Epoxy resin for optical fiber array and preparation method thereof

Abstract

The invention discloses epoxy resin for an optical fiber array and a preparation method thereof, and belongs to the technical field of epoxy resin preparation. The epoxy resin for the optical fiber array consists of the following components in parts by weight: 50-80 parts of epoxy resin, 5-30 parts of modified functional resin, 5-10 parts of a toughening agent, 1-5 parts of an auxiliary agent and 5-20 parts of a composite curing agent. The epoxy resin for the optical fiber array prepared by the method has excellent thermal stability and mechanical strength, also has low shrinkage and curing shrinkage stress, and avoids debonding of optical fibers and an adhesive layer.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of epoxy resin preparation, and particularly relates to an epoxy resin for optical fiber arrays and a preparation method thereof. BACKGROUND

[0002] Under the trend of continuous evolution of optical fiber communication technology towards high speed, integration and intelligence, the performance stability of the optical fiber array, as the core component for realizing accurate transmission and coupling of optical signals in an optical module, directly determines the reliability of the optical communication system. With the rapid development of 5G network construction, data center expansion and intelligent driving in various fields, the application scenarios of the optical fiber array are continuously expanding, and more stringent requirements are put forward for the comprehensive performance of the packaging material. The traditional adhesive gradually exposes limitations in the manufacturing process of the optical fiber array: on the one hand, the optical fiber has a small diameter and needs to achieve nanometer-level alignment accuracy, and the high solidification shrinkage rate of ordinary adhesive easily leads to position deviation of the optical fiber, thereby causing an increase in optical signal transmission loss; on the other hand, the optical module needs to be operated for a long time under complex environmental conditions, and the mismatch of the thermal expansion coefficients of the materials may cause stress concentration at the interface, resulting in cracking or performance degradation of the packaging structure. In addition, with the development of the optical module towards higher density and smaller size, the flowability, wettability and anti-vibration performance of the adhesive are put forward with higher challenges in the packaging process of the optical fiber array. The epoxy resin becomes an ideal choice in the field of packaging of the optical fiber array due to its unique molecular structure advantage.

[0003] Patent CN118931446A discloses an epoxy resin adhesive with fluorescence and a preparation method thereof, the epoxy resin adhesive is composed of A adhesive, B adhesive and oil-based fluorescent agent; the content of the oil-based fluorescent agent is 0.0001%-1%; the product can be identified whether the epoxy resin adhesive is overflowed or sputtered under the ultraviolet lamp through the naked eye or a visual system, thereby screening defective products, but the epoxy resin adhesive still has obvious deficiencies, the high solidification shrinkage rate of the epoxy resin adhesive itself has not been effectively improved, and the high shrinkage rate may cause large internal stress in the curing process, which not only may cause peeling and cracking between the adhesive layer and the adherend, affects the long-term stability and reliability of the adhesion, but also causes damage to precise devices such as the optical fiber array, leads to position deviation of the optical fiber, increases optical signal transmission loss and reduces product performance. SUMMARY

[0004] The purpose of the present application is to provide an epoxy resin for optical fiber arrays and a preparation method thereof, which are used to solve the technical problems of high solidification shrinkage rate and poor mechanical properties of the epoxy resin in the prior art.

[0005] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0006] The present application provides an epoxy resin for optical fiber array, which is composed of the following components in parts by weight: 50-80 parts of epoxy resin, 5-30 parts of modified functional resin, 5-10 parts of toughening agent, 1-5 parts of auxiliary agent, and 5-20 parts of composite curing agent.

[0007] As preferred, the preparation method of the modified functional resin comprises the following steps:

[0008] Q1: 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, di-tert-butyl dicarbonate and nano-ferric oxide are added into anhydrous ethanol, and the reaction is stirred at room temperature. After the reaction is completed, filtration, spin-drying, dissolution, washing, liquid separation, spin-drying are performed to obtain compound a;

[0009] Q2: Sodium tripolyphosphate, p-chlorophenylglycine and acetone are sequentially added into a container. Cinnamoyl chloride is added into acetone, and after being stirred and dissolved, it is added dropwise into the container. After the dropwise addition is completed, the reaction is continued. After filtration, washing and drying, compound b is obtained;

[0010] Q3: Compound a and triethylamine are added into dichloromethane, and after being stirred, they are placed in an ice bath environment for cooling. A mixed solution of compound b and dichloromethane is added, and the reaction is stirred at room temperature. After the reaction is completed, saturated sodium bicarbonate solution is added, and the organic phase is collected after being washed and separated. After drying and vacuum distillation, compound c is obtained after purification and filtration. Compound c is added into a container, and the reaction is heated in an oil bath. After the reaction is completed, cooling, purification and filtration are performed to obtain a modified diamine;

[0011] Q4: The modified diamine and 4,4'-diamino diphenyl ether are added into N-methyl pyrrolidone, and after being stirred and dissolved, they are cooled in an ice bath. Then, hexafluorodiphthalic anhydride is added, and the reaction is carried out in an ice bath. After the reaction is completed at room temperature, a mixed solution of anhydrous acetic anhydride and anhydrous triethylamine is added, and the reaction is carried out after being heated. Then, the reaction mixture is added into ethanol, washed, centrifuged and vacuum dried to obtain the modified functional resin.

