CN113355017B - Low-refractive-index optical fiber coating resin with high glass transition temperature - Google Patents

Low-refractive-index optical fiber coating resin with high glass transition temperature Download PDF

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CN113355017B
CN113355017B CN202110491754.1A CN202110491754A CN113355017B CN 113355017 B CN113355017 B CN 113355017B CN 202110491754 A CN202110491754 A CN 202110491754A CN 113355017 B CN113355017 B CN 113355017B
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prepolymer
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transition temperature
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崔丽云
余晓梦
黄星
万欢
桂振东
皮亚斌
高旭
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Wuhan Changyingxin Technology Co ltd
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Abstract

The optical fiber coating resin with high glass transition temperature and low refractive index comprises, by weight, 10-60% of a prepolymer A, 10-60% of a prepolymer B, 1-10% of an adhesion reinforcing agent C, 0.5-5% of a photoinitiator, 0-5% of a monofunctional reactive diluent, 5-30% of a multifunctional reactive diluent, and 0.1-1% of a fluorine-containing silane coupling agent, wherein the sum of the components is 100%. The optical fiber with low refractive index is coated with resin, has strong adhesive force, is not easy to break when being bent, has high glass transition temperature, and can improve the working temperature of special optical fiber.

Description

Low-refractive-index optical fiber coating resin with high glass transition temperature
Technical Field
The invention belongs to the field of optical fibers and optical fiber coatings, and particularly relates to a low-refractive-index optical fiber coating resin with a high glass transition temperature.
Background
The optical fiber coating resin is an indispensable key protective material in optical fiber production and application, and provides strength protection, water resistance, stress buffering and the like for the optical fiber, so that excellent mechanical and optical properties of the optical fiber are maintained. The most common of the optical fibers for communications is the ultraviolet UV curable optical fiber coating. The common optical fiber coating generally used for silica-based optical fiber materials is divided into an inner layer coating and an outer layer coating, the refractive index of the inner layer coating is larger than 1.48, the refractive index of the outer layer coating is larger than 1.50, after a glass optical rod is subjected to high-temperature melting and drawing and passes through a cooling system, microcracks on the surface of glass are not influenced by moisture in the air, and the optical fiber is prepared by quickly coating and solidifying the inner layer resin and the outer layer resin.
The low-refractive index optical fiber coating is a special optical fiber inner layer coating, is generally designed into organic fluorine or organic silicon ultraviolet curing acrylic resin materials, and is characterized by having a low refractive index, generally between 1.35 and 1.42. The cured film has low refractive index, can increase the numerical aperture of the optical fiber, effectively improves the long-distance transmission efficiency of optical energy and reduces optical loss on the premise of ensuring good mechanical performance. The low refractive index of the material is utilized to form the optical waveguide with the characteristic of high NA value together with the silicon-based glass material.
The refractive index of the low-refractive-index optical fiber coating resin which is common at present is between 1.36 and 1.41, and the glass transition temperature of the low-refractive-index optical fiber coating resin prepared by the prior art generally decreases along with the decrease of the refractive index, for example, the glass transition temperature of the low-refractive-index coating resin of 1.36 grade is already less than 25 ℃. If the glass transition temperature of the low-refractive-index coating is within the working temperature range of the optical fiber, the optical performance difference between the temperature region above the glass transition temperature and the temperature region below the glass transition temperature is huge, and the full-temperature performance of the prepared optical fiber is seriously influenced, so how to improve the glass transition temperature of the low-refractive-index coating resin becomes the key for the development of special optical fibers.
Disclosure of Invention
The invention aims to solve the technical problem of providing the low-refractive-index optical fiber coating resin with high glass transition temperature, which is low and adjustable in refractive index (1.36-1.41), high in glass transition temperature (60-120 ℃), strong in adhesive force, not easy to break when the optical fiber is bent and good in reliability, aiming at the defects in the prior art.
The technical scheme adopted by the invention for solving the problems is as follows:
the coating resin for the optical fiber with the high glass transition temperature and the low refractive index comprises the following components in percentage by weight: 10-60% of prepolymer A, 10-60% of prepolymer B, 1-10% of adhesion enhancer C, 0.5-5% of photoinitiator, 0-5% of monofunctional reactive diluent, 5-30% of multifunctional reactive diluent and 0.1-1% of fluorine-containing silane coupling agent, wherein the sum of all the components is 100%.
