Composite high-temperature resistant material containing glass fiber yarn and its preparation method

Abstract

The present invention belongs to the technical field of composite high-temperature resistant materials, and particularly relates to a composite high-temperature resistant material containing glass fiber yarns and a preparation method thereof. The modified sizing agent of the present invention has excellent adsorption and film-forming properties with a modified film-forming agent prepared from phenyl succinic anhydride-modified starch; 4-vinyl-2,6-dimethoxy-phenol is modified by 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane and then compounded with phenol, and the phenolic resin modified glue obtained by reacting with formaldehyde can enhance the thermal stability of the phenolic resin. The amino-functionalized boron nitride obtained by ball milling boron nitride and urea, and then compounded with alumina ceramic powder and carbon black powder to obtain a flame-retardant and antioxidant filler enhances the interfacial bonding force with the phenolic resin modified glue. After the glass fiber yarns are woven into glass fiber cloth, the flame-retardant and antioxidant filler is bonded by infiltrating the phenolic resin modified glue, and the composite high-temperature resistant material containing glass fiber yarns prepared has excellent antioxidant, high-temperature resistant and wear-resistant properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite high-temperature resistant materials, and particularly relates to a composite high-temperature resistant material containing glass fiber yarns and a preparation method thereof. Background Art

[0002] Glass fiber materials have characteristics such as high mechanical strength, small elongation, corrosion resistance, and good impact resistance, so they are widely used in fields such as construction, aerospace, and electronics and electrical appliances. Although glass fiber materials have high tensile strength, they have a large dynamic friction coefficient and a large bending stiffness, so they are prone to hairiness and yarn entanglement during the textile process.

[0003] The Chinese invention patent with the publication number CN110863360B discloses a preparation process of an electronic-grade glass fiber cloth with high temperature and corrosion resistance. The ordinary alkali-free fiber cloth is impregnated in a sizing solution containing 5-35% of polysiloxane emulsion, 0.5-5% of surfactant, 3-20% of ethanolamine solution, 1-5% of silane coupling agent, and the balance being water. Then, after acid treatment, it is impregnated again in a sizing solution containing 8-15% of epoxy resin, 1-5% of xanthan gum, 0.5-2.5% of EDTA, 0.1-1% of propylene glycol, 3-8% of trimethylolpropane triacrylate, 0.1-0.5% of stabilizer, 0.1-0.5% of antistatic agent, 1-12% of silane coupling agent, and the balance being water. Finally, surface treatment is carried out to make an electronic-grade glass fiber cloth with a unit area weight of 100-200 g / m 2 The Chinese invention patent with the publication number CN117484407A discloses an environment-friendly grinding wheel mesh sheet, which is composed of a glass fiber mesh cloth and an environment-friendly phenolic resin adhesive. The environment-friendly phenolic resin adhesive is composed of the following formulation in mass percentages: 30-35% of thermosetting phenolic resin, 4-6% of emulsifier, 0.4-0.6% of thickener, 0.1-0.3% of coupling agent, 4-6% of solvent, and 55-60% of water. However, the prior art has the technical problem that the glass fiber composite material is not modified by glass fiber sizing agent and phenolic resin components to improve the antioxidant, high-temperature resistant, and wear-resistant properties. Summary of the Invention

[0004] The purpose of the present invention is to provide a composite high-temperature resistant material containing glass fiber yarns and a preparation method thereof, which are used to solve the technical problem in the prior art that the glass fiber composite material is not modified by glass fiber sizing agent and phenolic resin components to improve the antioxidant, high-temperature resistant, and wear-resistant properties.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0006] The composite high-temperature resistant material containing glass fiber yarn, by mass, comprises the following raw materials: 80 - 100 parts of glass fiber cloth, 20 - 30 parts of modified sizing agent, 20 - 30 parts of phenolic resin modified glue, 1 - 3 parts of hexamine curing agent, and 5 - 6 parts of flame retardant and antioxidant filler;

[0007] The glass fiber cloth is made by plain weaving or twill weaving of glass fiber yarn. The glass fiber yarn, by mass, comprises the following raw materials: 64 - 66 parts of silica, 15 - 18 parts of alumina, 5 - 6 parts of boric acid, 5 - 8 parts of magnesium oxide, and 5 - 8 parts of calcium carbonate;

[0008] The modified sizing agent, by mass, comprises the following raw materials: 20 - 25 parts of modified film-forming agent, 0.5 - 1 part of antibacterial agent, 0.5 - 1 part of antistatic agent, 0.5 - 1 part of defoaming agent, and 7 - 10 parts of lubricating solvent;

[0009] The antibacterial agent is one or more combinations of dibutyltin maleate, tributyltin oxide, and dioctyltin dilaurate; the antistatic agent is one or more combinations of alkyl dicarboxymethyl ammonium inner ester, stearyl trimethyl quaternary ammonium salt, and antistatic agent 1631; the defoaming agent is one or more combinations of DF - 696, DF - 420, and AC - 10.

