CN108977071B - Optical fiber outer layer coating with interpenetrating network polymer structure and preparation method thereof - Google Patents
Optical fiber outer layer coating with interpenetrating network polymer structure and preparation method thereof Download PDFInfo
- Publication number
- CN108977071B CN108977071B CN201810668969.4A CN201810668969A CN108977071B CN 108977071 B CN108977071 B CN 108977071B CN 201810668969 A CN201810668969 A CN 201810668969A CN 108977071 B CN108977071 B CN 108977071B
- Authority
- CN
- China
- Prior art keywords
- optical fiber
- interpenetrating network
- alicyclic epoxy
- network polymer
- fiber outer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
-
- 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
-
- 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
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/005—Dendritic macromolecules
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- 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
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
Abstract
The invention discloses an optical fiber outer layer coating with an interpenetrating network polymer structure and a preparation method thereof, wherein the optical fiber outer layer coating comprises the following components in percentage by weight: 8-25% of organic silicon modified alicyclic epoxy acrylate; 4% -30% of hyperbranched prepolymer; 4-20% of acrylate reactive diluent; 50-80% of alicyclic epoxy active diluent; 0.5-8% of free radical photoinitiator; macromolecular sulfonium salt cation photoinitiator Esacure 11871-8%; 0.3-3% of a photocuring leveling agent; 0.01-1% of photocuring defoaming agent; 0.05 to 1 percent of inhibitor Omnistab IC; 0.5 to 5 percent of macromolecular active antioxidant Chinox GM; the sum of the components meets 100 percent; and is prepared by mixing the components and preserving the heat. The coating disclosed by the invention has the characteristics of high Tg, high modulus, high strength, low curing shrinkage, no yellowing, high temperature resistance, ageing resistance, stable reliability, environmental friendliness, no toxicity and the like, and can be used for UV curing and UV-LED curing.
Description
Technical Field
The invention relates to the field of new materials, in particular to an optical fiber outer layer coating with an interpenetrating network polymer structure and a preparation method thereof.
Background
The commercial fiber is a silica glass fiber which is produced by fusion-drawing a silica glass preform. The pure silica glass optical fiber is inevitably affected by various mechanical damages and environmental factors in the use process, and the actual application requirements cannot be met at all. Therefore, when the glass optical fiber is drawn out and molded in an insulating furnace, the protective resin-optical fiber coating should be applied in as short a time as possible. Due to the large additional losses in single-layer coating, the two-layer coating process is mainly used at present. The first layer, which is in direct contact with the fiber, is typically a soft, low modulus, low glass transition temperature buffer layer that minimizes microbend losses, referred to as the inner coating of the fiber, and the second layer, which coats the surface of the inner coating, is a tough, smooth, high modulus, high glass transition temperature, hard coating that protects the fiber mechanically and environmentally, referred to as the outer coating of the fiber.
Ultraviolet (UV) curing means that ultraviolet light is used as a light source, under the action of a photoinitiator, a prepolymer with active functional groups and a functional monomer in a system are initiated to carry out cross-linking polymerization at normal temperature, so that the UV curing is rapid and solvent-free, energy is saved, environmental protection is facilitated, the curing speed is high, the production efficiency is high, and in order to meet the requirement of high-speed drawing of optical fibers, the ultraviolet curing technology is adopted in all optical fiber coatings at present. Ultraviolet (UV) curing reactions are classified into radical type and cationic type. The curing process of the optical fiber outer layer coating on the market at present is a free radical polymerization reaction type, in the ultraviolet light initiated free radical polymerization curing process of the optical fiber outer layer coating, acrylate monomer molecules which are originally acted by van der Waals force are changed into covalent bond connection, and the distance between corresponding atoms is shortened to 0.154nm from 0.3-0.5 nm, and is shortened by about half. Thus, the atoms are much more tightly arranged in the polymer than in the monomer, resulting in greater volume shrinkage during curing. The monomers employed in cationic UV-curing systems are generally epoxy compounds or vinyl ethers. Vinyl ethers cure at a slower rate and are not as widely used as epoxies. The curing mechanism of the epoxy compound is that ring-opening polymerization reaction is carried out in the presence of a cationic photoinitiator, when the epoxy compound is subjected to ring-opening polymerization, a ring on an epoxy monomer is opened, the covalent bond distance in a molecule is changed to be similar to the Van der Waals distance between molecules, volume expansion is caused, volume shrinkage caused in other curing processes can be partially counteracted, and therefore the volume shrinkage of a cationic photocuring system is small.
Interpenetrating network polymers (IPNs) are a class of polymers formed by permanently intertwining two or more polymer networks with each other, wherein at least one of the polymer networks is synthesized or cross-linked in the presence of another polymer network, which has the advantage of combining the advantages of the respective properties.
The ultraviolet light curing optical fiber outer layer coating used by common single mode optical fiber manufacturers basically has the glass transition temperature (Tg) lower than 85 ℃, and the adopted main resin (oligomer) and the adopted diluent monomer are both acrylates which are cured by ultraviolet light initiated free radical polymerization. The prepolymer is generally high in molecular weight, the shrinkage after curing is generally 2-6%, in order to meet the requirement of a coating process of high-speed wire drawing, a monofunctional and multifunctional active monomer with small molecular weight is required to be used for adjusting the viscosity, and the volume shrinkage of a common active monomer with small molecular weight is large, so that the curing volume shrinkage of the ultraviolet curing optical fiber outer layer coating is basically over 5%. The optical fiber coating generates lateral force to the optical fiber due to curing shrinkage, so that microbending loss is increased at low temperature, and the optical performance of the optical fiber is directly influenced.