According to the scheme, the structural formula of the prepolymer A is shown as formula A, and R is shown as formula A1Is composed of
Figure BDA0003052603230000021
Figure BDA0003052603230000022
R2is-CH3or-H, R3is-CF3or-F, a is 3-8, PMZ has the structural formula
Figure BDA0003052603230000023
Wherein X has a structural formula
Figure BDA0003052603230000024
Figure BDA0003052603230000025
b＝2-20，c＝6-18，d＝0-2，e＝2-18，y＝1-20，R4＝-CH3or-H.
Figure BDA0003052603230000026
According to the scheme, the synthesis method of the prepolymer A comprises the following steps:
1) adding perfluorinated diacid and fluorine-containing diol into a reactor with stirring according to a molar ratio (y: y +1) (y is 1-20), adding a catalyst alpha, heating to 120 ℃ and 140 ℃, keeping the temperature for reaction until all solids become liquid, starting a vacuum pump, continuously keeping the temperature, vacuumizing and continuously reacting for 6-24 hours, keeping the relative vacuum degree between-0.09 MPa and-0.1 MPa, stopping the reaction when the acid value of materials in the reactor is less than 0.5(mgKOH/g), and discharging to obtain the fluorinated polyester diol; wherein, the adding amount of the catalyst alpha accounts for 0.03 to 1 percent of the total mass of the substances of the whole reaction system in the step;
2) according to the molar ratio of 1:2 of fluorinated polyester diol to diisocyanate, adding the fluorinated polyester diol and diisocyanate into a reactor with a stirrer to be uniformly mixed, then adding a catalyst beta and a polymerization inhibitor, and reacting the obtained mixed system at the temperature of 30-60 ℃ for 3-6 hours to obtain an intermediate of the terminal isocyanate; wherein, the adding amount of the catalyst beta accounts for 0.03-1% of the total mass of the substances of the whole reaction system in the step, and the adding amount of the polymerization inhibitor accounts for 0.01-1% of the total mass of the substances of the whole reaction system in the step;
3) according to the molar ratio of the fluorinated acrylate containing hydroxyl to the fluorinated polyester diol of 2:1, adding fluorinated acrylate containing hydroxyl into the intermediate of the terminal isocyanate obtained in the step 2), and reacting at the temperature of 60-80 ℃ for 3-6 hours to obtain prepolymer A. The scheme for the synthesis of the prepolymer is shown in FIG. 1.
In the method for synthesizing the prepolymer A, the fluorinated polyester diol is obtained by performing polycondensation reaction on perfluorinated diacid and fluorine-containing diol, and the number average molecular weight of the fluorinated polyester diol is between 600-4000.
Further, in the synthesis method of the prepolymer A, the structural formula of the fluorine-containing diol is shown as
Figure BDA0003052603230000031
Wherein c is 6-18; d is 0-2; e-2-18; r4＝-CH3or-H.
Further, in the synthesis method of the prepolymer A, the diisocyanate is one or a mixture of two of Hydrogenated Xylylene Diisocyanate (HXDI), isophorone diisocyanate (IPDI) and the like according to a proportion.
In the method for synthesizing prepolymer A, the catalyst alpha is preferably p-toluenesulfonic acid.
According to the scheme, the structural formula of the prepolymer B is shown as a formula B, the prepolymer belongs to a multifunctional prepolymer, the glass transition temperature is high, and 4 parts of the whole molecule are of a high-fluoro structure and have a very low refractive index; wherein b is 2-20, n is 3-18, and R is-CH3or-H.