[0010] The preparation method of the composite high-temperature resistant material containing glass fiber yarn comprises the following steps:

[0011] S1. Put silica, alumina, boric acid, magnesium oxide, and calcium carbonate into a blender and stir for 30 - 50 min to obtain a glass mixture. Preheat the crucible to 1200 - 1300 °C, add the glass mixture in multiple batches with an interval of 20 - 40 min between batches. After adding all the materials, raise the temperature to 1500 - 1600 °C and keep it warm for 4 - 8 h. After discharging the bubbles from the molten glass solution, make the glass solution flow out in filaments through a porous sieve plate, coat the filamentous glass fiber with the modified sizing agent through an oiling roller, and collect and draw the fiber with a take-up wheel to obtain glass fiber filaments;

[0012] S2. Pass the glass fiber filaments through a warping machine for impurity removal and winding and finishing to make glass fiber yarn. Use the glass fiber yarn as warp and weft yarns and weave them into glass fiber cloth through a loom;

[0013] S3. After adding the hexamine curing agent to the phenolic resin modified glue, soak the glass fiber cloth, bond the flame retardant and antioxidant filler on both sides of the glass cloth, and cure to obtain a crude composite flame retardant and antioxidant filler;

[0014] S4. Cut the crude composite flame retardant and antioxidant filler into the required specifications to obtain the composite high-temperature resistant material product containing glass fiber yarn.

[0015] Preferably, in S1, the mass ratio of silica to alumina is 3.8 to 4:1, and the mass ratio of magnesium oxide to calcium carbonate is 0.9 to 1:1.

[0016] Preferably, in S1, the wire drawing speed of the wire take-up wheel is 40 to 50 m / min, and the average diameter of the glass fiber filaments is 5 to 15 μm.

[0017] Preferably, in S2, the single yarn density of the warp and weft yarns is 27 to 30 tex.

[0018] Preferably, in S2, the mesh number of the glass fiber cloth is 6 to 7, and the gram weight is 200 to 220 g / m 2 。

[0019] Preferably, in S3, the curing reaction is carried out at 150 to 170 °C for 1 to 2 h.

[0020] Preferably, the preparation method of the modified sizing agent in S1 includes the following steps:

[0021] S11. By mass, add 15 to 20 parts of castor oil and 4.1 to 5.8 parts of methanol into the reaction kettle, heat up to 60 to 70 °C under stirring, add 0.2 to 0.5 part of alkali catalyst, after reacting for 1 to 2 h, add 5 wt% dilute sulfuric acid until the pH of the reaction system is 2 to 3, let it stand for 20 to 24 h for stratification, take the upper layer liquid, wash it with water until neutral, and remove impurities by low-pressure fractional distillation to obtain methyl ricinoleate. Blend 15 to 20 parts of methyl ricinoleate and 1.5 to 3 parts of dibutyl phthalate to obtain a lubricating solvent;

[0022] S12. By mass, add 10 to 20 parts of starch with a linear chain content of 55 to 60% into 80 to 100 parts of deionized water, stir evenly at low speed and then dropwise add 6 to 12 parts of phenyl succinic anhydride acetone solution, and adjust the pH to 8.4 to 8.6 with 10 wt% sodium hydroxide solution, finish dropping within 2 to 3 h, react at 30 to 35 °C for 2 to 3 h and then dropwise add 5 wt% dilute sulfuric acid until the pH is 6.5 to 7, filter and wash successively with deionized water and absolute ethanol, dry at 30 to 40 °C, and pulverize and sieve to obtain a modified film-forming agent;

[0023] S13. By mass, add 20 to 25 parts of the modified film-forming agent, 0.5 to 1 part of defoaming agent, 0.3 to 0.5 part of antibacterial agent and 0.5 to 1 part of antistatic agent into 7 to 10 parts of lubricating solvent, heat up to 85 to 95 °C under stirring and gelatinize for 1 to 2 h to obtain the modified sizing agent.

[0024] Preferably, in S11, the mass ratio of castor oil to methanol is 10:2.7 to 2.9.

[0025] Preferably, the base catalyst in S11 is one or a combination of dimethylamine, 4-dimethylaminopyridine, and tetramethylammonium hydroxide.

[0026] Preferably, the preparation method of the phenolic resin modified glue in S3 includes the following steps:

[0027] S21. According to parts by mass, add 10 - 15 parts of 4-vinyl-2,6-dimethoxyphenol to the reaction kettle, heat up to 50 - 55 °C, dropwise add 0.5 - 2 parts of the catalyst and 8 - 14 parts of 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane, and heat up to 80 - 90 °C for reaction for 2 - 3 h to obtain silane-modified 4-vinyl-2,6-dimethoxyphenol;

[0028] S22. According to parts by mass, add 100 - 115 parts of phenol and 10 - 15 parts of silane-modified 4-vinyl-2,6-dimethoxyphenol to the reaction kettle, heat up to 50 - 55 °C, after the phenol is completely melted, add 0.5 - 2 parts of the metal salt catalyst and 60 - 70 parts of 37 wt% formaldehyde solution, and react at 100 - 110 °C for 4 - 8 h to obtain the crude phenolic resin;

[0029] S23. Wash the crude phenolic resin with deionized water, then carry out vacuum distillation, and add 50 - 80 parts of ethanol for dilution to obtain the phenolic resin modified glue.