A special optical fiber such as a polarization maintaining optical fiber used for an optical fiber gyroscope is different from a common communication optical fiber, the applied environment has no multiple protection after the communication optical fiber is cabled, a bare fiber is directly prepared into an optical device, the diameter of a cladding/coating of the common single-mode optical fiber is 125 mu m/250 mu m, the diameter of the cladding/coating of the polarization maintaining optical fiber is generally 80 mu m/170 mu m, 80 mu m/165 mu m, 80 mu m/155 mu m, 80 mu m/135 mu m, 80 mu m/125 mu m, 40 mu m/120 mu m, 40 mu m/100 mu m, 40 mu m/80 mu m and the like, the polarization maintaining optical fiber is developed to be thin, the thickness of the coating layer is gradually reduced, and the aim is to realize the miniaturization of the optical device. The Tg of the material is less than 85 ℃, the modulus is less than 1300MPa, the tensile strength is less than 45MPa, and the effect of the coating layer on resisting various external influences is limited, so that aiming at the special development requirement, the optical fiber outer coating with an interpenetrating network polymer (IPN) structure is designed, and the typical properties of the optical fiber outer coating are shown in Table 1. The data in Table 1 illustrate that the optical fiber outer coating of the present invention performs better than the conventional outer coating.
Although the common optical fiber outer coating does not contain a solvent, small-molecule photoinitiators are used, unpleasant and even toxic small-molecule photolysis products can be generated in the production process, some of the photolysis products can be volatilized immediately at high temperature in production, the residual products on the surface layer of the finished optical fiber can be volatilized and dissipated for a long time, all the general auxiliary agents are small molecules, and the residual products and the auxiliary agents can be gradually migrated after the optical fiber outer coating is solidified into a film, so that the material performance is influenced, and the optical fiber outer coating is not environment-friendly.
Disclosure of Invention
Aiming at the special requirements that a special optical fiber has high modulus, high strength, impact resistance and Tg (temperature Tg) far greater than 80 ℃, small curing shrinkage, bending resistance and good high and low temperature resistance, the optical fiber outer layer coating has the characteristics of high Tg, high modulus, high strength, low curing shrinkage, no yellowing, high temperature resistance, aging resistance, environmental protection and no toxicity, can be used for UV curing and UV-LED curing, can be rapidly cured by ultraviolet light initiation, is beneficial to the improvement of the performance of the coated optical fiber, and is simple and easy to operate and high in product stability.
The technical scheme of the invention is as follows:
the optical fiber outer layer coating with the interpenetrating network polymer structure comprises the following components in percentage by weight: 8-25% of organic silicon modified alicyclic epoxy acrylate; 4% -30% of hyperbranched prepolymer; 4-20% of acrylate reactive diluent; 50-80% of alicyclic epoxy active diluent; 0.5-8% of free radical photoinitiator; macromolecular sulfonium salt cationic photoinitiator Esacure 11871-8%; 0.3-3% of a photocuring leveling agent; 0.01-1% of photocuring defoaming agent; 0.05 to 1 percent of polymerization inhibitor OmnistabICs; 0.5 to 5 percent of macromolecular active antioxidant ChinoxGMB; the sum of the components meets 100 percent.
The structure of the interpenetrating network polymer is specifically an IPN structure.
In the scheme, the organic silicon modified alicyclic epoxy acrylate is a tetrafunctional prepolymer, the fast photocuring performance of the prepolymer is guaranteed by the reaction activity of tetrafunctional groups, the special alicyclic structure provides the prepolymer with high strength, good weather resistance, high temperature resistance and non-yellowing performance, and the prepolymer has good low-temperature flexibility and good impact resistance and aging resistance while having excellent high-temperature performance through organic silicon modification, so that the coated optical fiber material is guaranteed to keep stable optical performance in a high-temperature and low-temperature environment.
Specifically, the specific preparation method of the organic silicon modified alicyclic epoxy acrylate comprises the following steps:
1) dripping acrylic acid, ammonium salt catalyst N, N-dimethylbenzylammonium and polymerization inhibitor p-hydroxyanisole mixed solution into alicyclic epoxy TTA21P, and fully reacting at the temperature of 100-110 ℃ to obtain a first intermediate;
2) uniformly mixing hydroxyalkyl-terminated modified silicone oil, diisocyanate, a catalyst and a polymerization inhibitor p-hydroxyanisole, fully reacting at 40-45 ℃, adding a mixed solution of hydroxyethyl acrylate, dibutyltin dilaurate as a catalyst and p-hydroxyanisole as a polymerization inhibitor, and fully reacting at 70-75 ℃ to obtain a second intermediate;
3) and (2) fully reacting the first intermediate obtained in the step 1), the second intermediate obtained in the step 2), a catalyst dibutyltin dilaurate and a polymerization inhibitor p-hydroxyanisole at 70-75 ℃ to obtain the tetrafunctional organosilicon modified alicyclic epoxy acrylate prepolymer.
Specifically, the cycloaliphatic epoxy is TTA 21P.
Specifically, the terminal hydroxyalkyl modified silicone oil is Tech-2110, Tech-2120, Tech-2127 or Tech-2140.
Specifically, the diisocyanate is isophorone diisocyanate (IPDI) or dicyclohexylmethane diisocyanate (HMDI).
In the technical scheme, the hyperbranched prepolymer is one or a mixture of more of CN2304, CN2302, BDE1029, 6363 or DR-E522 in any proportion. These hyperbranched prepolymers differ from the conventional linear structure acrylate prepolymers in that they have a spherical molecular appearance and are less likely to form segment entanglement between molecules, and therefore have much lower viscosity than linear macromolecules of the same molecular weight. The ultrahigh functionality of the coating enables the coating on the outer layer of the optical fiber to have excellent curing speed, and can meet the increasing production speed of optical fiber drawing. And the hyperbranched prepolymer has high curing crosslinking density, can provide higher Tg, tensile strength and impact resistance of the coating on the outer layer of the optical fiber, and ensures that the optical fiber can maintain stable optical performance in a high-temperature environment for a long time.