Figure BDA0003052603230000032
According to the scheme, the synthesis method of the prepolymer B comprises the following steps:
1) adding glycidyl (meth) acrylate and perfluorodiacid into a reactor with stirring according to the molar ratio of 2:1, uniformly mixing, then adding a catalyst gamma and a polymerization inhibitor, and reacting at the temperature of 80-110 ℃ for 2-8 hours to obtain an intermediate bifunctional fluorine-containing epoxy acrylate; wherein, the catalyst gamma accounts for 0.03 to 1 percent of the total mass of the substances in the step, and the polymerization inhibitor accounts for 0.01 to 1 percent of the total mass of the substances in the whole reaction system;
2) adding Hexamethylene Diisocyanate (HDI) and a catalyst beta into the intermediate bifunctional fluorine-containing epoxy acrylate, and reacting for 2-4 hours at 70-90 ℃ to obtain an intermediate urethane modified epoxy acrylate; wherein the catalyst beta accounts for 0.03-1% of the total mass of the substances in the first step and the second step, and the molar ratio of HDI to the perfluorinated diacid in the first step is 1: 2;
3) adding potassium carbonate into the intermediate urethane modified epoxy acrylate, uniformly stirring, cooling to 40-60 ℃, slowly adding perfluoroalkyl acyl chloride, reacting for 2-4 hours at 40-60 ℃, and filtering to remove solid particles to obtain a prepolymer B; wherein the molar ratio of the perfluoroalkyl acyl chloride to the perfluorinated diacid is 1:1, and the molar ratio of the perfluoroalkyl acyl chloride to the potassium carbonate is 1: 1-1: 2. The synthesis scheme of prepolymer B is shown in FIG. 2.
In the method for synthesizing prepolymer B, the catalyst gamma is preferably benzyltriethylammonium bromide or the like.
Further, in the synthesis method of the prepolymer A and the prepolymer B, the structural formula of the perfluorinated diacid is shown in the specification
Figure BDA0003052603230000041
Wherein b is 2-20.
Further, in the synthesis method of the prepolymer B, the structural formula of the perfluoroalkyl acyl chloride is shown as
Figure BDA0003052603230000042
Wherein n is 3-18. Suitable examples of the perfluoroalkyl acid chloride include, but are not limited to, one or more of perfluorohexanoyl chloride, perfluorooctanoyl chloride, perfluoroundecanoyl chloride, tridecafluoroheptanoyl chloride, heptadecafluorononanoyl chloride, and mixtures thereof in any proportion.
According to the scheme, the structural formula of the adhesion reinforcing agent C is shown as a formula C, the adhesion reinforcing agent C is prepared by reacting hydroxyl-containing fluorinated acrylate with a silane coupling agent containing an isocyanate bond, and the adhesion reinforcing agent C structurally comprises curable double bonds and has the advantages ofThe elastomeric urethane linkages and the low refractive high fluoroalkyl groups allow the adhesion enhancer to have good compatibility with other high fluorine containing prepolymers of the invention. The adhesive force reinforcing agent has good adhesive force on base materials such as glass, silicon dioxide, ceramics, photocuring coatings and the like, and has low refractive index and little influence on the refractive index of final optical fiber coating resin. Wherein f is 1-4; r5＝-OCH3or-OCH2CH3；R6＝-OCH3or-OCH2CH3or-CH3. The synthetic scheme for adhesion enhancer C is shown in fig. 3.
Figure BDA0003052603230000043
According to the scheme, the synthesis method of the adhesion reinforcing agent C comprises the following specific steps:
adding the hydroxyl-containing fluorinated acrylate and the silane coupling agent containing the isocyanate bond into a reactor with a stirrer according to the molar ratio of 1: 1-1.1: 1, uniformly stirring, adding a catalyst beta and a polymerization inhibitor, and reacting for 2-8 hours at 60-90 ℃ to obtain the adhesion force enhancer C. Wherein, the adding amount of the catalyst beta accounts for 0.03-1% of the total mass of the substances of the whole reaction system, and the polymerization inhibitor accounts for 0.01-1% of the total mass of the substances of the whole reaction system.
Further, in the synthesis method of the prepolymer A, the prepolymer B and the adhesion enhancer C, the catalyst beta is a fluorine-containing organic tin compound, and suitable examples include, but are not limited to, one or a mixture of more of bis (3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl) tin oxide, allyltris (1H,1H,2H, 2H-perfluorooctyl) stannane, allyltris (3,3,4,4,5,5,6,6, 6-nonafluorohexyl) stannane, hexafluoroacetylacetonatotin and the like in proportion.
Further, in the synthesis method of the prepolymer A and the adhesion reinforcing agent C, the typical structure of the fluorinated acrylate containing hydroxyl is shown as formula 1, wherein R is2is-CH3or-H, R3is-CF3or-F, a is 3-8. As can be seen from FIGS. 1 and 3, prepolymers A and BR in adhesion enhancer C2、R3And a are derived from fluorinated acrylates containing hydroxyl groups, so that R2、R3And a have the same meaning.