[0030] Preferably, the synthesis route of the silane-modified 4-vinyl-2,6-dimethoxyphenol is as follows:

[0031]

[0032] The result of mass spectrometry analysis is: m / z: 630.25 (100.0%), 631.25 (49.1%), 632.25(17.6%), 632.26 (5.8%), 633.25 (5.0%), 633.26 (2.1%), 634.25 (1.1%).

[0033] Preferably, the catalyst in S21 is one or a combination of chloroplatinic acid, nickel cyclooctadiene, and Karstedt's platinum catalyst.

[0034] Preferably, the metal salt catalyst in S22 is one or a combination of zinc acetate, magnesium tartrate, and tin oxalate.

[0035] Preferably, the preparation method of the flame retardant and antioxidant filler in S3 includes the following steps:

[0036] S31. By mass parts, mix 5 - 6 parts of boron nitride, 100 - 150 parts of urea, and 50 - 70 parts of deionized water evenly, add them to a ball mill and ball mill for 12 - 16 h, then add them to 200 parts of deionized water, ultrasonicate for 15 - 30 min, filter and collect the solid to obtain amino-functionalized boron nitride.

[0037] S32. By mass parts, mix 4 - 5 parts of amino-functionalized boron nitride, 5 - 6 parts of alumina ceramic powder, and 20 - 30 parts of carbon black powder evenly to obtain a flame-retardant and antioxidant filler.

[0038] Preferably, in S32, the average particle size of the alumina ceramic powder is 1 - 3 μm, and the average particle size of the carbon black powder is 10 - 30 μm.

[0039] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0040] 1. Based on the existing technology, the present invention optimizes the preparation process and composition of the fiberglass cloth. The modified film-forming agent prepared by modifying starch with phenyl succinic anhydride in the modified sizing agent has excellent adsorption and film-forming properties, avoiding the phenomenon of yarn entanglement when the fiberglass yarn is woven into the fiberglass cloth. Then, by infiltrating the phenolic resin-modified adhesive with the flame-retardant and antioxidant filler, the obtained product, i.e., the composite high-temperature resistant material containing fiberglass yarn, has excellent antioxidant, high-temperature resistant, and wear-resistant properties.

[0041] 2. The present invention uses the castor oil methyl ester and dibutyl ester obtained by reacting castor oil with methanol to blend and obtain a lubricating solvent, which has good lubricating and plasticizing properties; the modified film-forming agent prepared by modifying starch with a phenyl succinic anhydride acetone solution, where the hydroxyl group in the starch reacts with phenyl succinic anhydride to undergo an esterification reaction and graft a phenyl hydrophobic group on the side chain, improving the high-temperature stability of the starch; the modified sizing agent prepared by compounding with an antifoaming agent, an antibacterial agent, and an antistatic agent has good renewable, adhesive, and film-forming properties.

[0042] 3. The present invention modifies 4-vinyl-2,6-dimethoxyphenol with 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane and then compounds it with phenol, and reacts with formaldehyde to obtain a phenolic resin-modified adhesive. 4-vinyl-2,6-dimethoxyphenol has methoxy and butoxymethyl groups, which can enhance the thermal stability of the phenolic resin. First, silane modification and then synthesis of the phenolic resin enable the silicon element to be more evenly dispersed in the phenolic resin, making the phenolic resin-modified adhesive have excellent wear-resistant and weather-resistant properties.

[0043] 4. The flame-retardant and antioxidant filler obtained by ball-milling boron nitride and urea in the present invention and then compounding it with alumina ceramic powder and carbon black powder can react and combine with the hydroxyl or aldehyde group of the phenolic resin modified glue through the amino group, enhancing the interfacial bonding force between the flame-retardant and antioxidant filler and the phenolic resin modified glue, and making the product have better wear resistance and antioxidant performance. Detailed implementation mode

[0044] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0045] Example 1. The composite high-temperature resistant material containing glass fiber yarn in this example, by mass, includes the following raw materials: 100 parts of glass fiber cloth, 25 parts of modified sizing agent, 30 parts of phenolic resin modified glue, 3 parts of hexamine curing agent, and 6 parts of flame-retardant and antioxidant filler;

[0046] The glass fiber cloth is made by plain weaving of glass fiber yarn. The glass fiber yarn, by mass, includes the following raw materials: 64 parts of silicon dioxide, 16 parts of alumina, 6 parts of boric acid, 7 parts of magnesium oxide, and 7 parts of calcium carbonate;

[0047] The modified sizing agent, by mass, includes the following raw materials: 20 parts of modified film-forming agent, 0.5 part of antibacterial agent, 0.5 part of antistatic agent, 0.5 part of defoaming agent, and 7 parts of lubricating solvent;

[0048] The antibacterial agent is dibutyltin maleate; the antistatic agent is antistatic agent 1631; the defoaming agent is DF-696.