In the technical scheme, the acrylate reactive diluent is a mixture of one or more of tricyclodecane dimethanol diacrylate (DCPDA), tricyclodecane dimethanol dimethacrylate (TCDMA) and tris (2-hydroxyethyl) isocyanurate triacrylate (THEICATA) in any proportion. These reactive diluents have low cure shrinkage, fast cure speed, high Tg (all greater than 120 ℃), excellent yellowing resistance, and excellent heat and chemical resistance.
In the technical scheme, the alicyclic epoxy reactive diluent is a mixture of one or more of TTA21P, TTA2083 and ERL4299 according to any proportion. The alicyclic epoxy reactive diluent has low viscosity, low curing shrinkage and high curing speed, and can endow the outer coating of the optical fiber with excellent yellowing resistance, weather resistance, heat resistance and ultraviolet ray and radiation resistance, so that the optical fiber can be used for a long time under a high-temperature condition.
In the above technical scheme, the radical photoinitiator is one or a mixture of more of Omnipol TX, Omnipol 910, Omnipol BL728, ECX 14-027, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L), phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (bat a), and 4-chlorobenzophenone (1046) in any proportion. The free radical photoinitiator has low odor and yellowing resistance, can be used for carrying out common UV light source initiated curing and UV-LED curing, and is more energy-saving and environment-friendly.
In the technical scheme, the macromolecular sulfonium salt cation photoinitiator is Esacure 1187. The structure is as follows:
currently available sulfonium salt cationic photoinitiators generate some unpleasant odor (diphenyl sulfide) and toxic byproduct (benzene) during curing, and iodonium salt cationic photoinitiators have low reactivity and still emit the unpleasant byproduct and toluene during curing, which is unfavorable for optical fiber production and environmental protection. And the Esacure1187 macromolecular sulfonium salt cationic photoinitiator uses thianthrene as a molecular skeleton to introduce a phenyl sulfur group into a ring structure, has the same high initiation efficiency as a common sulfonium salt cationic photoinitiator, is free from yellowing, has good compatibility with other components in a formula, simultaneously inhibits the release of toxic and unpleasant photolysis byproducts, and is completely environment-friendly and nontoxic.
In the technical scheme, the photocuring leveling agent is a mixture of one or more of BYK-UV3535, BYK-UV3576, TEG RAD 2300 and TEG RAD 2250 in any proportion. The leveling agents have good compatibility, have low to medium surface tension reducing capacity, can improve the wettability and the leveling property of a base material, have a certain defoaming effect on unstable foam, and can promote the rapid leveling of the optical fiber outer coating in the processes of rapid wire drawing coating and curing. Which contain polyacrylate functionality that can be radiation cured to crosslink with the optical fiber over-coating, thereby providing a durable effect without migration.
In the technical scheme, the light-curing defoaming agent is a mixture of one or more of TEG RAD 2500, TEG RAD 2600, TEG RAD2650 and TEG RAD 2700 according to any proportion. The defoaming agent has the characteristics of accelerating defoaming and breaking, can quickly eliminate bubbles in the coating of the outer layer of the optical fiber, and prevents the optical fiber from being scrapped due to coating film defects generated by the bubbles in the process of quick wire drawing and coating. Different from other defoaming agents, the acrylate functional group can participate in radiation crosslinking curing of the optical fiber outer layer coating system, so that the problem that the optical fiber is difficult to be coated with other materials in the subsequent use process due to the fact that the defoaming agent migrates to the surface of the coating layer is avoided, and the release of small molecular substances in the optical fiber outer layer coating system is reduced.
In the technical scheme, the polymerization inhibitor Omnistab IC is a non-yellowing polymerization inhibitor and is used for improving the storage stability of the optical fiber outer layer coating.
In the technical scheme, the macromolecular active antioxidant Chinox GM is an excellent space-hindered phenol antioxidant which does not change color and pollute, has excellent thermal stability and illumination stability, and can protect the outer coating of the optical fiber from thermal oxidation and low thermal aging. Because the acrylate functional group is contained, the acrylate functional group can participate in radiation crosslinking curing of an optical fiber outer coating system, does not migrate, can generate a lasting effect in the optical fiber outer coating, and ensures that the optical fiber has high reliability and stability even if being used in a high-temperature environment for a long time.
The preparation method of the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure comprises the following steps: weighing the raw material components according to the proportion, heating to 50-60 ℃, keeping the temperature, stirring for 2-3 hours, and finally filtering and defoaming to obtain the finished optical fiber outer layer coating.
The invention has the beneficial effects that:
firstly, the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure has high Tg, high modulus, high strength, impact resistance, bending resistance and good high and low temperature resistance, and is particularly suitable for the production and use requirements of special optical fibers with thin diameter and thin coating;
secondly, the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure can be used in a working environment higher than 120 ℃ for a long time, and is free of yellowing, ageing-resistant and stable in long-term use reliability;
thirdly, the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure has the IPN structure and small curing volume shrinkage;
fourthly, the optical fiber outer coating with the interpenetrating network polymer (IPN) structure does not contain solvent, does not have a large amount of unpleasant odor during the production and use processes, and is very environment-friendly.
Detailed Description
The application and effects of the present invention will be further described with reference to the following specific examples.
The following examples are given as particular embodiments of the present invention and to illustrate the practice and advantages thereof. It should be understood that these examples are illustrative only and are not intended to limit this specification or the appended claims in any way.
The preparation method of the organic silicon modified alicyclic epoxy acrylate is as follows:
1. synthesis of silicone-modified alicyclic epoxy acrylate SIEA 1:
252.31g of alicyclic epoxy TTA21P is heated and stirred, 144.12g of acrylic acid, 1.19g of ammonium salt catalyst N, N-dimethylbenzylammonium and 1.98g of polymerization inhibitor p-hydroxyanisole are weighed, stirred and dissolved uniformly, and when the temperature of the alicyclic epoxy TTA21P is raised to 110 ℃, the mixed solution of the acrylic acid, the ammonium salt catalyst and the polymerization inhibitor is dripped at a constant speed, and the dripping time is controlled within 1 hour. After the dropwise addition, the reaction temperature is controlled to be about 100-110 ℃, and the intermediate A1 is obtained after the reflux reaction for 4 hours.