Figure BDA0003052603230000051
Further, in the synthesis method of the adhesion reinforcing agent C, the structure of the silane coupling agent containing the isocyanate bond is
Figure BDA0003052603230000052
Wherein f is 1-4; r5＝-OCH3or-OCH2CH3；R6＝-OCH3or-OCH2CH3or-CH3. Suitable examples include, but are not limited to, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethylethoxysilane, 1-dimethoxy (methyl) silylmethyl isocyanate, in any desired ratio.
Furthermore, in the synthesis method of the prepolymer A, the prepolymer B and the adhesion enhancer C, the polymerization inhibitor is p-hydroxyanisole, p-tert-butylphenol or the like.
According to the above scheme, the photoinitiator is a non-yellowing photoinitiator, and can be a conventional photoinitiator or a fluorine modified photoinitiator, and suitable examples include but are not limited to one or a mixture of several of 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1-hydroxy-cyclohexyl-phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl acetone (1173), 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl phenylpropanone (2959).
As mentioned above, the monofunctional reactive diluent is a fluorinated alkyl acrylate, and suitable examples include, but are not limited to, one or a mixture of several of 1H,1H,2H, 2H-perfluorooctyl (meth) acrylate, 1H,2H, 2H-perfluorodecyl (meth) acrylate, 1H,2H, 2H-perfluorohexyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2,2,3,3,4,4, 4-heptafluorobutyl acrylate, 2,2, 2-trifluoroethyl acrylate, and the like, in proportions.
As mentioned above, the multifunctional reactive diluent is a fluorinated multifunctional acrylate, and suitable examples include, but are not limited to, one or a mixture of several of 1H,1H,6H, 6H-perfluorohexyl diacrylate, 1H,8H, 8H-perfluorooctyl diacrylate, 1H,10H, 10H-perfluorodecyl diacrylate, etc. in proportion.
According to the above scheme, the fluorine-containing silane coupling agent is siloxane containing fluoroalkyl structure, which has a very low refractive index per se to increase the adhesion of the coating resin to the optical fiber and repair microcracks of the optical fiber, and suitable examples include, but are not limited to, one or a mixture of several of heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, perfluorooctyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, etc. in proportion.
The low-refractive-index optical fiber coating resin has the refractive index of 1.36-1.41, the viscosity of 1000-10000mpa.s, and the preferable viscosity of 2000-6000mpa.s, can adjust the viscosity according to the process to meet the requirement of stable wire drawing, and can also obtain different refractive indexes by adjusting the proportion according to different grades of prepared optical fibers.
The low-refractive-index optical fiber coating resin with high glass transition temperature provided by the invention not only meets the requirement of low refractive index of a special optical fiber (the lowest refractive index can reach 1.36), but also can realize higher glass transition temperature (60-120 ℃), so that the special optical fiber can work at higher temperature and can realize higher-power laser transmission on a laser energy transmission optical fiber. Compared with the prior art, the invention has the beneficial effects that:
firstly, the viscosity of the optical fiber coating resin is 1000-10000mpa.s, the glass transition temperature is high (60-120 ℃), the toughness is good, the adhesion is strong, the optical fiber is not easy to break when being bent, the refractive index is low, the refractive index is 1.36-1.41, the digital transmission aperture of the optical fiber can be enlarged, the viscosity and the refractive index of a product can be adjusted according to different requirements of customers, and the requirements of more customizations can be met when preparing a novel special optical fiber, so that the novel special optical fiber which cannot be compared with the traditional coating can be prepared.
Secondly, the prepolymer A adopted by the invention is 2-functional tough polyester polyurethane acrylate, so that the optical fiber coating resin has good strength and extremely low refractive index; prepolymer B is a multifunctional prepolymer, has a larger modulus and a higher glass transition temperature, and optical fiber coating resins with different glass transition temperatures and different refractive indexes can be obtained by adjusting the ratio of prepolymer A to prepolymer B.
Drawings
FIG. 1 is a scheme for the synthesis of prepolymer A.
FIG. 2 is a scheme for the synthesis of prepolymer B.