[0012] In the above process, the synthesis reaction formula of the modified functional resin is as follows:

[0013]

[0014] The mass spectrometry analysis results of compound a are: m / z: 566.19 (100.0%), 567.19 (27.6%), 568.19 (5.1%); the mass spectrometry analysis results of compound b are: m / z: 315.07 (100.0%), 317.06 (32.0%), 316.07 (18.7%), 318.07 (6.1%), 317.07 (2.3%); the mass spectrometry analysis results of compound c are: m / z: 1124.36 (100.0%), 1125.37 (64.9%), 1126.37 (23.2%), 1127.37 (6.1%), 1125.36 (1.5%), 1128.38 (1.2%), 1126.36 (1.0%); the mass spectrometry analysis results of modified diamine are: m / z: 924.26 (100.0%), 925.26 (54.8%), 926.27 (14.1%), 927.27 (3.3%), 926.26 (2.4%).

[0015] As preferred, in the Q1, the amount ratio of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, di-tert-butyl dicarbonate, nano-tetrairon oxide and anhydrous ethanol is (6.32-7.01) g:(4.38-4.59) g:(0.21-0.35) g:(55-65) mL, the stirring reaction time is 10-12 h, the filtration is performed by using a 0.45 μm organic filter membrane, the dissolution is performed by using ethyl acetate, and the washing is performed by using a saturated ammonium chloride solution.

[0016] As preferred, in the Q2, the amount ratio of sodium tripolyphosphate, p-chlorophenylglycine and cinnamoyl chloride is (8.52-9.16) g:(5.38-5.46) g:(7.81-8.17) g, and the continuous reaction time is 4-6 h; in the Q3, the molar ratio of compound a, triethylamine and compound b is (1-1.3):(2.2-2.6):(2.2-2.8), the cooling time is 10-15 min, the stirring reaction time at room temperature is 30-45 min, and the oil bath heating reaction temperature is 200-220 °C.

[0017] As preferred, in the Q4, the amount ratio of modified diamine, 4,4'-diaminodiphenyl ether, N-methylpyrrolidone, hexafluorodianhydride, anhydrous acetic anhydride and anhydrous triethylamine is (0.073-0.082) g:(0.64-0.78) g:(6.5-8.5) mL:(1.91-2.17) g:(2.11-2.32) mL:(3.12-3.28) mL, the ice bath cooling time is 10-20 min, the ice bath reaction time is 1-2 h, the room temperature reaction time is 10-12 h, the temperature rising reaction temperature is 90-100 °C, and the reaction time is 10-12 h.

[0018] Preferably, the preparation method of the composite curing agent comprises the following steps:

[0019] S1: Add 2,3,6,7-tetramethylanthracene-9,10-dione to a container, add cesium fluoride and tetrahydrofuran under nitrogen protection, stir at low temperature, add trimethyl (trifluoromethyl) silane, continue stirring, heat to react, and after the reaction is completed, filter, wash, and purify to obtain product 1; add product 1 to tetrahydrofuran, heat and reflux until dissolved, then add concentrated hydrochloric acid, stir to react, cool, filter, and wash to obtain product 2;

[0020] S2: Under nitrogen protection, product 2 is added to a container filled with anhydrous benzene, stirred, cooled, trifluoromethanesulfonic acid is added, the reaction is continued, distilled water is added, extraction is carried out, spin-dried, and purified to obtain product 3; product 3 is added to a mixed solution of pyridine and distilled water, heated under reflux to dissolve, and then potassium permanganate is added, the reaction is continued, and ethanol is subsequently added, filtered, concentrated, and purified to obtain product 4;

[0021] S3: Add product 4 to acetic anhydride, heat under reflux until dissolved, stir to react, concentrate, and purify to obtain product 5. Mix product 5, epoxy acrylate and 2-hydroxy-2-methyl-1-phenylacetone and stir to obtain a composite curing agent.

