is increased during later photocuring of the coating, the maximum drawing speed of the optical fiber is obviously increased, and the manufacturing efficiency of the optical fiber is improved. In addition, the addition of the fluorine-containing tetraacrylate can improve the crosslinking density of the coating after curing, so that the strength and modulus of the coating after curing can be improved. However, it is understood from example 1 and comparative examples 3 to 5 that the fluorine-containing tetraacrylate needs to be used in combination with fluorine-containing monoacrylate and fluorine-containing diacrylate to obtain a low refractive index optical fiber coating having excellent overall properties, and it is understood from example 1, examples 3 to 6 and comparative examples 6 to 7 that the fluorine-containing tetraacrylate can obtain a coating having excellent overall properties within a certain amount range, and when the amount of the fluorine-containing tetraacrylate is too much or too little, the other properties are still poor in the case of similar viscosity.
It is understood from examples 1 and 2 and comparative example 1 that by incorporating fluorine-containing epoxy acrylate into fluorine-containing urethane acrylate, the modulus of the coating after curing is improved and the adhesion of the coating to glass is also remarkably improved. The chemical bonding force is generated between the hydroxyl in the molecular chain of the fluorine-containing epoxy acrylate and the glass, so that the bonding force between the coating and the glass is improved, and meanwhile, the fluorine-containing epoxy acrylate can participate in the photocuring reaction, so that the mechanical property of the coating is improved. However, it is understood from comparative example 2 that the excessive addition of the fluorine-containing epoxy acrylate causes a decrease in glass adhesion and drawing speed, because the excessive addition of the fluorine-containing epoxy acrylate causes an excessive increase in modulus after curing of the coating material, decreases adhesion to glass fibers, and further causes defects more easily during drawing, resulting in a decrease in maximum drawing speed.
As can be seen from example 1 and comparative examples 8 to 9, the addition of the fluorine-containing silane coupling agent containing a photocurable group to the low refractive index optical fiber coating provided in example 1 can significantly improve the glass adhesion and drawing speed of the coating. Alkoxy in the fluorine-containing silane coupling agent containing the photo-curable group is combined with optical fiber glass, and the photo-curable group (acrylate group) can be subjected to curing reaction with the coating, so that the interface combination of the coating and the glass is improved, the adhesive force of the coating and the glass is further improved, and the curing speed is greatly improved compared with the silane coupling agent containing no photo-curable group. In addition, after the fluorine-containing silane coupling agent containing the photocurable group is added into a coating system, colorless to faint yellow clear liquid can be obtained, the compatibility is good, and the problems that the common silane coupling agent has poor compatibility in the fluorine-containing coating system and cannot be produced are solved.

Claims (9)