Fig. 3 is a synthetic route diagram for adhesion enhancer C.
FIG. 4 is a synthetic scheme of fluorinated modified photoinitiator 17R-2959.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Some of the specific raw materials used in the following examples are shown in table 1.
TABLE 1
Figure BDA0003052603230000071
In the following examples, prepolymer A, B and adhesion enhancer C were used and were prepared by the following methods:
1. synthesis of prepolymer a:
1) 660.14g (1.5mol) of perfluoroazelaic acid and 1025.28g (2.5mol) of 1H,1H,11H, 11H-perfluoro-3, 6, 9-trioxaundecane-1, 11-diol are added into a reactor with stirring, 1.6g of catalyst p-toluenesulfonic acid is added, the temperature is increased to 120 ℃ and 130 ℃ for reaction, the temperature is kept for reaction until all solids become liquid, a vacuum pump is started to keep the temperature and vacuum pumping is carried out for reaction for 6 to 24 hours, and the relative vacuum degree is kept between-0.09 MPa and-0.1 MPa. Stopping the reaction when the acid value of the materials in the reactor is less than 0.5(mgKOH/g), discharging to obtain the fluorinated polyester diol, and determining the number average molecular weight of the fluorinated polyester diol to be 1606.20.
2) Adding 803.1g (0.5mol) of fluorinated polyester diol and 222.24g (1.0mol) of isophorone diisocyanate into a reactor with a stirrer, uniformly mixing the fluorinated polyester diol and the diisocyanate, adding 1.0g of hexafluoroacetylacetone tin as a catalyst and 0.5g of p-hydroxyanisole as a polymerization inhibitor, and reacting the obtained mixed system at 50 ℃ for 4 hours to obtain an intermediate of the terminal isocyanate;
3) 498.03g (1.0mol) of 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate was added to the intermediate of the terminal isocyanate obtained in step 2) and reacted at a temperature of 70 to 80 ℃ for 5 hours to obtain prepolymer A-1.
The prepolymer A-1 thus obtained was found to have a viscosity of 3200mpa.s (60 ℃ C.), a refractive index of 1.361(25 ℃ C.), a tensile modulus of 265.5MPa, an elongation of 75% and a tensile strength of 21.6 MPa.
2. Synthesis of prepolymer B:
1) 256.26g (2.0mol) of glycidyl acrylate and 440.09g (1.0mol) of perfluoroazelaic acid are uniformly mixed according to the mol ratio of 2:1, then 0.7g of benzyltriethylammonium bromide as a catalyst and 0.65g of p-hydroxyanisole as a polymerization inhibitor are added, and the reaction is carried out for 6 hours at the temperature of 100 ℃ and 110 ℃ to obtain the intermediate bifunctional fluorine-containing epoxy acrylate.
2) To the product obtained in step 1 were added 84.1g (0.5mol) of Hexamethylene Diisocyanate (HDI) and 0.7g of allyltris (3,3,4,4,5,5,6,6, 6-nonafluorohexyl) stannane as a catalyst, and reacted at 75 to 80 ℃ for 3 hours to obtain an intermediate urethane-modified epoxy acrylate.
3) Adding 207.32g (1.5mol) of potassium carbonate into the product obtained in the step 2), uniformly stirring, cooling to 50-55 ℃, slowly adding 632.54g (1.0mol) of perfluoro-n-dodecanoyl chloride, keeping the temperature at 50-55 ℃ for reaction for 4 hours, and filtering to remove solid particles to obtain the prepolymer B-1.
The prepolymer B-1 thus obtained was found to have a viscosity of 1305mpa.s (60 ℃ C.), a refractive index of 1.371(25 ℃ C.), a tensile modulus of 1325.5MPa, an elongation of 17.5% and a tensile strength of 43.6 MPa.
3. Synthesis of adhesion enhancer C:
498.03g (1.0mol) of 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate and 177.23g (1.0mol) of isocyanate methyltrimethoxysilane are added into a reactor with a stirrer to be uniformly stirred, 0.5g of tin hexafluoroacetylacetonate and 0.55g of p-hydroxyanisole serving as a polymerization inhibitor are added, and the mixture is kept at 70-80 ℃ to react for 6 hours to obtain the adhesion enhancer C-1.