[0022] In the above process, the synthetic reaction formula of product 5 is as follows:

[0023]

[0024] The results of mass spectrometry analysis of product 1 were: m / z: 406.16 (100.0%), 407.16 (29.2%), 408.16 (4.3%), 408.15 (3.3%), 409.16 (1.0%); the results of mass spectrometry analysis of product 2 were: m / z: 334.12 (100.0%), 335.12 (20.8%), 336.12 (2.4%); the results of mass spectrometry analysis of product 3 were: m / z: 394.15 (100.0%), 395.16 (27.3%), 396.16 (3.8%); the results of mass spectrometry analysis of product 4 were: m / z: 514.05 (100.0%), 515.05 (27.0%), 516.06 (5.5%); the results of mass spectrometry analysis of product 5 were: m / z: 478.03 (100.0%), 479.03 (27.3%), 480.04 (3.6%), 480.03 (1.4%).

[0025] As preferred, in the S1, the amount ratio of 2,3,6,7-tetramethylanthracene-9,10-dione, cesium fluoride, tetrahydrofuran and trimethyl(trifluoromethyl)silane is (10-12) g:(0.057-0.082) g:(500-600) mL:(6-9) mL, the low-temperature stirring temperature is -10 to -15℃, the stirring time is 10-15 min, the continuous stirring time is 10-20 min, the temperature is increased to 10-12℃, and the reaction is carried out for 3-5 h; the amount ratio of the product 1 and tetrahydrofuran is (10-12) g:(20-25) mL, and the stirring reaction time is 4-6 h.

[0026] As preferred, in the S2, the amount ratio of the product 2, anhydrous benzene and trifluoromethanesulfonic acid is (5-7.5) g:(10-20) mL:(10-14) mL, after stirring for 10-15 min, the temperature is decreased to 0-1℃, and the continuous reaction time is 14-18 h; the amount ratio of the product 3, pyridine, distilled water and potassium permanganate is (5-7.5) g:(160-180) mL:(20-40) mL:(18-22) g, and the continuous reaction time is 14-18 h.

[0027] As preferred, in the S3, the amount ratio of the product 4 and acetic anhydride is (5-7) g:(30-45) mL, and the stirring reaction time is 3-5 h; the amount ratio of the product 5, epoxy acrylate and 2-hydroxy-2-methyl-1-phenylpropanone is (3-8) g:(2-7) g:(0.03-0.05) g.

[0028] As preferred, the preparation method of the epoxy resin for optical fiber array comprises the following steps:

[0029] In step one, the epoxy resin and the modified functional resin are added into a reaction kettle under nitrogen protection, heated and stirred to obtain a mixture;

[0030] In step two, the toughening agent and the auxiliary agent are added into the mixture, and the stirring is continued, the temperature is decreased, the composite curing agent is added, the stirring is continued, vacuum defoaming is carried out, and filtration is carried out to obtain the epoxy resin for optical fiber array.

[0031] As described above, due to the adoption of the above technical solutions, the present application has the following beneficial effects:

[0032] 1. In the process of preparing the epoxy resin for optical fiber array, the modified functional resin and the composite curing agent are added, so that the prepared epoxy resin has excellent heat resistance and mechanical properties, and also has low shrinkage and curing shrinkage stress.

[0033] 2. The modified functional resin prepared by the present application can be used as one of the raw materials of the epoxy resin for optical fiber array, which can effectively improve the heat resistance and mechanical properties, and also can reduce the shrinkage and curing shrinkage stress. The modified functional resin has excellent thermal stability, and the introduced fluorine atoms can further reduce the polarity of the material, reduce the energy loss during thermal motion, and improve the heat resistance. At the same time, the high-strength molecular chain structure contained in the modified functional resin forms an interpenetrating structure with the crosslinked network of the epoxy resin, which synergistically improves the tensile strength and modulus. The low shrinkage property of the modified functional resin can effectively balance the volume shrinkage of the epoxy resin during curing, reduce the curing shrinkage stress, and prevent the optical fiber from being detached from the adhesive layer.

[0034] 3. The composite curing agent prepared by the present application can be used as a curing component of the epoxy resin for optical fiber array, which can effectively improve the heat resistance and mechanical properties, and also can reduce the shrinkage and internal stress. The composite curing agent undergoes ring-opening addition reaction with the epoxy groups of the epoxy resin to form a three-dimensional network structure with high crosslinking density, which greatly improves the thermal stability. The introduced fluorinated groups further reduce the molecular polarity, reduce the energy loss during thermal motion, and improve the heat resistance. At the same time, the rigid network structure formed by the composite curing agent effectively enhances the rigidity and hardness of the epoxy resin. The excellent compatibility between the anhydride contained in the composite curing agent and the epoxy resin makes the volume shrinkage during the curing process very small, and the curing shrinkage stress is greatly reduced, thereby effectively preventing the optical fiber from being detached from the adhesive layer, improving the structural stability of the optical fiber array, and improving the signal transmission reliability. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0036] Embodiment 1: The present embodiment discloses a preparation method of a modified functional resin, comprising the following steps:

[0037] Q1: 6.68g of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 4.48g of di-tert-butyl dicarbonate and 0.28g of nano four-iron oxide were added to 60mL of anhydrous ethanol, stirred at room temperature for 12h, filtered with 0.45μm organic filter membrane after the reaction was completed, spin-dried, dissolved with ethyl acetate, washed with saturated ammonium chloride solution, separated, spin-dried, and compound a was obtained;

[0038] Q2: 8.84 g of sodium tripolyphosphate, 5.42 g of p-chlorophenylglycine and 10 mL of acetone were sequentially added to the container, 7.93 g of cinnamoyl chloride was added to 15 mL of acetone, after stirring and dissolving, it was added dropwise to the container, after the dropwise addition was completed, the reaction was continued for 6 h, and then filtration, washing and drying were performed to obtain compound b;

[0039] Q3: 0.68 g of compound a and 0.25 g of triethylamine were added to 10 mL of dichloromethane, after stirring, it was cooled in an ice bath environment for 10 min, and then a mixture solution of 1.91 g of compound b and 5 mL of dichloromethane was added, and the reaction was stirred at room temperature for 45 min, after the reaction was completed, saturated sodium bicarbonate solution was added, and then the organic phase was collected by washing, drying and vacuum distillation, and then compound c was obtained by purification and filtration; compound c was added to the container, and the reaction was heated in an oil bath at 200°C, after the reaction was completed, it was cooled, purified, and filtered to obtain a modified diamine;

[0040] Q4: 0.077 g of the modified diamine and 0.71 g of 4,4'-diamino diphenyl ether were added to 7.5 g of N-methyl pyrrolidone, and then stirred and dissolved, cooled in an ice bath for 20 min, and then 2.04 g of hexafluoro dianhydride was added, and the reaction was carried out in an ice bath for 2 h, and then the reaction was carried out at room temperature for 12 h, and then a mixture solution of 2.21 g of anhydrous acetic anhydride and 3.2 mL of anhydrous triethylamine was added, and the reaction was carried out at 90°C for 12 h, and then added to ethanol, washed, centrifuged, and dried in vacuum to obtain a modified functional resin.

[0041] The present embodiment discloses a preparation method of a composite curing agent, comprising the following steps:

[0042] S1: 11 g of 2,3,6,7-tetramethylanthracene-9,10-dione was added to a container, 0.068 g of cesium fluoride and 550 mL of tetrahydrofuran were added under nitrogen protection, and then stirred at -10°C for 15 min, and then 7.5 mL of trimethyl(trifluoromethyl)silane was added, and then the stirring was continued for 20 min, and then the temperature was increased to 10°C for 5 h, and then the reaction was completed, and then filtered, washed and purified to obtain product 1; 11 g of product 1 was added to 22.5 mL of tetrahydrofuran, and then heated to reflux to dissolve, and then concentrated hydrochloric acid was added until the white precipitate no longer increased, and then stirred for 4 h, and then cooled, filtered and washed to obtain product 2;

[0043] S2: 6.25 g of product 2 was added to a container containing 15 mL of anhydrous benzene under nitrogen protection, and then stirred for 15 min, and then cooled to 0°C, and then 12 mL of trifluoromethanesulfonic acid was added, and then the reaction was continued for 14 h, and then distilled water was added, and then extracted, and then dried by rotary evaporation, and then purified to obtain product 3; 6.25 g of product 3 was added to a mixture solution of 170 mL of pyridine and 30 mL of distilled water, and then heated to reflux to dissolve, and then 20 g of potassium permanganate was added, and then the reaction was continued for 18 h, and then ethanol was added, and then filtered, concentrated and purified to obtain product 4;

[0044] S3: Add 6 g of product 4 to 37.5 mL of acetic anhydride, heat under reflux until dissolved, stir and react for 4 h, concentrate, and purify to obtain product 5. 5.5 g of product 5, 4.5 g of epoxy acrylate, and 0.04 g of 2-hydroxy-2-methyl-1-phenylacetone were mixed and stirred to obtain a composite curing agent.

[0045] This embodiment discloses an epoxy resin for optical fiber arrays, which is composed of the following components by weight: 65 parts of bisphenol F epoxy resin, 17.5 parts of modified functional resin, 7.5 parts of dibutyl phthalate, 3 parts of silane coupling agent KH-550, and 12.5 parts of composite curing agent.