[0049] The preparation method of the composite high-temperature resistant material containing glass fiber yarn in this example includes the following steps:

[0050] S1. By mass, put silicon dioxide, alumina, boric acid, magnesium oxide, and calcium carbonate into a mixer and stir for 30 min to obtain a glass mixture. Preheat the crucible to 1300 °C, add the glass mixture in multiple batches with an interval of 20 min between batches. After adding the materials, raise the temperature to 1550 °C and keep it warm for 6 h. After discharging the bubbles from the molten glass solution, make the glass solution flow out in filaments through a porous sieve plate. Coat the filamentous glass fiber with the modified sizing agent through an oiling roller, and wind up the drawing with a winding wheel at a drawing rate of 50 m / min to obtain glass fiber filaments with an average diameter of 7.5 μm;

[0051] S2. According to parts by mass, glass fiber filaments are made into glass fiber yarn through warping machines for impurity removal and winding and finishing. The glass fiber yarn is used as warp and weft yarns, and woven into a glass fiber cloth with a mesh number of 6 and a grammage of 211 g / m 2 of the glass fiber cloth;

[0052] S3. According to parts by mass, after adding hexamine curing agent to the phenolic resin modified glue, the glass fiber cloth is infiltrated, and flame retardant and antioxidant fillers are bonded to both sides of the glass cloth, and reacted and cured at 170 °C for 1 h to obtain a crude composite flame retardant and antioxidant filler;

[0053] S4. The crude composite flame retardant and antioxidant filler is cut into the required specifications to obtain a composite high-temperature resistant material product containing glass fiber yarn.

[0054] The preparation method of the modified sizing agent in this embodiment includes the following steps:

[0055] S11. According to parts by mass, 20 parts of castor oil and 5.8 parts of methanol are added to a reaction kettle, heated to 70 °C under stirring, 0.4 part of an alkali catalyst is added, after reacting for 2 h, 5 wt% dilute sulfuric acid is added until the pH of the reaction system is 3, left standing for 24 h for stratification, the upper layer liquid is taken, washed with water until neutral, and fractionated under low pressure to remove impurities to obtain methyl ricinoleate. 20 parts of methyl ricinoleate and 3 parts of dibutyl phthalate are blended to obtain a lubricating solvent;

[0056] S12. According to parts by mass, 10 parts of starch with a linear content of 60% is added to 80 parts of deionized water, stirred evenly at low speed, 6 parts of phenyl succinic anhydride acetone solution is added dropwise, and the pH is adjusted to 8.5 with 10 wt% sodium hydroxide solution, added dropwise within 2 h, reacted at 35 °C for 3 h, then 5 wt% dilute sulfuric acid is added dropwise until the pH is 7, filtered and washed successively with deionized water and absolute ethanol, dried at 40 °C, and pulverized and sieved to obtain a modified film-forming agent;

[0057] S13. According to parts by mass, 20 parts of the modified film-forming agent, 0.5 part of defoaming agent, 0.5 part of antibacterial agent and 0.5 part of antistatic agent are added to 7 parts of lubricating solvent, heated to 95 °C under stirring for gelatinization for 1 h to obtain a modified sizing agent.

[0058] The preparation method of the phenolic resin modified glue in this embodiment includes the following steps:

[0059] S21. According to parts by mass, 15 parts of 4-vinyl-2,6-dimethoxyphenol are added to a reaction kettle, heated to 55 °C, 2 parts of Karstedt's platinum catalyst and 13.5 parts of 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane are added dropwise, and heated to 85 °C for reaction for 2 h to obtain silane-modified 4-vinyl-2,6-dimethoxyphenol;

[0060] S22. By mass, add 115 parts of phenol and 15 parts of silane-modified 4-vinyl-2,6-dimethoxyphenol into a reaction kettle, heat up to 55 °C, after the phenol is completely melted, add 1 part of magnesium tartrate and 70 parts of 37 wt% formaldehyde solution, and react at 105 °C for 4 h to obtain a crude phenolic resin.

[0061] S23. Wash the crude phenolic resin with deionized water, then perform vacuum distillation, and add 80 parts of ethanol for dilution to obtain a modified phenolic resin adhesive.

[0062] The preparation method of the flame-retardant and antioxidant filler in this example includes the following steps:

[0063] S31. By mass, mix 6 parts of boron nitride, 150 parts of urea and 70 parts of deionized water evenly, add them into a ball mill and ball mill for 16 h, then add them into 200 parts of deionized water, ultrasonic for 30 min, filter and collect the solid to obtain aminated boron nitride.