4. Synthesis of fluorinated modified photoinitiator 17R-2959:
22.4g of photoinitiator 2959 (molecular weight 224) and 13.8g of potassium carbonate are added into a flask, cooled to 0-5 ℃ by an ice water bath, 43.25g of perfluorooctanoyl chloride is slowly added, and after the addition of the acyl chloride is finished, the reaction is maintained at 25 ℃ for 12 hours. And filtering the product in the flask to remove precipitates to obtain a product, cleaning the product by using 50.4g of hexafluoroisopropanol, filtering to obtain a filtrate, removing most of hexafluoroisopropanol from the filtrate by using a rotary evaporator, and drying for 24 hours at 40 ℃ by using a vacuum drying oven to obtain a fluorine-containing photoinitiator, namely, a fluorinated modified photoinitiator 17R-2959. The synthetic route of the fluorinated modified photoinitiator 17R-2959 is shown in FIG. 4.
Example 1
The coating resin for the optical fiber with the high glass transition temperature and the low refractive index comprises the following components in percentage by weight: the adhesive comprises, by weight, 100% of a prepolymer A, 150% of a prepolymer B, 115% of an adhesion force enhancer C, 13% of a fluorinated modified photoinitiator 17R, 29592.0% of 1H,1H,2H, 2H-perfluorodecyl acrylate 5%, 1H,1H,8H, 8H-perfluorooctyl diacrylate 10%, 1H,1H,10H, 10H-perfluorodecyl diacrylate 14.5% and heptadecafluorodecyl trimethoxy silane 0.5%.
The preparation method of the optical fiber coating resin comprises the following steps: weighing the raw material components according to the proportion, stirring the raw material components for 60 minutes at the rotating speed of 1000 r/min at about 70 ℃ by using a dispersion machine, filtering the mixture by using a 1500-mesh filter after the photoinitiator is completely dissolved, and defoaming the mixture in a 40 ℃ oven for 1 day to obtain a finished product, wherein the serial number of the finished product is YOCC-1.
Example 2
The coating resin for the optical fiber with the high glass transition temperature and the low refractive index comprises the following components in percentage by weight: the adhesive comprises, by weight, 135% of a prepolymer A, 130% of a prepolymer B, 15% of an adhesion enhancer C, 17R-29591.0% of a fluorinated modified photoinitiator, 1.0% of a photoinitiator TPO, 1841.0% of a photoinitiator, 20% of 1H,1H,8H, 8H-perfluorooctyl diacrylate, 6% of 1H,1H,10H, 10H-perfluorodecyl diacrylate, 0.5% of heptadecafluorodecyl trimethoxy silane, and 0.5% of tridecafluorooctyl trimethoxy silane, wherein the sum of the components is 100%.
The preparation method of the optical fiber coating resin comprises the following steps: weighing the raw material components according to the proportion, stirring the raw material components for 60 minutes at the rotating speed of 1000 r/min at about 70 ℃ by using a dispersion machine, filtering the mixture by using a 1500-mesh filter after the photoinitiator is completely dissolved, and defoaming the mixture in a 40 ℃ oven for 1 day to obtain a finished product, wherein the serial number of the finished product is YOCC-2.
Example 3
The coating resin for the optical fiber with the high glass transition temperature and the low refractive index comprises the following components in percentage by weight: prepolymer A-115%, prepolymer B-150%, adhesion reinforcing agent C-14%, photoinitiator TPO 1.0%, photoinitiator 1841.0%, 2,2,3,3,4,4, 4-heptafluorobutyl acrylate 3.5%, 1H,1H,6H, 6H-perfluorohexyl diacrylate 25%, and tridecafluorooctyl trimethoxysilane 0.5%, wherein the sum of the components is 100%.
The preparation method of the optical fiber coating resin comprises the following steps: weighing the raw material components according to the proportion, stirring the raw material components for 60 minutes at the rotating speed of 1000 r/min at about 70 ℃ by using a dispersion machine, filtering the mixture by using a 1500-mesh filter after the photoinitiator is completely dissolved, and defoaming the mixture in a 40 ℃ oven for 1 day to obtain a finished product, wherein the serial number of the finished product is YOCC-3.
Performance testing
The technical specifications of examples 1-3 and some commercially available types of low index optical fiber coatings are compared as shown in Table 2.