[0046] This embodiment discloses a method for preparing an epoxy resin for an optical fiber array, comprising the following steps:

[0047] Step 1: Under nitrogen protection, add bisphenol F epoxy resin and modified functional resin into a reactor, heat and stir to react, and obtain a mixture;

[0048] Step 2: Add dibutyl phthalate and silane coupling agent KH-550 to the mixture, continue stirring, cool down, add composite curing agent, stir, vacuum degas, filter, and obtain epoxy resin for optical fiber array.

[0049] Example 2: This example discloses a method for preparing a modified functional resin, comprising the following steps:

[0050] Q1: 6.32 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4.38 g of di-tert-butyl dicarbonate and 0.35 g of nano-ferrosoferric oxide were added to 65 mL of anhydrous ethanol and stirred at room temperature for 12 h. After the reaction, the mixture was filtered with a 0.45 μm organic filter membrane, dried by spin drying, dissolved with ethyl acetate, washed with saturated ammonium chloride solution, separated, and dried by spin drying to obtain compound a;

[0051] Q2: 8.52 g of sodium tripolyphosphate, 5.38 g of p-chlorophenylglycine, and 10 mL of acetone were sequentially added to a container, 7.81 g of cinnamoyl chloride was added to 15 mL of acetone, stirred to dissolve, and then added dropwise to the container. After the addition was complete, the reaction was continued for 6 h, filtered, washed, and dried to obtain compound b;

[0052] Q3: 0.56 g of compound a and 0.22 g of triethylamine were added to 10 mL of dichloromethane, after stirring, a mixed solution of 1.68 g of compound b and 5 mL of dichloromethane was added in an ice bath environment for 10 min, the reaction was stirred at room temperature for 45 min, after the reaction was completed, saturated sodium bicarbonate solution was added, washed, separated and collected the organic phase, dried, distilled under reduced pressure, purified, filtered to obtain compound c; compound c was added to the container, heated in an oil bath at 200°C, after the reaction was completed, it was cooled, purified, filtered to obtain a modified diamine;

[0053] Q4: 0.073 g of modified diamine and 0.64 g of 4,4'-diamino diphenyl ether were added to 8.5 g of N-methyl pyrrolidone, stirred and dissolved, cooled in an ice bath for 20 min, then 1.91 g of hexafluoro dianhydride was added, reacted in an ice bath for 2 h, then reacted at room temperature for 12 h, then a mixed solution of 2.11 g of anhydrous acetic anhydride and 3.12 mL of anhydrous triethylamine was added, and the temperature was raised to 90°C for 12 h, then added to ethanol, washed, centrifuged, and dried under vacuum to obtain a modified functional resin.

[0054] The embodiment discloses a preparation method of a composite curing agent, comprising the following steps:

[0055] S1: 12 g of 2,3,6,7-tetramethylanthracene-9,10-dione was added to a container, 0.057 g of cesium fluoride and 600 mL of tetrahydrofuran were added under nitrogen protection, and stirred at -10°C for 15 min, then 6 mL of trimethyl(trifluoromethyl) silane was added, and the stirring was continued for 20 min, then the temperature was raised to 10°C for 5 h, after the reaction was completed, the product 1 was obtained after filtration, washing and purification; 10 g of product 1 was added to 25 mL of tetrahydrofuran, heated to reflux to dissolve, then concentrated hydrochloric acid was added until no white precipitate was formed, stirred for 4 h, then cooled, filtered and washed to obtain product 2;

[0056] S2: 5 g of product 2 was added to a container containing 20 mL of anhydrous benzene under nitrogen protection, stirred for 15 min, then cooled to 0°C, 10 mL of trifluoromethanesulfonic acid was added, and the reaction was continued for 14 h, then distilled water was added, extracted, rotary dried, and purified to obtain product 3; 5 g of product 3 was added to a mixed solution of 180 mL of pyridine and 40 mL of distilled water, heated to reflux to dissolve, then 18 g of potassium permanganate was added, and the reaction was continued for 18 h, then ethanol was added, filtered, concentrated, and purified to obtain product 4;

[0057] S3: 5 g of product 4 was added to 30 mL of acetic anhydride, heated to reflux to dissolve, stirred for 4 h, concentrated, and purified to obtain product 5, then 3 g of product 5, 2 g of epoxy acrylate and 0.05 g of 2-hydroxy-2-methyl-1-phenylpropanone were mixed and stirred to obtain a composite curing agent.

[0058] The embodiment discloses an epoxy resin for optical fiber array, which is composed of the following components in parts by weight: 50 parts of bisphenol F type epoxy resin, 30 parts of modified functional resin, 10 parts of dibutyl phthalate, 1 part of silane coupling agent KH-550 and 20 parts of composite curing agent.