[0064] S32. By mass, mix 5 parts of aminated boron nitride, 6 parts of alumina ceramic powder and 20 parts of carbon black powder evenly to obtain the flame-retardant and antioxidant filler.

[0065] Example 2. The composite high-temperature resistant material containing fiberglass yarn in this example, by mass, includes the following raw materials: 100 parts of fiberglass cloth, 30 parts of modified sizing agent, 30 parts of modified phenolic resin adhesive, 3 parts of hexamine curing agent and 5 parts of flame-retardant and antioxidant filler.

[0066] The fiberglass cloth is made by plain weaving of fiberglass yarn. By mass, the fiberglass yarn includes the following raw materials: 65 parts of silica, 17 parts of alumina, 6 parts of boric acid, 5.7 parts of magnesium oxide and 6.3 parts of calcium carbonate.

[0067] By mass, the modified sizing agent includes the following raw materials: 20 parts of modified film-forming agent, 0.5 part of antibacterial agent, 0.5 part of antistatic agent, 0.5 part of defoaming agent and 7 parts of lubricating solvent.

[0068] The antibacterial agent is tributyltin oxide; the antistatic agent is alkyl dicarboxymethyl ammonium inner ester; the defoaming agent is AC-10.

[0069] The preparation method of the composite high-temperature resistant material containing fiberglass yarn in this example includes the following steps:

[0070] S1. By mass parts, put silica, alumina, boric acid, magnesia and calcium carbonate into a blender and stir for 35 min to obtain a glass mixture. Preheat a crucible to 1210 °C, add the glass mixture in multiple batches with an interval of 25 min between each addition. After the addition is completed, raise the temperature to 1570 °C and keep it warm for 4 h. After removing the bubbles from the molten glass solution, make the glass solution flow out in filaments through a perforated sieve plate. Coat the filamentous glass fiber with a modified sizing agent through an oiling roller, and wind the wire with a wire winding wheel at a wire drawing rate of 40 m / min to obtain glass fiber filaments, and the average diameter of the glass fiber filaments is 13.1 μm;

[0071] S2. By mass parts, pass the glass fiber filaments through a warping machine for impurity removal and winding and finishing to make glass fiber yarns. Use the glass fiber yarns as warp yarns and weft yarns, and weave them into a glass fiber cloth with a mesh number of 6 and a grammage of 216 g / m 2 of the glass fiber cloth;

[0072] S3. By mass parts, add hexamine curing agent to the phenolic resin modified glue and then infiltrate the glass fiber cloth. Bond flame retardant and antioxidant fillers on both sides of the glass cloth, and cure to obtain a crude composite flame retardant and antioxidant filler;

[0073] S4. Cut the crude composite flame retardant and antioxidant filler into the required specifications to obtain a composite high-temperature resistant material product containing glass fiber yarns.

[0074] The preparation methods of the modified sizing agent and the flame retardant and antioxidant filler in this example are the same as those in Example 1.

[0075] The difference between the phenolic resin modified adhesive in this example and that in Example 1 is that by mass parts, the parts of phenol, silane-modified 4-vinyl-2,6-dimethoxyphenol and 37 wt% formaldehyde solution are replaced by 100 parts of phenol, 10 parts of silane-modified 4-vinyl-2,6-dimethoxyphenol and 65 parts of 37 wt% formaldehyde solution.

[0076] Example 3. The composite high-temperature resistant material containing glass fiber yarns in this example, by mass parts, includes the following raw materials: 80 parts of glass fiber cloth, 20 parts of modified sizing agent, 30 parts of phenolic resin modified glue, 1 part of hexamine curing agent and 5 parts of flame retardant and antioxidant filler;

[0077] The glass fiber cloth is made by plain weaving of glass fiber yarns. The glass fiber yarns, by mass parts, include the following raw materials: 65 parts of silica, 17 parts of alumina, 6 parts of boric acid, 5.7 parts of magnesia and 6.3 parts of calcium carbonate;

[0078] The modified sizing agent, by mass parts, includes the following raw materials: 20 parts of modified film-forming agent, 0.8 part of antibacterial agent, 1 part of antistatic agent, 0.5 part of defoaming agent and 7 parts of lubricating solvent;

[0079] The antibacterial agent is dioctyltin dilaurate; the antistatic agent is alkyl dimethylammonium ethyl lactone; the defoaming agent is DF-420.