Table 2: examples 1-3 comparison of Performance with commercially available type Low refractive coatings
Figure BDA0003052603230000101
Note that1: the recommended maximum operating temperature is empirically 10 c above the glass transition temperature.
As can be seen from Table 2, the cured refractive indexes of the YOCC-1, YOCC-2 and YOCC-3 of the invention cover the existing PC363AP, PC373AP and PC409AP, and the comparison of the key elastic modulus, tensile strength and glass transition temperature indexes shows that the cured refractive indexes of the cured YOCC-1, YOCC-2 and YOCC-3 of the invention can be used for coating resin with a single cladding layer with a large core diameter and multi-cladding layer coating resin with high power. Under the condition of the same refractive index, the glass transition temperature of the YOCC-1, YOCC-2 and YOCC-3 is higher than that of competitive products (the existing PC363AP, PC373AP and PC409AP), the elastic modulus and the strength are higher, the external stress resistance is better, the mechanical property of the prepared optical fiber is better, and the working temperature of the special optical fiber can be improved. Provides wider choice for preparing optical fiber in the field of multipurpose optical fiber laser.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.

Claims (10)

1. The low-refractive-index optical fiber coating resin with high glass transition temperature is characterized by comprising the following components in percentage by weight: 10-60% of prepolymer A, 10-60% of prepolymer B, 1-10% of adhesion enhancer C, 0.5-5% of photoinitiator, 0-5% of monofunctional reactive diluent, 5-30% of multifunctional reactive diluent and 0.1-1% of fluorine-containing silane coupling agent, wherein the sum of the components is 100%;
the structure of the prepolymer A is shown as the formula AIn the formula A, R1Is composed of
Figure FDA0003546659240000011
R2is-CH3or-H, R3is-CF3or-F, a is 3-8;
PMZ has the structural formula
Figure FDA0003546659240000012
Wherein X has a structural formula
Figure FDA0003546659240000013
b＝2-20，c＝6-18，d＝0-2，e＝2-18，y＝1-20，R4＝-CH3or-H;
the structure of the prepolymer B is shown as a formula B, wherein in the formula B, B is 2-20, n is 3-18, and R is-CH3or-H;
Figure FDA0003546659240000014
Figure FDA0003546659240000021
the structure of the adhesion reinforcing agent C is shown as a formula C, wherein f is 1-4; r5＝-OCH3or-OCH2CH3；R6＝-OCH3or-OCH2CH3or-CH3，R2is-CH3or-H, R3is-CF3or-F, a is 3-8.
2. The resin for coating an optical fiber with a low refractive index and a high glass transition temperature according to claim 1, wherein the method for synthesizing the prepolymer A comprises the following steps:
1) mixing fluorinated polyester diol and diisocyanate in a molar ratio of 1:2 in a reactor, adding a catalyst beta and a polymerization inhibitor, and reacting at 30-60 ℃ for 3-6 hours to obtain an intermediate of isocyanate-terminated product; wherein, the adding amount of the catalyst beta accounts for 0.03-1% of the total mass of the substances of the whole reaction system in the step, and the adding amount of the polymerization inhibitor accounts for 0.01-0.3% of the total mass of the substances of the whole reaction system in the step;
2) adding fluorinated acrylate containing hydroxyl into the intermediate of the end isocyanate obtained in the step 1), and reacting at the temperature of 60-80 ℃ for 3-6 hours to obtain prepolymer A; the molar ratio of the fluorinated acrylate containing hydroxyl in the step to the fluorinated polyester diol in the step 1) is 2: 1.
3. the resin for coating an optical fiber with a low refractive index and a high glass transition temperature as claimed in claim 1, wherein the fluorinated polyester diol has a number average molecular weight of 600-4000 and is obtained by a polycondensation reaction of perfluoro diacid and fluoro diol; wherein the structural formula of the fluorine-containing diol is shown in the specification
Figure FDA0003546659240000022
The structural formula of the perfluorinated diacid is
Figure FDA0003546659240000023
Wherein b is 2-20, c is 6-18, d is 0-2, e is 2-18, R4＝-CH3or-H.