[0059] The embodiment discloses a preparation method of an epoxy resin for optical fiber array, which comprises the following steps:

[0060] Step one: under the protection of nitrogen, the bisphenol F type epoxy resin and the modified functional resin are added into a reaction kettle, heated and stirred to react, and a mixture is obtained;

[0061] Step two: the dibutyl phthalate and the silane coupling agent KH-550 are added into the mixture, and stirring, cooling, adding the composite curing agent, stirring, vacuum degassing, filtering are carried out, and the epoxy resin for optical fiber array is obtained.

[0062] Embodiment 3: the embodiment discloses a preparation method of a modified functional resin, which comprises the following steps:

[0063] Q1: 7.01g of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 4.59g of di-tert-butyl dicarbonate and 0.21g of nano four-iron oxide are added into 55mL of anhydrous ethanol, stirred at room temperature for 12h, after the reaction is completed, filtered with a 0.45μm organic filter membrane, spin-dried, dissolved with ethyl acetate, washed with a saturated ammonium chloride solution, separated, spin-dried, and the compound a is obtained;

[0064] Q2: 9.16g of sodium tripolyphosphate, 5.46g of p-chlorophenyl glycine and 10mL of acetone are sequentially added into a container, 8.17g of cinnamoyl chloride is added into 15mL of acetone, after stirring and dissolving, the mixture is added dropwise into the container, after the dropwise addition is completed, the reaction is continued for 6h, the mixture is filtered, washed and dried, and the compound b is obtained;

[0065] Q3: 0.73g of the compound a and 0.28g of triethylamine are added into 10mL of dichloromethane, after stirring, the mixture is placed in an ice bath environment and cooled for 10min, 2.13g of the compound b and 5mL of dichloromethane are added into the mixture, the mixture is stirred at room temperature for 45min, after the reaction is completed, a saturated sodium bicarbonate solution is added, the mixture is washed, separated and the organic phase is collected, dried, distilled under reduced pressure, purified, filtered, and the compound c is obtained; the compound c is added into a container, and the mixture is heated to react in an oil bath at 200℃, after the reaction is completed, the mixture is cooled, purified, filtered, and the modified diamine is obtained.

[0066] Q4: 0.082 g of modified diamine and 0.78 g of 4,4'-diamino diphenyl ether were added to 6.5 g of N-methyl pyrrolidone, stirred and dissolved, cooled in an ice bath for 20 min, then 2.17 g of hexafluoro dianhydride was added, reacted in an ice bath for 2 h, then reacted at room temperature for 12 h, then a mixed solution of 2.32 g of anhydrous acetic anhydride and 3.28 mL of anhydrous triethylamine was added, and the temperature was raised to 90°C for reaction for 12 h, then added to ethanol, washed, centrifuged, and vacuum dried to obtain a modified functional resin.

[0067] The embodiment discloses a preparation method of a composite curing agent, comprising the following steps:

[0068] S1: 10 g of 2,3,6,7-tetramethylanthracene-9,10-dione was added to a container, 0.082 g of cesium fluoride and 500 mL of tetrahydrofuran were added under nitrogen protection, and stirred at -10°C for 15 min, then 9 mL of trimethyl(trifluoromethyl)silane was added, and stirred for 20 min, then the temperature was raised to 10°C for reaction for 5 h, after the reaction was completed, filtration, washing, and purification were performed to obtain product 1; 12 g of product 1 was added to 20 mL of tetrahydrofuran, heated to reflux to dissolve, then concentrated hydrochloric acid was added until the white precipitate no longer increased, stirred for 4 h, cooled, and filtered to obtain product 2;

[0069] S2: 7.5 g of product 2 was added to a container containing 10 mL of anhydrous benzene under nitrogen protection, stirred for 15 min, then the temperature was lowered to 0°C, 14 mL of trifluoromethanesulfonic acid was added, and the reaction was continued for 14 h, distilled water was added, extracted, rotary dried, and purified to obtain product 3; 7.5 g of product 3 was added to a mixed solution of 160 mL of pyridine and 20 mL of distilled water, heated to reflux to dissolve, then 22 g of potassium permanganate was added, and the reaction was continued for 18 h, then ethanol was added, filtered, concentrated, and purified to obtain product 4;

[0070] S3: 7 g of product 4 was added to 45 mL of acetic anhydride, heated to reflux to dissolve, stirred for 4 h, concentrated, and purified to obtain product 5; 8 g of product 5, 7 g of epoxy acrylate, and 0.03 g of 2-hydroxy-2-methyl-1-phenylpropanone were mixed and stirred to obtain a composite curing agent.