1000g of hydroxyalkyl modified silicone oil Tech-2110 and 444.58g of isophorone diisocyanate (IPDI) are mixed uniformly, 7.22g of catalyst dibutyltin dilaurate and 1.44g of polymerization inhibitor p-hydroxyanisole are added, then the temperature is increased to 40-45 ℃, constant temperature reaction is continued for 4-6 hours, 116.12g of hydroxyethyl acrylate, 0.58g of catalyst dibutyltin dilaurate and 0.12g of polymerization inhibitor p-hydroxyanisole are added, the temperature is increased to 70-75 ℃, constant temperature reaction is continued for 4-6 hours, and an intermediate B1 is obtained.
396.43g of intermediate A1 and 1560.7g of intermediate B1 are mixed uniformly, 9.79g of catalyst dibutyltin dilaurate and 1.96g of polymerization inhibitor p-hydroxyanisole are added in the mixture, and then the mixture is heated to 70-75 ℃ to react for 6-8 hours at constant temperature, so that the organic silicon modified alicyclic epoxy acrylate SIEA1 is obtained.
2. Synthesis of silicone-modified alicyclic epoxy acrylate SIEA 2:
252.31g of alicyclic epoxy TTA21P is heated and stirred, 144.12g of acrylic acid, 1.19g of ammonium salt catalyst N, N-dimethylbenzylammonium and 1.98g of polymerization inhibitor p-hydroxyanisole are weighed, stirred and dissolved uniformly, and when the temperature of the alicyclic epoxy TTA21P is raised to 110 ℃, the mixed solution of the acrylic acid, the ammonium salt catalyst and the polymerization inhibitor is dripped at a constant speed, and the dripping time is controlled within 1 hour. After the dropwise addition, the reaction temperature is controlled to be about 100-110 ℃, and the intermediate A1 is obtained after the reflux reaction for 4 hours.
2244g of hydroxyalkyl modified silicone oil Tech-2120 and 444.58g of isophorone diisocyanate (IPDI) are mixed uniformly, 13.44g of dibutyltin dilaurate serving as a catalyst and 2.69g of p-hydroxyanisole serving as a polymerization inhibitor are added, then the temperature is increased to 40-45 ℃, constant-temperature reaction is continued for 4-6 hours, 116.12g of hydroxyethyl acrylate, 0.58g of dibutyltin dilaurate serving as a catalyst and 0.12g of p-hydroxyanisole serving as a polymerization inhibitor are added, the temperature is increased to 70-75 ℃, constant-temperature reaction is continued for 4-6 hours, and an intermediate B2 is obtained.
396.43g of intermediate A1 and 2804.7g of intermediate B2 are mixed uniformly, 16g of catalyst dibutyltin dilaurate and 3.2g of polymerization inhibitor p-hydroxyanisole in total mass are added, and then the mixture is heated to 70-75 ℃ to react for 6-8 hours at constant temperature, so that the organosilicon modified alicyclic epoxy acrylate SIEA2 is obtained.
3. Synthesis of silicone-modified alicyclic epoxy acrylate SIEA 3:
252.31g of alicyclic epoxy TTA21P is heated and stirred, 144.12g of acrylic acid, 1.19g of ammonium salt catalyst N, N-dimethylbenzylammonium and 1.98g of polymerization inhibitor p-hydroxyanisole are weighed, stirred and dissolved uniformly, and when the temperature of the alicyclic epoxy TTA21P is raised to 110 ℃, the mixed solution of the acrylic acid, the ammonium salt catalyst and the polymerization inhibitor is dripped at a constant speed, and the dripping time is controlled within 1 hour. After the dropwise addition, the reaction temperature is controlled to be about 100-110 ℃, and the intermediate A1 is obtained after the reflux reaction for 4 hours.
2200g of hydroxyalkyl modified silicone oil Tech-2127 and 524.7g of dicyclohexylmethane diisocyanate (HMDI) are mixed uniformly, 13.62g of catalyst dibutyltin dilaurate and 2.72g of polymerization inhibitor p-hydroxyanisole are added, then the temperature is raised to 40-45 ℃ for continuous constant temperature reaction for 4-6 hours, 116.12g of hydroxyethyl acrylate, 0.58g of catalyst dibutyltin dilaurate and 0.12g of polymerization inhibitor p-hydroxyanisole are added, the temperature is raised to 70-75 ℃ for continuous constant temperature reaction for 4-6 hours, and the intermediate B3 is obtained.
396.43g of intermediate A1 and 2840.82g of intermediate B3 are uniformly mixed, 16.19g of catalyst dibutyltin dilaurate and 3.24g of polymerization inhibitor p-hydroxyanisole are added in total mass, and then the mixture is heated to 70-75 ℃ to react for 6-8 hours at constant temperature, so that the organic silicon modified alicyclic epoxy acrylate SIEA3 is obtained.
4. Synthesis of silicone-modified alicyclic epoxy acrylate SIEA 4:
252.31g of alicyclic epoxy TTA21P is heated and stirred, 144.12g of acrylic acid, 1.19g of ammonium salt catalyst N, N-dimethylbenzylammonium and 1.98g of polymerization inhibitor p-hydroxyanisole are weighed, stirred and dissolved uniformly, and when the temperature of the alicyclic epoxy TTA21P is raised to 110 ℃, the mixed solution of the acrylic acid, the ammonium salt catalyst and the polymerization inhibitor is dripped at a constant speed, and the dripping time is controlled within 1 hour. After the dropwise addition, the reaction temperature is controlled to be about 100-110 ℃, and the intermediate A1 is obtained after the reflux reaction for 4 hours.