4. The resin for coating an optical fiber with a low refractive index and a high glass transition temperature according to claim 1, wherein the method for synthesizing the prepolymer B comprises the following steps:
1) mixing glycidyl (meth) acrylate and perfluorodiacid in a molar ratio of 2:1 in a reactor, adding a catalyst gamma and a polymerization inhibitor, and reacting at 80-110 ℃ for 2-8 hours to obtain an intermediate bifunctional fluorine-containing epoxy acrylate FEA; wherein, the catalyst gamma accounts for 0.03 to 1 percent of the total mass of the substances in the step, and the polymerization inhibitor accounts for 0.01 to 1 percent of the total mass of the substances in the whole reaction system;
2) adding hexamethylene diisocyanate and a catalyst beta into the intermediate bifunctional fluorine-containing epoxy acrylate FEA obtained in the step 1), and then keeping the temperature of 70-90 ℃ for reacting for 2-4 hours to obtain an intermediate urethane modified epoxy acrylate; wherein the catalyst beta accounts for 0.03-1% of the total mass of the substances in the step 1) and the step 2), and the molar ratio of HDI to FEA in the first step is 1: 2;
3) adding potassium carbonate into the intermediate urethane-modified epoxy acrylate obtained in the step 2), uniformly stirring, cooling to 40-60 ℃, slowly adding perfluoroalkyl acyl chloride, reacting for 2-4 hours at 40-60 ℃, and filtering to remove solid particles to obtain a prepolymer B; wherein, the molar ratio of the perfluoroalkyl acyl chloride in the step and the perfluorinated diacid in the step 1) is 1: 1; the molar ratio of the perfluoroalkyl acyl chloride to the potassium carbonate is 1: 1-1: 2.
5. The high Tg low refractive index optical fiber coating resin of claim 4, wherein in the prepolymer B synthesis process, the catalyst γ is benzyltriethylammonium bromide; the structural formula of the perfluorinated diacid is
Figure FDA0003546659240000031
Wherein b is 2-20.
6. The resin for coating an optical fiber with a high glass transition temperature and a low refractive index according to claim 1, wherein the adhesion enhancer C is synthesized by the following method:
mixing hydroxyl-containing fluorinated acrylate and a silane coupling agent containing an isocyanate bond in a molar ratio of 1: 1-1.1: 1 in a reactor, adding a catalyst beta and a polymerization inhibitor, and reacting for 2-8 hours at 60-90 ℃ to obtain an adhesion reinforcing agent C; wherein, the adding amount of the catalyst beta accounts for 0.03-1% of the total mass of the substances of the whole reaction system, and the polymerization inhibitor accounts for 0.01-1% of the total mass of the substances of the whole reaction system.
7. The coating resin for optical fiber with high glass transition temperature and low refractive index according to any one of claims 2, 4 and 6, wherein the catalyst β is a fluorine-containing organotin compound; the polymerization inhibitor is p-hydroxyanisole or p-tert-butylphenol.
8. The high glass transition temperature, low refractive index optical fiber coating resin of claim 1, wherein said fluorine-containing silane coupling agent is a siloxane having a fluoroalkyl structure; the monofunctional reactive diluent is a fluorinated alkyl acrylate; the multifunctional reactive diluent is a fluorinated multifunctional acrylate.
9. The resin for coating an optical fiber with a high glass transition temperature and a low refractive index according to claim 1, wherein the fluorine-containing silane coupling agent includes but is not limited to one or a mixture of heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, perfluorooctyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, nonafluorohexyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane; the photoinitiator includes but is not limited to one or a mixture of several of 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone and 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl phenylpropyl ketone according to a proportion.
10. The high Tg low index fiber coating resin of claim 1, wherein the monofunctional reactive diluent comprises but is not limited to one or a mixture of 1H,1H,2H, 2H-perfluorooctyl (meth) acrylate, 1H,2H, 2H-perfluorodecyl (meth) acrylate, 1H,2H, 2H-perfluorohexyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2,2,3,3,4,4, 4-heptafluorobutyl acrylate, 2,2, 2-trifluoroethyl acrylate;
the multifunctional reactive diluent comprises but is not limited to one or a mixture of more than one of 1H,1H,6H, 6H-perfluorohexyl diacrylate, 1H,8H, 8H-perfluorooctyl diacrylate, 1H,10H, 10H-perfluorodecyl diacrylate according to a proportion.
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