1. A low refractive index optical fiber coating, comprising: the coating comprises the following components in percentage by weight: 20 to 70 weight percent of fluorine-containing oligomer, 10 to 70 weight percent of fluorine-containing active monomer diluent, 1 to 10 weight percent of photoinitiator, 0.1 to 2 weight percent of polymerization inhibitor, 0.5 to 5 weight percent of fluorine-containing adhesion promoter and 0 to 5 weight percent of auxiliary agent;
wherein the fluorine-containing oligomer is a fluorine-containing epoxy urethane acrylate oligomer, and the fluorine-containing epoxy urethane acrylate oligomer is obtained by blending fluorine-containing urethane acrylate and fluorine-containing epoxy acrylate, wherein the mass ratio of the fluorine-containing urethane acrylate to the fluorine-containing epoxy acrylate is (1) - (10);
the fluorine-containing active monomer diluent is fluorine-containing monoacrylate, fluorine-containing diacrylate and fluorine-containing polyacrylate, wherein the fluorine-containing polyacrylate accounts for 10-45% by mass, and the fluorine-containing polyacrylate is fluorine-containing tetraacrylate;
the fluorine-containing adhesion promoter is a fluorine-containing silane coupling agent containing a photocurable group.
2. The low refractive index optical fiber coating of claim 1, wherein: the preparation method of the fluorine-containing epoxy urethane acrylate oligomer comprises the following steps: (1) preparation of fluorine-containing epoxy acrylate: sequentially adding fluorine-containing epoxy resin and a polymerization inhibitor into a three-neck flask provided with a mechanical stirrer, a thermometer and a constant-pressure funnel, controlling the reaction temperature to be 100 +/-5 ℃, dropwise adding a mixture of acrylic acid and a catalyst through the constant-pressure funnel, wherein the molar ratio of epoxy groups in the fluorine-containing epoxy resin to the acrylic acid is 1 to 1.05, the dosage of the catalyst is 0.1-1% of the total mass of reactants, the dosage of the polymerization inhibitor is 0.1-1% of the total mass of the reactants, carrying out heat preservation reaction for 3-4 h after the dropwise adding is finished, measuring the acid value at intervals by sampling, and stopping the reaction when the interval acid value is not changed to obtain the fluorine-containing epoxy acrylate for later use;
(2) Sequentially adding fluorine-containing polyol, isocyanate and a catalyst into a three-neck flask provided with a mechanical stirrer and a thermometer, heating to 60-70 ℃, and reacting for 2-2.5 hours under heat preservation; and (2) adding hydroxyl (meth) acrylate and a polymerization inhibitor, continuing to react for 2 to 3 hours at 60-70 ℃, sampling, determining the content of isocyanate, after the content is zero, adding the fluorine-containing epoxy acrylate prepared in the step (1), continuing to stir for 0.5 to 1h, and cooling to room temperature to obtain the fluorine-containing epoxy urethane acrylate oligomer, wherein the dosage of the catalyst is 0.1-1% of the total mass of the reactants, and the dosage of the polymerization inhibitor is 0.1-1% of the total mass of the reactants.
3. The low refractive index optical fiber coating of claim 2, wherein: the fluorine-containing epoxy resin is 2, 2-bisphenol-based hexafluoropropane diglycidyl ether, octafluorobiphenyl diglycidyl ether and 1,3- (bis-hexafluoro) benzeneLight propyl) benzene diglycidyl ether, 1, 4-bis (hexafluoro-antelope-inner) benzene diglycidyl ether and epoxy-CF (fluorine substituted benzene diglycidyl ether) with the general structural formula 2 O-(CF 2 CF 2 O) m -(CF 2 O) n -CF 2 One or more mixtures of epoxy oligomers, wherein m ranges from 1 to 20, and n ranges from 1 to 20.
4. The low refractive index optical fiber coating of claim 2, wherein: the fluorine-containing polyol is one or a mixture of more than two of fluorine-containing polyether monohydric alcohol, fluorine-containing polyether dihydric alcohol, fluorine-containing polyester monohydric alcohol and fluorine-containing polyester dihydric alcohol.
5. The low refractive index optical fiber coating of claim 2, wherein: the isocyanate is any one or a mixture of more than two of toluene diisocyanate, 4' -diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate, diethyl trans-butadiene diisocyanate, methyl cyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and tetramethyl xylylene diisocyanate.
6. The low refractive index optical fiber coating of claim 2, wherein: the hydroxyl (meth) acrylate is one or a mixture of two or more of hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolethane di (meth) acrylate.
7. The low refractive index optical fiber coating of claim 2, wherein: the polymerization inhibitor is one of hydroquinone and p-hydroxyanisole; the catalyst is one or a mixture of more than two of dibutyl tin dilaurate, bismuth carboxylate, bismuth isooctanoate, N, N-dimethyl cyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethyl alkylene diamine, triethylamine, N, N-dimethyl benzylamine, solid amine, N-ethyl morpholine, N, N '-diethyl piperazine, triethanolamine, dimethyl amino ethanol, pyridine and N, N' -dimethyl pyridine.
8. The low refractive index optical fiber coating of claim 1, wherein: the photoinitiator is one or a mixture of more than two of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone.
9. The low refractive index optical fiber coating of claim 1, wherein: the auxiliary agent comprises a defoaming agent, a leveling agent, an antioxidant and a stabilizing agent.
CN202210485756.4A 2022-05-06 2022-05-06 Low-refractive-index optical fiber coating Active CN114773985B (en)

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