5000g of hydroxyalkyl modified silicone oil Tech-2140 and 524.7g of dicyclohexylmethane diisocyanate (HMDI) are mixed uniformly, 27.62g of dibutyltin dilaurate serving as a catalyst and 5.52g of p-hydroxyanisole serving as a polymerization inhibitor are added, then the temperature is increased to 40-45 ℃, constant-temperature reaction is continued for 4-6 hours, 116.12g of hydroxyethyl acrylate, 0.58g of dibutyltin dilaurate serving as a catalyst and 0.12g of p-hydroxyanisole serving as a polymerization inhibitor are added, and the temperature is increased to 70-75 ℃ to continue constant-temperature reaction for 4-6 hours, so that an intermediate B4 is obtained.
396.43g of intermediate A1 and 5640.82g of intermediate B4 are mixed uniformly, catalyst dibutyltin dilaurate with the total mass of 30.19g and polymerization inhibitor p-hydroxyanisole with the total mass of 6.04g are added, and then the mixture is heated to 70-75 ℃ to react for 6-8 hours at constant temperature, so that the organic silicon modified alicyclic epoxy acrylate SIEA4 is obtained.
Example 1
An optical fiber outer layer coating with an interpenetrating network polymer (IPN) structure comprises the following components in percentage by weight:
11% of organic silicon modified alicyclic epoxy acrylate (SIEA1), 23049% of hyperbranched prepolymer CN, 14% of acrylate reactive diluent, 58% of alicyclic epoxy reactive diluent, 1.7% of free radical photoinitiator, 0.4% of macromolecular sulfonium salt cationic photoinitiator Esacure 11872.32% of photocuring leveling agent, 0.02% of photocuring defoaming agent, 0.07% of polymerization inhibitor Omnistab IC, 3.49% of macromolecular active antioxidant Chinox GM, and the sum of the components is 100%.
The acrylate reactive diluent comprises the following components in percentage by weight: 33% tricyclodecane dimethanol diacrylate (DCPDA), 67% tris (2-hydroxyethyl) isocyanurate triacrylate (THEICATA); the alicyclic epoxy active diluent comprises the following components in percentage by weight: 72% TTA21P, 28% ERL 4299; the free radical photoinitiator comprises the following components in percentage by weight: 30% of photoinitiator Omnipol BL728, 40% of photoinitiator ECX 14-027, 30% of photoinitiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L); the photocuring leveling agent comprises the following components in percentage by weight: 50% BYK-UV3576, 50% TEG RAD 2250; the photocuring defoaming agent comprises the following components in percentage by weight: 50% of a leveling agent TEG RAD 2500 and 50% of a leveling agent TEGRAD 2650.
The preparation method of the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure comprises the following steps: weighing the raw material components according to the proportion; after all the raw material components are initially mixed uniformly, stirring the mixture for 2.5 hours by using a dispersion machine at the rotating speed of 1000 revolutions per minute at about 60 ℃; after the raw materials are completely and uniformly mixed, filtering by using a filter with the diameter less than or equal to 0.45 mu m to obtain the optical fiber outer layer coating; and then placing the optical fiber outer layer coating in a 40 ℃ oven to be heated and defoamed for 12 hours in a dark place to obtain the finished optical fiber outer layer coating.
The performance of the optical fiber outer coating prepared in this example was tested, and the results are shown in Table 2.
TABLE 1 technical indices of example 1
As shown in Table 1, the coating material for the outer layer of the optical fiber having the interpenetrating network polymer (IPN) structure according to example 1 had an elongation at break (25 ℃ C.) of 10%, a specific modulus (25 ℃ C., 2.5% elongation) of 2100MPa, a tensile strength (25 ℃ C.) of 72MPa, a Tg of 147 ℃ and a curing shrinkage of 2%.
Example 2
An optical fiber outer layer coating with an interpenetrating network polymer (IPN) structure comprises the following components in percentage by weight:
10% of organic silicon modified alicyclic epoxy acrylate (SIEA4), 15% of hyperbranched prepolymer, 17% of acrylate reactive diluent, 51% of alicyclic epoxy reactive diluent, 1.2% of free radical photoinitiator, 11872.75% of macromolecular sulfonium salt cationic photoinitiator, 0.3% of photocuring leveling agent, 0.02% of photocuring defoaming agent, 0.05% of polymerization inhibitor OmnistabIC, 2.68% of macromolecular active antioxidant Chinox GM, and the sum of the components is 100%.
The hyperbranched prepolymer comprises the following components in percentage by weight: 62% CN2302, 38% BDE 1029; the acrylate reactive diluent comprises the following components in percentage by weight: 44% tricyclodecane dimethanol dimethacrylate (TCDMA), 56% tris (2-hydroxyethyl) isocyanurate triacrylate (THEICATA); the alicyclic epoxy active diluent comprises the following components in percentage by weight: 72% TTA21P, 28% ERL 4299; the free radical photoinitiator comprises the following components in percentage by weight: 45% of photoinitiator Omnipol BL728, 20% of photoinitiator Omnipol 910, 35% of photoinitiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (BATA); the photocuring leveling agent comprises the following components in percentage by weight: 55% of BYK-UV3535, 45% of TEG RAD 2250; the photocuring defoaming agent comprises the following components in percentage by weight: 50% of a leveling agent TEG RAD 2500 and 50% of a leveling agent TEGRAD 2700.
The preparation method of the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure comprises the following steps: weighing the raw material components according to the proportion; after all the raw material components are initially mixed uniformly, stirring the mixture for 2.5 hours by using a dispersion machine at the rotating speed of 1000 revolutions per minute at about 60 ℃; after the raw materials are completely and uniformly mixed, filtering by using a filter with the diameter less than or equal to 0.45 mu m to obtain the optical fiber outer layer coating; and then placing the optical fiber outer layer coating in a 40 ℃ oven to be heated and defoamed for 12 hours in a dark place to obtain the finished optical fiber outer layer coating.
The performance of the optical fiber outer coating prepared in this example was tested, and the results are shown in Table 3.