[0080] The preparation method of the composite high-temperature resistant material containing glass fiber yarn in this embodiment includes the following steps:

[0081] S1. By mass, put silica, alumina, boric acid, magnesium oxide and calcium carbonate into a blender and stir for 50 min to obtain a glass mixture. Preheat the crucible to 1240 °C, add the glass mixture in multiple batches with an interval of 40 min between each addition. After the addition is completed, raise the temperature to 1510 °C and keep it warm for 8 h. After removing the bubbles from the molten glass solution, make the glass solution flow out in filaments through a porous sieve plate. Coat the filamentous glass fiber with a modified sizing agent through an oiling roller, and use a winding wheel to collect and draw the wire at a drawing rate of 50 m / min to obtain glass fiber filaments with an average diameter of 6.5 μm.

[0082] S2. By mass, pass the glass fiber filaments through a warping machine for impurity removal and winding arrangement to make glass fiber yarn. Use the glass fiber yarn as the warp and weft yarns, and weave them into a glass fiber cloth with a mesh number of 7 and a gram weight of 217 g / m 2 2.

[0083] S3. By mass, add hexamine curing agent to the phenolic resin modified adhesive and infiltrate the glass fiber cloth. Bond flame retardant and antioxidant fillers on both sides of the glass cloth, and react and cure at 170 °C for 1 h to obtain a crude composite flame retardant and antioxidant filler.

[0084] S4. Cut the crude composite flame retardant and antioxidant filler into the required specifications to obtain a composite high-temperature resistant material product containing glass fiber yarn.

[0085] The preparation methods of the phenolic resin modified adhesive and the flame retardant and antioxidant filler in this embodiment are the same as those in Example 1.

[0086] The difference between the modified sizing agent in this embodiment and that in Example 1 is that by mass, 15 parts of starch with a straight-chain content of 55% is used to replace 60% of the starch with a straight-chain content.

[0087] Example 4. The composite high-temperature resistant material containing glass fiber yarn in this embodiment, by mass, includes the following raw materials: 100 parts of glass fiber cloth, 25 parts of modified sizing agent, 30 parts of phenolic resin modified adhesive, 3 parts of hexamine curing agent and 6 parts of flame retardant and antioxidant filler;

[0088] The glass fiber cloth is made by plain weaving of glass fiber yarn. By mass, the glass fiber yarn includes the following raw materials: 65 parts of silica, 17 parts of alumina, 6 parts of boric acid, 5.7 parts of magnesium oxide and 6.3 parts of calcium carbonate;

[0089] The modified sizing agent, by mass parts, comprises the following raw materials: 25 parts of modified film-forming agent, 1 part of antibacterial agent, 1 part of antistatic agent, 1 part of defoaming agent and 10 parts of lubricating solvent;

[0090] The antibacterial agent is dibutyltin maleate; the antistatic agent is stearyl trimethyl quaternary ammonium salt; the defoaming agent is DF-420.

[0091] The preparation method of the composite high-temperature resistant material containing glass fiber yarn in this embodiment comprises the following steps:

[0092] S1. By mass parts, put silicon dioxide, alumina, boric acid, magnesium oxide and calcium carbonate into a blender and stir for 30 min to obtain a glass mixture. Preheat a crucible to 1210 °C, add the glass mixture in multiple batches with an interval of 20 min between batches. After adding the materials, raise the temperature to 1590 °C and keep it warm for 4 h. After removing the bubbles from the molten glass solution, make the glass solution flow out in filaments through a porous sieve plate. Coat the filamentous glass fiber with the modified sizing agent through an oiling roller, and wind and draw the glass fiber with a winding wheel at a drawing rate of 45 m / min to obtain glass fiber filaments, and the average diameter of the glass fiber filaments is 6.2 μm;

[0093] S2. By mass parts, pass the glass fiber filaments through a warping machine for impurity removal and winding and finishing to make glass fiber yarn. Use the glass fiber yarn as warp and weft yarns, and weave them into a glass fiber cloth with a mesh number of 7 and a grammage of 214 g / m 2 of glass fiber cloth;

[0094] S3. By mass parts, after adding hexamine curing agent to the phenolic resin modified glue, soak the glass fiber cloth, bond flame retardant and antioxidant fillers on both sides of the glass cloth, and react and cure at 150 °C for 2 h to obtain a crude product of composite flame retardant and antioxidant filler;

[0095] S4. Cut the crude product of the composite flame retardant and antioxidant filler into the required specifications to obtain a composite high-temperature resistant material product containing glass fiber yarn.

[0096] The preparation methods of the modified sizing agent and the phenolic resin modified glue in this embodiment are the same as those in Embodiment 1.

[0097] The difference between the flame retardant and antioxidant filler in this embodiment and that in Embodiment 1 is that by mass parts, the parts of boron nitride and urea are replaced with 5 parts of boron nitride and 100 parts of urea.

[0098] Comparative Example 1. The difference between this comparative example and Embodiment 1 is that the modified sizing agent is replaced with a paraffin wax type sizing agent.

[0099] Comparative Example 2. The difference between this comparative example and Embodiment 1 is that by mass parts, the parts of silane-modified 4-vinyl-2,6-dimethoxyphenol are replaced with 50 parts.