[0071] The embodiment discloses an epoxy resin for an optical fiber array, which is composed of the following components in parts by weight: 80 parts of bisphenol F type epoxy resin, 5 parts of modified functional resin, 5 parts of dibutyl phthalate, 5 parts of silane coupling agent KH-550, and 5 parts of composite curing agent.

[0072] The embodiment discloses a preparation method of an epoxy resin for an optical fiber array, comprising the following steps:

[0073] Step one: under nitrogen protection, the bisphenol F type epoxy resin and the modified functional resin are added into a reaction kettle, heated and stirred to react, to obtain a mixture;

[0074] Step two: the dibutyl phthalate and the silane coupling agent KH-550 are added into the mixture, continue to stir, cool, add a composite curing agent, stir, vacuum degassing, filter, to obtain an epoxy resin for optical fiber array.

[0075] Comparative example 1: compared with example 1, in the preparation of the epoxy resin, no modified functional resin is added, and other conditions are unchanged.

[0076] Comparative example 2: compared with example 1, in the preparation of the epoxy resin, the composite curing agent is replaced by epoxy acrylate and 2-hydroxy-2-methyl-1-phenylpropanone, and other conditions are unchanged.

[0077] Performance test

[0078] The samples prepared according to examples 1-3 and comparative examples 1-2 are tested for performance, the samples are cured at 700mW UV for 200s, then heated at 85℃ for 120min, the thermal stability of the samples is tested by thermogravimetric analysis, the tensile properties and compression properties of the samples are tested according to GB / T 2567-2021, the density of the samples before curing (ρ1) is tested according to GB / T 15223-2008, the density of the samples after curing (ρ2) is tested according to GB / T 1033.1-2022, the shrinkage rate is [(ρ2-ρ1) / ρ2]×100%, and the test results are shown in Table 1:

[0079] Table 1

[0080] Item Decomposition temperature / °C Tensile strength / MPa Compressive strength / MPa Shrinkage / % Example 1 415.96 98.64 164.56 0.92 Example 2 415.32 97.83 163.75 0.95 Example 3 415.41 98.12 163.62 0.96 Comparative Example 1 362.43 74.34 115.75 1.47 Comparative Example 2 361.48 72.57 113.22 1.52

[0081] From the test results in Table 1, it can be seen that by using the method of examples 1-3, an epoxy resin with excellent thermal stability, mechanical properties and low shrinkage rate can be prepared. It can be found from the comparison of comparative example 1 and examples 1-3 that the addition of modified functional resin can effectively improve the thermal stability, mechanical properties of the epoxy resin, and also reduce its shrinkage rate; it can be found from the comparison of comparative example 2 and examples 1-3 that the addition of composite curing agent can effectively improve the thermal stability, mechanical properties of the epoxy resin, and also reduce its shrinkage rate.

[0082] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can make equivalent replacement or change according to the technical solution and inventive concept of the present application within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

[0083] The preferred embodiments of the application disclosed above are only to help explain the application. The preferred embodiments are not intended to describe all the details of the application and are not intended to limit the application to the specific form disclosed. Obviously, many modifications and variations are possible in light of the above teachings. The preferred embodiments are selected and described so that one skilled in the art can best understand and utilize the application. The application is limited only by the claims and their full scope and equivalents.

Claims

1. An epoxy resin for optical fiber array, characterized in that: The invention is composed of the following components in parts by weight: 50-80 parts of epoxy resin, 5-30 parts of modified functional resin, 5-10 parts of toughening agent, 1-5 parts of auxiliary agent and 5-20 parts of composite curing agent.

2. The epoxy resin for optical fiber array according to claim 1, characterized in that: The preparation method of the modified functional resin comprises the following steps: Q1: Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, di-tert-butyl dicarbonate and nano-ferrosoferric oxide to anhydrous ethanol, stir at room temperature for reaction, filter, spin-dry, dissolve, wash, separate, and spin-dry to obtain compound a; Q2: Sodium tripolyphosphate, p-chlorophenylglycine, and acetone were sequentially added to a container, cinnamoyl chloride was added to the acetone, stirred to dissolve, and then added dropwise to the container. After the addition was complete, the reaction was continued, filtered, washed, and dried to obtain compound b; Q3: Compound a and triethylamine were added to dichloromethane, stirred, placed in an ice bath, cooled, and a mixed solution of compound b and dichloromethane was added. The mixture was stirred at room temperature for reaction. After the reaction was completed, a saturated sodium bicarbonate solution was added, washed, separated, and the organic phase was collected, dried, distilled under reduced pressure, purified, and filtered to obtain compound c. Compound c was added to a container, heated in an oil bath for reaction. After the reaction was completed, cooled, purified, and filtered to obtain a modified diamine. Q4: Add the modified diamine and 4,4'-diaminodiphenyl ether to N-methylpyrrolidone, stir to dissolve, cool in an ice bath, then add hexafluorodianhydride, react in an ice bath, react at room temperature, then add a mixed solution of anhydrous acetic anhydride and anhydrous triethylamine, heat to react, then add to ethanol, wash, centrifuge, and vacuum dry to obtain a modified functional resin.