TABLE 2 technical indices of example 2
As shown in Table 2, the coating for the outer layer of the optical fiber having the interpenetrating network polymer (IPN) structure of example 2 had an elongation at break (25 ℃ C.) of 25%, a specific modulus (25 ℃ C., 2.5% elongation) of 1146MPa, a tensile strength (25 ℃ C.) of 62MPa, a Tg of 133 ℃ C., and a curing shrinkage of 1.8%.
Example 3
An optical fiber outer layer coating with an interpenetrating network polymer (IPN) structure comprises the following components in percentage by weight:
11% of organic silicon modified alicyclic epoxy acrylate (SIEA2), 8% of hyperbranched prepolymer, 18% of acrylate reactive diluent, 55% of alicyclic epoxy reactive diluent, 1.3% of free radical photoinitiator, 11872.75% of macromolecular sulfonium salt cationic photoinitiator, 0.45% of photocuring leveling agent, 0.04% of photocuring defoaming agent, 0.05% of polymerization inhibitor Omnistab IC, 3.41% of macromolecular reactive antioxidant Chinox GM, and the sum of the components is 100%.
The hyperbranched prepolymer comprises the following components in percentage by weight: 57% BDE1029, 43% DR-E522; the acrylate reactive diluent comprises the following components in percentage by weight: 27% tricyclodecane dimethanol dimethacrylate (TCDMA), 73% tricyclodecane dimethanol diacrylate (DCPDA); the alicyclic epoxy active diluent comprises the following components in percentage by weight: 56% TTA21P, 44% ERL 4299; the free radical photoinitiator comprises the following components in percentage by weight: 31% photoinitiator Omnipol BL728, 47% photoinitiator Omnipol TX, 22% photoinitiator 4-chlorobenzophenone (1046); the photocuring leveling agent comprises the following components in percentage by weight: 20% TEG RAD 2300, 80% TEG RAD 2250; the photocuring defoaming agent comprises the following components in percentage by weight: 40% of a leveling agent TEG RAD 2500, and 60% of a leveling agent TEG RAD 2600.
The preparation method of the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure comprises the following steps: weighing the raw material components according to the proportion; after all the raw material components are initially mixed uniformly, stirring the mixture for 2.5 hours by using a dispersion machine at the rotating speed of 1000 revolutions per minute at about 60 ℃; after the raw materials are completely and uniformly mixed, filtering by using a filter with the diameter less than or equal to 0.45 mu m to obtain the optical fiber outer layer coating; and then placing the optical fiber outer layer coating in a 40 ℃ oven to be heated and defoamed for 12 hours in a dark place to obtain the finished optical fiber outer layer coating.
The performance of the optical fiber outer coating prepared in this example was tested, and the results are shown in Table 4.
TABLE 3 technical indices of example 3
As shown in Table 3, the coating material for the outer layer of the optical fiber having the interpenetrating network polymer (IPN) structure of example 3 had an elongation at break (25 ℃ C.) of 11%, a specific modulus (25 ℃ C., 2.5% elongation) of 1814MPa, a tensile strength (25 ℃ C.) of 68MPa, a Tg of 143 ℃ and a curing shrinkage of 1.743%.
Example 4
An optical fiber outer layer coating with an interpenetrating network polymer (IPN) structure comprises the following components in percentage by weight:
12% of organic silicon modified alicyclic epoxy acrylate (SIEA3), 14% of hyperbranched prepolymer, 11% of acrylate reactive diluent, 53% of alicyclic epoxy reactive diluent, 1.85% of free radical photoinitiator, 11873.18% of macromolecular sulfonium salt cationic photoinitiator, 0.4% of photocuring leveling agent, 0.05% of photocuring defoaming agent, 0.07% of polymerization inhibitor Omnistab IC, 4.45% of macromolecular reactive antioxidant Chinox GM, and the sum of the components is 100%.
The hyperbranched prepolymer comprises the following components in percentage by weight: 90% CN2304, 10% 6363; the acrylate reactive diluent comprises the following components in percentage by weight: 30% tricyclodecane dimethanol dimethacrylate (TCDMA), 48% tricyclodecane dimethanol diacrylate (DCPDA), 22% tris (2-hydroxyethyl) isocyanurate triacrylate (THEICATA); the alicyclic epoxy active diluent comprises the following components in percentage by weight: 40% TTA21P, 60% ERL 4299; the free radical photoinitiator comprises the following components in percentage by weight: 47% of photoinitiator Omnipol 910, 53% of photoinitiator Omnipol TX; the photocuring leveling agent comprises the following components in percentage by weight: 30% TEG RAD 2300, 70% TEG RAD 2250; the photocuring defoaming agent comprises the following components in percentage by weight: 50% of a leveling agent TEG RAD 2500 and 50% of a leveling agent TEG RAD 2650.
The preparation method of the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure comprises the following steps: weighing the raw material components according to the proportion; after all the raw material components are initially mixed uniformly, stirring the mixture for 2.5 hours by using a dispersion machine at the rotating speed of 1000 revolutions per minute at about 60 ℃; after the raw materials are completely and uniformly mixed, filtering by using a filter with the diameter less than or equal to 0.45 mu m to obtain the optical fiber outer layer coating; and then placing the optical fiber outer layer coating in a 40 ℃ oven to be heated and defoamed for 12 hours in a dark place to obtain the finished optical fiber outer layer coating.
The performance of the optical fiber outer coating prepared in this example was tested, and the results are shown in Table 5.
Table 4 technical indices of example 4
As shown in Table 4, the coating for the outer layer of the optical fiber having the interpenetrating network polymer (IPN) structure of example 4 had an elongation at break (25 ℃ C.) of 15%, a specific modulus (25 ℃ C., 2.5% elongation) of 1600MPa, a tensile strength (25 ℃ C.) of 65MPa, a Tg of 141 ℃ and a curing shrinkage of 1.89%.