[0100] Comparative Example 3. The difference between this comparative example and Example 1 is that the amino-functionalized boron nitride in the flame retardant and antioxidant filler is replaced by boron nitride.

[0101] Performance Test

[0102] According to JC / T 841-2007 "Alkali-resistant fiberglass mesh", the radial fracture strength and weft fracture strength of the composite high-temperature resistant materials prepared in each example and comparative example were measured; the composite high-temperature resistant materials prepared in each example and comparative example were placed in a resistance box and heat-treated at 450 °C for 1 h, and then the appearance, radial fracture strength and weft fracture strength of the composite high-temperature resistant materials after heat treatment were measured. The test results are shown in Table 1:

[0103] Table 1 Appearance, Radial Fracture Strength and Weft Fracture Strength Test

[0104]

[0105] According to GB 3960-83 "Test Method for Sliding Friction and Wear of Plastics", the wear rate of the composite high-temperature resistant materials prepared in each example and comparative example was measured on a friction and wear testing machine. The test results are shown in Table 2:

[0106] Table 2 Wear Rate Test

[0107] Serial number Wear rate (%) Example 1 0.63 Example 2 0.61 Example 3 0.58 Example 4 0.60 Comparative example 1 0.74 Comparative example 2 0.85 Comparative example 3 0.88

[0108] From the data in the above table, it can be seen that the radial fracture strength of the composite high-temperature resistant materials prepared in Examples 1 to 4 before heat treatment is between 2443 and 2478 N / 50 mm, and the weft fracture strength is between 2403 and 2441 N / 50 mm, indicating that the composite high-temperature resistant materials containing fiberglass yarn prepared by the present invention have excellent mechanical properties; after heat treatment, there are no cracks on the surface of the composite high-temperature resistant materials prepared in Examples 1 to 4, and the radial fracture strength after heat treatment is between 2401 and 2433 N / 50 mm, and the weft fracture strength is between 2353 and 2377 N / 50 mm. In Comparative Example 1, the fiberglass cloth prepared with a paraffin-type sizing agent generates fluff during the weaving process, resulting in poor wetting effect with the phenolic resin modified glue. Therefore, there are cracks on the surface of the material after heat treatment, and the radial fracture strength and weft fracture strength are much lower than the data of each example, indicating that the composite high-temperature resistant materials prepared by the present invention have excellent high-temperature resistance and antioxidant properties; the wear rate of the composite high-temperature resistant materials prepared in Examples 1 to 4 is between 0.58 and 0.63%, indicating that the composite high-temperature resistant materials prepared by the present invention have excellent wear resistance.

[0109] As described above, it is only the preferred specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