3. The epoxy resin for optical fiber array according to claim 2, characterized in that: In Q1, the usage ratio of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, di-tert-butyl dicarbonate, nano-ferrosoferric oxide and anhydrous ethanol is (6.32-7.01) g: (4.38-4.59) g: (0.21-0.35) g: (55-65) mL.

4. The epoxy resin for optical fiber array according to claim 2, characterized in that: In Q2, the usage ratio of sodium tripolyphosphate, p-chlorophenylglycine and cinnamoyl chloride is (8.52-9.16) g: (5.38-5.46) g: (7.81-8.17) g; in Q3, the molar ratio of compound a, triethylamine and compound b is (1-1.3): (2.2-2.6): (2.2-2.8).

5. The epoxy resin for optical fiber array according to claim 2, characterized in that: In Q4, the usage ratio of modified diamine, 4,4'-diaminodiphenyl ether, N-methylpyrrolidone, hexafluorodianhydride, anhydrous acetic anhydride and anhydrous triethylamine is (0.073-0.082) g: (0.64-0.78) g: (6.5-8.5) mL: (1.91-2.17) g: (2.11-2.32) mL: (3.12-3.28) mL.

6. The epoxy resin for optical fiber array according to claim 1, characterized in that: The preparation method of the composite curing agent comprises the following steps: S1: Add 2,3,6,7-tetramethylanthracene-9,10-dione to a container, add cesium fluoride and tetrahydrofuran under nitrogen protection, stir at low temperature, add trimethyl (trifluoromethyl) silane, continue stirring, heat to react, and after the reaction is completed, filter, wash, and purify to obtain product 1; add product 1 to tetrahydrofuran, heat and reflux until dissolved, then add concentrated hydrochloric acid, stir to react, cool, filter, and wash to obtain product 2; S2: Under nitrogen protection, product 2 is added to a container filled with anhydrous benzene, stirred, cooled, trifluoromethanesulfonic acid is added, the reaction is continued, distilled water is added, extraction is carried out, spin-dried, and purified to obtain product 3; product 3 is added to a mixed solution of pyridine and distilled water, heated under reflux to dissolve, and then potassium permanganate is added, the reaction is continued, and ethanol is subsequently added, filtered, concentrated, and purified to obtain product 4; S3: Add product 4 to acetic anhydride, heat under reflux until dissolved, stir to react, concentrate, and purify to obtain product 5. Mix product 5, epoxy acrylate and 2-hydroxy-2-methyl-1-phenylacetone and stir to obtain a composite curing agent.

7. The epoxy resin for optical fiber array according to claim 6, characterized in that: In the S1, the amount ratio of 2,3,6,7-tetramethylanthracene-9,10-dione, cesium fluoride, tetrahydrofuran and trimethyl (trifluoromethyl) silane is (10-12) g: (0.057-0.082) g: (500-600) mL: (6-9) mL; the amount ratio of product 1 and tetrahydrofuran is (10-12) g: (20-25) mL.

8. The epoxy resin for optical fiber array according to claim 6, characterized in that: In S2, the usage ratio of product 2, anhydrous benzene and trifluoromethanesulfonic acid is (5-7.5) g: (10-20) mL: (10-14) mL; the usage ratio of product 3, pyridine, distilled water and potassium permanganate is (5-7.5) g: (160-180) mL: (20-40) mL: (18-22) g.

9. The epoxy resin for optical fiber array according to claim 6, characterized in that: In S3, the usage ratio of product 4 and acetic anhydride is (5-7) g: (30-45) mL; the usage ratio of product 5, epoxy acrylate and 2-hydroxy-2-methyl-1-phenylpropanone is (3-8) g: (2-7) g: (0.03-0.05) g.

10. The method for preparing an epoxy resin for an optical fiber array according to any one of claims 1 to 9, wherein: The following steps are involved: Step 1: Under nitrogen protection, add epoxy resin and modified functional resin into a reactor, heat and stir to react, and obtain a mixture; Step 2: Add the toughening agent and the auxiliary agent to the mixture, continue stirring, cool down, add the composite curing agent, stir, vacuum degas, filter, and obtain the epoxy resin for optical fiber array.

Images