According to the results of tables 1 to 4, the results are shown in Table 5, compared with the conventional optical fiber coating on the market:
TABLE 5 comparison of basic Properties of conventional optical fiber outer coating with those of the present invention
As can be seen from Table 5, the optical fiber outer coating of the present invention has the characteristics of high modulus, high strength, high Tg and low curing shrinkage compared with the common optical fiber outer coating.
Testing the performance of the special polarization maintaining optical fiber drawn by the optical fiber outer layer coating:
drawing conditions: the cladding/coating diameter was 80 μm/135 μm; the drawing speed was 2800 m/min.
According to the test method provided in the national standard GB/T15972-2008 "optical fiber test method specification", the special polarization maintaining optical fibers drawn from the optical fiber outer layer coating of the interpenetrating network polymer (IPN) structure described in examples 1-4 are correspondingly ordered into 1-4, and the results of the tests on the peeling force, attenuation, and the like are shown in table 6.
TABLE 6
As shown in table 6, the thin-diameter special optical fiber prepared by using the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure described in examples 1 to 4 is environment-friendly, non-toxic, free from extraneous odor, small in macrobend loss, small in attenuation change before and after aging, and stable in reliability after long-term use, and the stripping force meets the labeling requirements.
In conclusion, the optical fiber outer layer coating with the interpenetrating network polymer (IPN) structure has the advantages of high Tg, high modulus, high strength, low curing shrinkage, no yellowing, high temperature resistance, aging resistance, environmental friendliness and no toxicity, no organic matter volatilization and no yellowing in the production and use processes, can be used for UV curing and UV-LED curing, and is particularly suitable for preparation and production of special optical fibers with thin and thin coatings.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The optical fiber outer layer coating with the interpenetrating network polymer structure is characterized by comprising the following components in percentage by weight:
8-25% of organic silicon modified alicyclic epoxy acrylate;
4% -30% of hyperbranched prepolymer;
4-20% of acrylate reactive diluent;
50-80% of alicyclic epoxy active diluent;
0.5-8% of free radical photoinitiator;
macromolecular sulfonium salt cation photoinitiator Esacure 11871-8%;
0.3-3% of a photocuring leveling agent;
0.01-1% of photocuring defoaming agent;
0.05 to 1 percent of inhibitor Omnistab IC;
0.5 to 5 percent of macromolecular active antioxidant Chinox GM;
the sum of the components meets 100 percent;
the organic silicon modified alicyclic epoxy acrylate is a tetrafunctional prepolymer, and is prepared by the following steps:
1) dripping acrylic acid, ammonium salt catalyst N, N-dimethylbenzylammonium and polymerization inhibitor p-hydroxyanisole mixed solution into alicyclic epoxy TTA21P, and fully reacting at the temperature of 100-110 ℃ to obtain a first intermediate;
2) uniformly mixing hydroxyalkyl-terminated modified silicone oil, diisocyanate, a catalyst and a polymerization inhibitor p-hydroxyanisole, fully reacting at 40-45 ℃, adding a mixed solution of hydroxyethyl acrylate, dibutyltin dilaurate as a catalyst and p-hydroxyanisole as a polymerization inhibitor, and fully reacting at 70-75 ℃ to obtain a second intermediate;
3) and (2) fully reacting the first intermediate obtained in the step 1), the second intermediate obtained in the step 2), a catalyst dibutyltin dilaurate and a polymerization inhibitor p-hydroxyanisole at 70-75 ℃ to obtain the organic silicon modified alicyclic epoxy acrylate.
2. The optical fiber outer coating material with the interpenetrating network polymer structure of claim 1, wherein the hyperbranched prepolymer is one or more of CN2304, CN2302, BDE1029, 6363 or DR-E522.
3. The optical fiber outer coating material with an interpenetrating network polymer structure as claimed in claim 1, wherein the acrylate reactive diluent is one or more of tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate or tris (2-hydroxyethyl) isocyanurate triacrylate.
4. The optical fiber outer coating material with an interpenetrating network polymer structure of claim 1, wherein the alicyclic epoxy reactive diluent is one or more of TTA21P, TTA2083 and ERL 4299.
5. The optical fiber outer coating material with an interpenetrating network polymer structure as claimed in claim 1, wherein the radical photoinitiator is one or more of Omnipol TX, Omnipol 910, Omnipol BL728, ECX 14-027, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, and 4-chlorobenzophenone.
6. The optical fiber outer coating with the interpenetrating network polymer structure as claimed in claim 1, wherein the light curing leveling agent is one or more of BYK-UV3535, BYK-UV3576, TEG RAD 2300 and TEG RAD 2250.
7. The optical fiber outer coating with the interpenetrating network polymer structure of claim 1, wherein the light-cured defoaming agent is one or more of TEG RAD 2500, TEG RAD 2600, TEG RAD2650 and TEG RAD 2700.
8. The method for preparing the outer coating of the optical fiber with the interpenetrating network polymer structure of any one of claims 1 to 7, wherein the outer coating of the optical fiber with the interpenetrating network polymer structure is obtained by mixing all the components, heating to 50-60 ℃, stirring for 2-3 hours under heat preservation, filtering and defoaming the mixture obtained under heat preservation.
9. The method for preparing the optical fiber outer coating with the interpenetrating network polymer structure according to claim 8, wherein the silicone modified alicyclic epoxy acrylate is prepared by the following steps:
1) dripping acrylic acid, ammonium salt catalyst N, N-dimethylbenzylammonium and polymerization inhibitor p-hydroxyanisole mixed solution into alicyclic epoxy TTA21P, and fully reacting at the temperature of 100-110 ℃ to obtain a first intermediate;
2) uniformly mixing hydroxyalkyl-terminated modified silicone oil, diisocyanate, a catalyst and a polymerization inhibitor p-hydroxyanisole, fully reacting at 40-45 ℃, adding a mixed solution of hydroxyethyl acrylate, dibutyltin dilaurate as a catalyst and p-hydroxyanisole as a polymerization inhibitor, and fully reacting at 70-75 ℃ to obtain a second intermediate;
3) and (2) fully reacting the first intermediate obtained in the step 1), the second intermediate obtained in the step 2), a catalyst dibutyltin dilaurate and a polymerization inhibitor p-hydroxyanisole at 70-75 ℃ to obtain the organic silicon modified alicyclic epoxy acrylate.