[0110] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific implementation modes. Obviously, according to the content of this specification, many modifications and changes can be made. This specification selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art in the relevant technical field can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A method for preparing a composite high temperature resistant material comprising glass fiber yarn, characterized in that: The composite high temperature resistant material containing glass fiber yarn includes the following raw materials by mass: 80-100 parts of glass fiber cloth, 20-30 parts of modified impregnation agent, 20-30 parts of phenolic resin modified glue, 1-3 parts of urotropine curing agent and 5-6 parts of flame retardant antioxidant filler; The glass fiber cloth is made of glass fiber yarn through plain weaving or twisting weaving. The glass fiber yarn includes the following raw materials by mass: 64-66 parts of silicon dioxide, 15-18 parts of aluminum oxide, 5-6 parts of boric acid, 5-8 parts of magnesium oxide and 5-8 parts of calcium carbonate; The modified impregnating agent comprises the following raw materials by weight: 20-25 parts of modified film-forming agent, 0.5-1 parts of antibacterial agent, 0.5-1 parts of antistatic agent, 0.5-1 parts of defoaming agent and 7-10 parts of lubricating solvent; A method for preparing a composite high temperature resistant material containing glass fiber yarn comprises the following steps: S1. Put silicon dioxide, aluminum oxide, boric acid, magnesium oxide and calcium carbonate into a mixer and stir for 30-50 minutes to obtain a glass mixture. Preheat the crucible to 1200-1300° C., add the glass mixture several times, with a feeding interval of 20-40 minutes. After the feeding is completed, heat it to 1500-1600° C. and keep it warm for 4-8 hours. After the bubbles are discharged from the molten glass solution, the glass solution is made to flow out in the form of filaments through a porous plate. The filamentary glass fiber is coated with a modified sizing agent through an oiling roller, and the filamentary glass fiber is bundled and drawn with a wire collection wheel to obtain glass fiber filaments. The preparation method of the modified sizing agent in S1 comprises the following steps: S11. Add 15-20 parts of castor oil and 4.1-5.8 parts of methanol to a reactor by weight, heat to 60-70°C under stirring, add 0.2-0.5 parts of an alkali catalyst, react for 1-2 hours, add 5wt% of dilute sulfuric acid until the pH of the reaction system is 2-3, let stand for 20-24 hours to separate the layers, take the upper layer of liquid, wash with water until neutral, remove impurities by low-pressure fractionation to obtain castor oil methyl ester, blend 15-20 parts of castor oil methyl ester and 1.5-3 parts of dibutyl ester to obtain a lubricating solvent; S12, according to mass parts, add 10-20 parts of starch with a linear content of 55-60% to 80-100 parts of deionized water, stir evenly at a low speed, then drop 6-12 parts of phenylsuccinic anhydride acetone solution, and adjust the pH to 8.4-8.6 with 10wt% sodium hydroxide solution, and drip it within 2-3 hours, react at 30-35°C for 2-3 hours, then drop 5wt% of dilute sulfuric acid to a pH of 6.5-7, filter and wash with deionized water and anhydrous ethanol in turn, dry at 30-40°C, and pulverize and sieve to obtain a modified film-forming agent; S13, according to the mass parts, add 20-25 parts of the modified film-forming agent, 0.5-1 parts of the defoaming agent, 0.3-0.5 parts of the antibacterial agent and 0.5-1 parts of the antistatic agent to 7-10 parts of the lubricating solvent, raise the temperature to 85-95° C. under stirring, and gelatinize for 1-2 hours to obtain a modified impregnating agent; S2, passing the glass fiber yarn through a warping machine to remove impurities and wind the wire to make glass fiber yarn, and using the glass fiber yarn as warp yarn and weft yarn to weave glass fiber cloth through a loom; S3, adding urotropine curing agent to the phenolic resin modified glue to soak the glass fiber cloth, bonding the flame retardant and antioxidant filler on both sides of the glass cloth, and curing to obtain a crude composite flame retardant and antioxidant filler; the preparation method of the phenolic resin modified glue in S3 comprises the following steps: S21, according to the mass parts, add 10-15 parts of 4-vinyl-2,6-dimethoxy-phenol into the reaction kettle, heat it to 50-55°C, dropwise add 0.5-2 parts of catalyst and 8-14 parts of 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane, heat it to 80-90°C and react for 2-3h to obtain silane-modified 4-vinyl-2,6-dimethoxy-phenol; S22, according to the mass parts, add 100-115 parts of phenol and 10-15 parts of silane-modified 4-vinyl-2,6-dimethoxy-phenol into the reaction kettle, heat it to 50-55° C., add 0.5-2 parts of metal salt catalyst and 60-70 parts of 37wt% formaldehyde solution after the phenol is completely melted, react at 100-110° C. for 4-8h, and obtain a crude phenolic resin; S23, washing the crude phenolic resin with deionized water, distilling under reduced pressure, and adding 50-80 parts of ethanol to dilute to obtain a phenolic resin modified glue; The method for preparing the flame retardant and antioxidant filler in S3 comprises the following steps: S31, according to the mass parts, 5-6 parts of boron nitride, 100-150 parts of urea and 50-70 parts of deionized water were mixed evenly, added to a ball mill, and ball milled for 12-16 hours, then added to 200 parts of deionized water, ultrasonicated for 15-30 minutes, and filtered to collect the solid to obtain aminated boron nitride; S32, according to mass parts, 4-5 parts of amidated boron nitride, 5-6 parts of alumina ceramic powder and 20-30 parts of carbon black powder are mixed uniformly to prepare a flame retardant and antioxidant filler; S4. Cutting the crude composite flame retardant and antioxidant filler into required specifications to obtain a composite high temperature resistant material product containing glass fiber yarn.

2. The method for preparing a composite high temperature resistant material comprising glass fiber yarn according to claim 1, characterized in that: The mass ratio of silicon dioxide to aluminum oxide in S1 is 3.8-4:1, the mass ratio of magnesium oxide to calcium carbonate is 0.9-1:1, the drawing speed of the wire drawing wheel is 40-50 m / min, and the average diameter of the glass fiber is 5-15 μm; the single yarn density of the warp and weft in S2 is 27-30 tex, the mesh number of the glass fiber is 6-7, and the gram weight is 200-220 g / m 2 ; The curing in S3 is carried out at 150-170° C. for 1-2 hours.

3. The method for preparing a composite high temperature resistant material containing glass fiber yarn according to claim 1, characterized in that: The mass ratio of castor oil to methanol in the S11 is 10:2.7-2.

9.

4. The method for preparing a composite high temperature resistant material comprising glass fiber yarn according to claim 1, characterized in that: The catalyst in S21 is one or more combinations of platinum chloride, cyclooctadiene nickel, and Custer platinum catalyst, and the metal salt catalyst in S22 is one or more combinations of zinc acetate, magnesium tartrate, and tin oxalate.

5. The method for preparing a composite high temperature resistant material containing glass fiber yarn according to claim 1, characterized in that: The average particle size of the alumina ceramic powder in S32 is 1-3 μm, and the average particle size of the carbon black powder is 10-30 μm.

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