10. The method for preparing the optical fiber outer coating with the interpenetrating network polymer structure according to claim 9, wherein the terminal hydroxyalkyl modified silicone oil is one or more of Tech-2110, Tech-2120, Tech-2127 or Tech-2140; the diisocyanate is one or two of isophorone diisocyanate or dicyclohexylmethane diisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810668969.4A CN108977071B (en) | 2018-06-26 | 2018-06-26 | Optical fiber outer layer coating with interpenetrating network polymer structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810668969.4A CN108977071B (en) | 2018-06-26 | 2018-06-26 | Optical fiber outer layer coating with interpenetrating network polymer structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108977071A CN108977071A (en) | 2018-12-11 |
| CN108977071B true CN108977071B (en) | 2020-10-16 |
Family
ID=64538256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810668969.4A Active CN108977071B (en) | 2018-06-26 | 2018-06-26 | Optical fiber outer layer coating with interpenetrating network polymer structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108977071B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114280720B (en) * | 2021-12-28 | 2023-03-10 | 长飞光纤光缆股份有限公司 | Optical fiber and optical signal sensing system |
| CN114924346B (en) * | 2022-05-31 | 2024-01-05 | 长飞光纤光缆股份有限公司 | Polarization-maintaining three-layer coated optical fiber, coating method, optical fiber ring preparation method and application |
| WO2024135280A1 (en) * | 2022-12-21 | 2024-06-27 | 住友電気工業株式会社 | Resin composition for color-coating of optical fibers, optical fiber, and optical fiber ribbon |
| US20240343642A1 (en) * | 2023-07-18 | 2024-10-17 | Sumitomo Electric Industries, Ltd. | Resin composition for colored coating on optical fiber, optical fiber, and optical fiber ribbon |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2794766B1 (en) * | 1999-06-11 | 2001-08-17 | Rhodia Chimie Sa | PROCESS FOR REALIZING AN ANTI-STICK AND WATERPROOF COATING APPLIED TO A CYLINDER HEAD GASKET, USING A SILICONE MATERIAL |
| CN101300527B (en) * | 2005-10-27 | 2011-11-23 | 亨斯迈先进材料（瑞士）有限公司 | Antimony-free photocurable resin composition and three dimensional article |
| US20100119835A1 (en) * | 2007-03-14 | 2010-05-13 | Huntsman International Llc | Photocurable compositions for preparing abs-like articles |
| CN103045050B (en) * | 2013-01-17 | 2016-09-14 | 浙江佑谦特种材料有限公司 | A kind of antirusting paint for metallic conduit |
| CN103613987B (en) * | 2013-11-04 | 2016-02-24 | 中钞油墨有限公司 | Ultraviolet drying bed photoluminescence silk-screen ink composition |
| CN107936746B (en) * | 2017-11-28 | 2020-08-07 | 中科院广州化学有限公司南雄材料生产基地 | An organosilicon modified cationic light-curing alicyclic epoxy resin coating and its application |
-
2018
- 2018-06-26 CN CN201810668969.4A patent/CN108977071B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108977071A (en) | 2018-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108977071B (en) | Optical fiber outer layer coating with interpenetrating network polymer structure and preparation method thereof | |
| JP3784068B2 (en) | Radiation curable optical fiber coating composition | |
| CN104470999B (en) | Primary optical fiber coating composition containing non-radiation curable component | |
| KR100454809B1 (en) | A solvent-free, radiation-curable, optical glass fiber coating composition and solvent-free method for making a solvent-free, radiation-curable, optical glass fiber coating composition | |
| US4992524A (en) | Composition for optical fiber coating comprising a polyether diol, a polyisocyanate, and a methacrylate | |
| CN103937437B (en) | Photocurable polysiloxane urethane (meth) acrylate composition, adhesive, and cured product | |
| EP1948697A1 (en) | Non-reactive additives for fiber coatings | |
| WO2007040946A2 (en) | Fast curing primary optical fiber coatings | |
| WO2004031091A1 (en) | Optical fiber with cured polymeric coating | |
| JP4268406B2 (en) | Coated optical fiber | |
| JP3288869B2 (en) | Liquid curable resin composition | |
| KR910008558B1 (en) | Light curing composition | |
| CN103113554B (en) | Ultraviolet-curable extinction resin and preparation method thereof | |
| JP2014118319A (en) | Resin composition for coating optical fiber, optical fiber strand and method for manufacturing optical fiber strand | |
| RU2320590C2 (en) | Optical fiber with hardened polymer coat | |
| JPS63275619A (en) | Composition for coating optical fiber | |
| EP0970978B1 (en) | Radiation-curable liquid resin composition suitable for coating optical fibers and optical fiber coated therewith | |
| KR20140025625A (en) | Uv curable urethane-bonded link polysiloxane resin with vinyl or acryl polysiloxane end group and method of manufacturing | |
| JP4869548B2 (en) | Optical fiber coating resin composition, optical fiber and optical fiber unit using the same | |
| CN107418423A (en) | It is a kind of to be used to protect the UV LED of telecommunication optical fiber coating material solidified | |
| EP1397408B1 (en) | Colored, radiation-curable compositions | |
| CN114555736A (en) | Resin composition, method for producing resin composition, optical fiber, and method for producing optical fiber | |
| CN115836239A (en) | Resin composition, optical fiber, and method for producing optical fiber | |
| CN108192071B (en) | Light-cured resin and liquid light-cured composition | |
| JP4038713B2 (en) | Optical fiber coating resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |