High-uniformity glass fiber cloth and weaving process thereof

Abstract

The invention discloses high-uniformity glass fiber cloth and a weaving process thereof, and belongs to the technical field of glass fiber cloth. The preparation method is used for solving the technical problems of uneven coating and difficult degradation caused by poor mechanical property and overhigh viscosity of glass fiber cloth impregnated with organic resin in the prior art. A weaving technology of high-uniformity glass fiber cloth comprises the following steps that the front face and the back face of modified glass fiber cloth are coated with modified polymer resin, the front face and the back face of the modified glass fiber cloth are coated with a layer of modified glass fiber cloth, and composite fiber cloth is formed; and drying and curing the composite fiber cloth to obtain the high-uniformity glass fiber cloth. The glass fiber cloth is modified by adopting a coupling agent mixed solution, so that the polarity of the glass fiber cloth and the chemical reaction activity of modified polymerized polyester are improved; the modified polymer resin takes polylactic acid as a base and is modified by a multi-epoxy-group chain extender; the coated and cured glass fiber cloth has the advantages that the mechanical strength is high, and the coated modified polyester is easy to degrade.

Description

Technical Field

[0001] The present invention relates to the technical field of fiberglass cloth, and particularly relates to a highly uniform fiberglass cloth and its weaving process. Background Art

[0002] Fiberglass refers to glass filaments with a diameter ranging from several hundred nanometers to dozens of micrometers obtained by melting glass with silica as the main body and adding oxides such as calcium, boron, and aluminum, and then stretching it through a special process. As an inorganic non-metallic high-strength reinforcing material, fiberglass has the advantages of light weight, high strength modulus, low density, and high temperature resistance, and can be widely used in fields such as aerospace, automobiles, and industry. In addition, the composite thermoplastic composite material prepared by compounding an alkali-free fiberglass cloth with an organic resin has excellent mechanical properties, easy molding, a short production cycle, and recyclability, and has stronger competitiveness when applied to the fields of aerospace, national defense, energy, and the electronics industry. It is regarded as an ideal choice for structural materials and has broad application potential. However, due to the high viscosity of thermoplastic resins, it is not conducive to the uniform impregnation of reinforcing materials in the molten state; how to effectively disperse the load of composite materials and improve the degradability of prepared composite fiberglass cloth has become a popular research field.

[0003] Patent application CN103497349A discloses a pre-cured fiberglass cloth impregnating material and its preparation method. The fiberglass cloth is prepared into a fiberglass cloth of a composite structural material by coating an organic adhesive and baking; the above-mentioned organic adhesive includes a benzoxazine-maleimide resin solution and a linear m-phenylene unsaturated polyester; by using the heterocyclic structure of the benzoxazine-maleimide resin solution and the benzene ring structure of the linear m-phenylene unsaturated polyester, the mechanical properties and mechanical strength of the impregnated fiberglass cloth are improved. However, the above fiberglass has the disadvantages of poor degradation performance, uneven impregnation due to the too high viscosity of the organic adhesive, and uneven mechanical properties of the fiber cloth.

[0004] In view of the technical defects in this regard, a solution is now proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a highly uniform fiberglass cloth and its weaving process, which are used to solve the technical problems of poor mechanical properties, uneven coating due to too high viscosity, and difficult degradation when using an organic resin to impregnate a fiberglass cloth in the prior art.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A weaving process for a highly uniform fiberglass cloth includes the following steps:

[0008] S1. Both the front and back sides of the modified glass fiber cloth are coated with a modified polymeric resin to obtain the sprayed modified glass fiber cloth; the sprayed modified glass fiber cloth is used as the intermediate layer, and a modified glass fiber cloth is laminated on both its front and back sides to form a composite fiber cloth;

[0009] S2. The composite fiber cloth is dried and cured to synthesize a highly uniform glass fiber cloth.

[0010] In the present invention, the glass fiber cloth is pre-modified to obtain a modified glass fiber cloth. Then, a modified polymeric resin is coated on the modified glass fiber cloth, and the same modified glass fiber cloth is placed thereon to form a composite structure of modified glass fiber cloth - modified polymeric resin - modified glass fiber cloth - modified polymeric resin - modified glass fiber cloth from bottom to top. The above composite fiber cloth is heated, dried, and cured to finally obtain a glass fiber cloth with uniform coating.

[0011] Further, in step S1, the preparation method of the modified glass fiber cloth includes the following steps:

[0012] B1. The glass fiber cloth is placed in a muffle furnace, the muffle furnace is heated up and then kept warm to remove carbon to obtain the pretreated glass fiber cloth;

[0013] The glass fiber undergoes a carbon removal process to remove the sizing agent on the fabric surface that hinders adhesion to other substances.

[0014] B2. n-Hexyltrichlorosilane and diethyl ether are mixed evenly. At 2 - 5 °C, sulfur dioxide gas and chlorine gas are introduced, and then reflux reaction is carried out at 40 - 45 °C for 5 - 6 h to obtain a product; the product is distilled at 63 - 65 °C under 0.045 - 0.047 kPa, and the oily mixture is collected, which is the prepared coupling agent mixture solution;

[0015] Using diethyl ether as a solvent, sulfur dioxide and chlorine generate ClSO2+ at low temperature, which attacks the alkyl chain in n-hexyltrichlorosilane. The reaction causes the H in the alkyl chain to be replaced by a sulfonyl chloride group, generating a coupling agent mixture solution containing various isomers.

[0016] B3. The coupling agent mixture solution and deionized water are mixed evenly to obtain a coupling agent hydrolysis solution; the pretreated glass fiber cloth is immersed in the coupling agent hydrolysis solution, then taken out and heated to dry to obtain the modified glass fiber cloth.

[0017] The glass fiber cloth is impregnated in the coupling agent hydrolysis solution, and through a chemical reaction and chemical bond combination, a modified glass fiber cloth is obtained.

[0018] Further, in step B1, the heating rate is 10 - 20 °C / min, the temperature for heat preservation and carbon removal is 500 - 600 °C, and the duration for heat preservation and carbon removal is 20 - 30 h; in step B2, the dosage ratio of n - hexyltrichlorosilane, diethyl ether, sulfur dioxide gas, and chlorine gas is 11 - 22 g:100 g:30 - 50 mL:20 - 30 mL; the immersion temperature is 25 - 35 °C, the immersion duration is 2 - 4 h, and the drying temperature is 70 - 80 °C.

[0019] Further, in step S1, the preparation method of the modified polymeric resin includes the following steps:

[0020] A1. Hexachlorocyclotriphosphazene is dissolved in tetrahydrofuran, and then triethylamine is added to obtain a mixed solution; 2,3 - epoxy - 1 - propanol is added to the mixed solution, and the reaction is carried out at 25 - 30 °C for 40 - 45 h to obtain a product; the product is subjected to post - process treatment to prepare a multi - epoxy - group chain extender.

[0021] Using tetrahydrofuran as a solvent, hexachlorocyclotriphosphazene and 2,3 - epoxy - 1 - propanol undergo a nucleophilic substitution reaction to synthesize a multi - epoxy - group chain extender. The reaction formula is as follows:

[0022]

[0023] A2. An 88 - 95% wt aqueous lactic acid solution is transferred to a prepolymerization reactor for oligomerization reaction to generate a lactic acid prepolymer; the lactic acid prepolymer is added to a static mixing tank, and then stannous oxide is added and reacted to generate lactide.

[0024] Using stannous oxide as a tin - oxide catalyst, under the action of the catalyst, the lactic acid prepolymer is depolymerized to generate lactide.

[0025] A3. The lactide is transferred to two serially connected continuous stirred - tank reactors, and a catalyst, a stabilizer, and a multi - epoxy - group chain extender are added to the above - mentioned serially connected continuous stirred - tank reactors for polymerization to synthesize a polymer melt; the polymer melt is vacuum - stripped of volatile components to synthesize a modified polymeric resin.

[0026] Under the action of relevant additives, the multi - epoxy - group chain extender and lactide are polymerized to obtain a high - molecular - weight modified polymeric resin.

[0027] Further, in step A1, the dosage ratio of hexachlorocyclotriphosphazene, tetrahydrofuran, and triethylamine is 8.7 - 17.4 g:100 mL:1.2 - 1.5 g; the post - process treatment steps include: filtering the product to remove triethylamine hydrochloride, rotary - evaporating to remove the tetrahydrofuran solvent at 35 - 45 °C to obtain a solid; dissolving the solid in dichloromethane, where the mass ratio of the solid to dichloromethane is 1:8 - 10; then washing with water, drying with sodium sulfate, and removing dichloromethane at 40 - 45 °C to obtain a multi - epoxy - group chain extender.

[0028] Further, in step A2, the temperature of the oligomerization reaction is 155 - 175 °C, the pressure of the oligomerization reaction is 2.5 - 2.8 kPa, and the duration of the oligomerization reaction is 6 - 8 h; the dosage ratio of the aqueous lactic acid solution to tin dioxide is 200 - 300 mL:0.1 - 0.2 g, the reaction temperature is 210 - 220 °C, the reaction pressure is 1.33 - 1.35 kPa, and the reaction duration is 1 - 2 h.

[0029] Further, in step A3, the catalyst is stannous zincate, and the stabilizer is sodium sulfite; the dosage ratio of lactide, catalyst, stabilizer, and polyepoxy chain extender is 100 mL:0.5 - 1 g:1 - 2 g:5 - 10 g; the temperature of the polymerization reaction is 170 - 180 °C, the residence time in the first continuous tank reactor is 0.5 - 1 h, and the residence time in the second continuous tank reactor is 3.3 - 3.5 h; the temperature of vacuum devolatilization is 70 - 80 °C.

[0030] Further, in step S1, the spraying thickness on both the front and back sides is 0.2 - 0.4 mm; in step S2, the drying and curing temperature is 75 - 85 °C, and the drying and curing duration is 4 - 6 h.

[0031] As another aspect of the present invention, a highly uniform fiberglass cloth prepared by a weaving process of a highly uniform fiberglass cloth.

[0032] The present invention has the following beneficial effects:

[0033] 1. The fiberglass cloth used in the present invention is obtained by impregnating bidirectional warp-knitted fiberglass in epoxy resin and through a curing process; the synthesized fiberglass cloth itself has the advantages of high strength, high stiffness, and good compatibility with organic substances. Further, the present invention uses a coupling agent mixture containing multiple isomers with sulfonyl chloride group functional groups to modify the fiberglass cloth; compared with conventional coupling agents, the fiberglass cloth modified by the above coupling agent mixture has stronger polarity and reactivity, and better compatibility with the modified polymer resin; through a simple coating and curing process, a highly uniform fiberglass cloth can be prepared by chemical bond combination.

[0034] 2. The present invention synthesizes polylactic acid by continuous production polymerization using a solvent-free method. The aqueous lactic acid solution is pre-oligomerized to form oligomers; an appropriate amount of polyepoxy chain extender is added during the formation of the oligomers, and the polyepoxy chain extender can be used as a component for synthesizing polylactic acid to increase the crosslinking density and the number of functional groups of the oligomers; wherein, the polyepoxy chain extender is obtained by grafting 2,3-epoxy-1-propanol using hexachlorocyclotriphosphazene as the matrix; the synthesized polylactic acid-based modified polymer resin has high mechanical properties and degradability. The above-prepared polylactic acid-based modified polymer resin is uniformly coated on the surface of the modified glass fiber cloth, and through a curing process, it can be tightly combined with the modified glass fiber cloth to obtain a highly uniform glass fiber cloth with excellent mechanical properties such as shear strength, tensile strength, and flexural strength. Detailed Embodiments

[0035] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0036] The glass fiber yarn used in Example 1 of the present invention was purchased from Renqiu Jingjian Glass Fiber Factory, and the product number was 50 / 2; the lactic acid used in Examples 2-4 of the present invention was purchased from Shandong Ruifeng New Materials Co., Ltd., and the single product number was RF040206.

[0037] Example 1

[0038] This example provides a weaving process for a glass fiber cloth used for a highly uniform glass fiber cloth, including the following steps:

[0039] The glass fiber yarns are respectively used as warp yarns and weft yarns for warping, and then through the reed threading process and then weaving; wherein, the rotational speed of the weaving machine is 500 r / min; the linear density of the warp yarns is 20 pieces / cm, and the linear density of the weft yarns is 20 pieces / cm, to obtain a glass fiber cloth.

[0040] Example 2

[0041] This example provides a preparation method for a modified polymer resin used for a highly uniform glass fiber cloth, including the following steps:

[0042] A1. Weigh 8.7 g of hexachlorocyclotriphosphazene and 100 mL of tetrahydrofuran and place them in a 250 mL three-necked flask. Stir until the hexachlorocyclotriphosphazene is completely dissolved. Then add 1.2 g of triethylamine to the three-necked flask to obtain a mixed solution. Add 14.8 g of 2,3-epoxy-1-propanol to the above mixed solution, and then react at 25 °C for 40 h to obtain a product. The product is filtered to remove triethylamine hydrochloride, and then the tetrahydrofuran solvent is removed by rotary evaporation at a temperature of 35 °C to obtain a solid. The solid is dissolved in dichloromethane (the mass ratio of the solid to dichloromethane is 1:8), washed with water successively, dried with sodium sulfate, and the dichloromethane is removed at 40 °C to obtain a polyepoxy chain extender.

[0043] A2. Add lactic acid to deionized water to prepare 200 mL of an 88% wt aqueous lactic acid solution. Transfer 200 mL of the aqueous lactic acid solution to a 500 mL prepolymerization reactor for oligomerization. The temperature of the prepolymerization reactor is set at 155 °C, the pressure is set at 2.5 kPa, and the oligomerization time is 6 h to produce a lactic acid prepolymer. The lactic acid prepolymer is transferred to a static mixing tank, and 0.1 g of stannous oxide is added. React at 210 °C and 1.33 kPa for 1 h to produce lactide.

[0044] A3. Transfer 100 mL of lactide to two series-connected continuous stirred tank reactors. Add 0.5 g of the catalyst stannous zincate, 1 g of the stabilizer sodium sulfite, and 5 g of the polyepoxy chain extender to the first continuous stirred tank reactor for polymerization. The polymerization temperature of the above two continuous stirred tank reactors is 170 °C; the residence time in the first continuous stirred tank reactor is 0.5 h, and the residence time in the second continuous stirred tank reactor is 3.3 h to finally synthesize a polymer melt. The polymer melt is de-volatilized under vacuum conditions, and the vacuum temperature is 70 °C to synthesize a modified polymer resin.

[0045] Example 3

[0046] This example provides a method for preparing a modified polymer resin for a highly uniform fiberglass cloth, including the following steps:

[0047] A1. Weigh 13 g of hexachlorocyclotriphosphazene and 100 mL of tetrahydrofuran and place them in a 250 mL three-necked flask. Stir until the hexachlorocyclotriphosphazene is completely dissolved. Then add 1.3 g of triethylamine to the three-necked flask to obtain a mixed solution. Add 22 g of 2,3-epoxy-1-propanol to the above mixed solution, and then react at 28 °C for 42 h to obtain a product. The product is filtered to remove triethylamine hydrochloride, and then the tetrahydrofuran solvent is removed by rotary evaporation at a temperature of 40 °C to obtain a solid. The solid is dissolved in dichloromethane (the mass ratio of the solid to dichloromethane is 1:9), washed with water successively, dried with sodium sulfate, and the dichloromethane is removed at 42 °C to obtain a polyepoxy chain extender.

[0048] A2. Add lactic acid to deionized water to prepare 260 mL of a 92% wt aqueous lactic acid solution; send 260 mL of the aqueous lactic acid solution and 8 g of the polyepoxy chain extender to a 500 mL prepolymerization reactor for oligomerization reaction. The temperature of the prepolymerization reactor is set at 165 °C, the pressure is set at 2.6 kPa, and the oligomerization reaction time is 7 h to produce a lactic acid prepolymer. The lactic acid prepolymer is transferred to a static mixing tank, and 0.15 g of tin dioxide (tin oxide catalyst) is added, and the reaction is carried out at 215 °C and 1.33 kPa for 1.5 h to produce lactide.

[0049] A3. Transfer 100 mL of lactide to two series-connected continuous stirred tank reactors. Add 0.8 g of the catalyst stannous zincate and 1.5 g of the stabilizer sodium sulfite to the first continuous stirred tank reactor for polymerization. The polymerization temperature of the above two continuous stirred tank reactors is 172 °C; the residence time in the first continuous stirred tank reactor is 0.8 h, and the residence time in the second continuous stirred tank reactor is 3.4 h to finally synthesize a polymer melt. The polymer melt is de-volatilized under vacuum conditions, and the vacuum temperature is 72 °C to synthesize a modified polymer resin.

[0050] Example 4

[0051] This example provides a method for preparing a modified polymer resin for a highly uniform fiberglass cloth, including the following steps:

[0052] A1. Weigh 17.4 g of hexachlorocyclotriphosphazene and 100 mL of tetrahydrofuran and place them in a 250 mL three-necked flask, and stir until the hexachlorocyclotriphosphazene is completely dissolved; then add 1.5 g of triethylamine to the three-necked flask to obtain a mixed solution. Add 29.6 g of 2,3-epoxy-1-propanol to the above mixed solution, and then react at 30 °C for 45 h to obtain a product. The product is filtered to remove triethylamine hydrochloride, and then the tetrahydrofuran solvent is removed by rotary evaporation. The rotary evaporation temperature is 45 °C to obtain a solid. The solid is dissolved in dichloromethane (the mass ratio of the solid to dichloromethane is 1:10), washed with water successively, dried with sodium sulfate, and the dichloromethane is removed at 45 °C to obtain a polyepoxy chain extender.

[0053] A2. Add lactic acid to deionized water to prepare 300 mL of a 95% wt aqueous lactic acid solution; send 300 mL of the aqueous lactic acid solution to a 500 mL prepolymerization reactor for oligomerization reaction. The temperature of the prepolymerization reactor is set at 175 °C, the pressure is set at 2.8 kPa, and the oligomerization reaction time is 8 h to produce a lactic acid prepolymer. The lactic acid prepolymer is transferred to a static mixing tank, and 0.2 g of tin dioxide is added, and the reaction is carried out at 220 °C and 1.35 kPa for 2 h to produce lactide.

[0054] A3. Transfer 100 mL of lactide into two continuously stirred tank reactors connected in series. Add 1 g of stannous zincate catalyst, 2 g of sodium sulfite stabilizer, and 10 g of polyepoxy chain extender to the first continuously stirred tank reactor for polymerization. The polymerization temperature of the above two continuously stirred tank reactors is 180 °C; the residence time in the first continuously stirred tank reactor is 1 h, and the residence time in the second continuously stirred tank reactor is 3.5 h to finally synthesize a polymer melt. The polymer melt is de-volatilized under vacuum conditions, and the vacuum temperature is 80 °C to synthesize a modified polymer resin.

[0055] Example 5

[0056] This example provides a method for preparing a modified glass fiber cloth for high-uniform glass fiber cloth, including the following steps:

[0057] B1. Place the glass fiber cloth woven in Example 1 in a muffle furnace, set the power of the muffle furnace to 12 KW; set the decarbonization parameters of the muffle furnace, with a heating rate of 10 °C / min, heat up to 500 °C, and keep warm for 20 h. After decarbonization, a pretreated glass fiber cloth is obtained.

[0058] B2. Add 11 g of n-hexyltrichlorosilane and 100 g of diethyl ether to a 250 mL three-necked flask according to weight parts, stir evenly at 100 r / min; then transfer the three-necked flask to a water bath, keep the temperature at 2 °C, and then introduce 30 mL of sulfur dioxide gas and 20 mL of chlorine gas; then reflux and react at 40 °C for 5 h to obtain a product. The product is distilled at 0.045 kPa and 63 °C, and the oily mixture is collected, which is the prepared coupling agent mixture.

[0059] B3. Mix 10 g of the coupling agent mixture and 100 mL of deionized water to prepare a coupling agent hydrolysis solution. Immerse the pretreated glass fiber cloth in the coupling agent hydrolysis solution for infiltration, with an infiltration temperature of 25 °C and an infiltration time of 2 h, then take it out and dry it at 70 °C to obtain a modified glass fiber cloth.

[0060] Example 6

[0061] This example provides a method for preparing a modified glass fiber cloth for high-uniform glass fiber cloth, including the following steps:

[0062] B1. Place the glass fiber cloth woven in Example 1 in a muffle furnace, set the power of the muffle furnace to 13 KW; set the decarbonization parameters of the muffle furnace, with a heating rate of 15 °C / min until it heats up to 550 °C, and keep warm for 25 h. After decarbonization, a pretreated glass fiber cloth is obtained.

[0063] B2. Add 16 g of n - hexyltrichlorosilane and 100 g of diethyl ether to a 250 - mL three - necked flask by weight, and stir evenly at 150 r / min. Then transfer the three - necked flask to a water bath, keep the temperature at 3 °C. Then introduce 40 mL of sulfur dioxide gas and 25 mL of chlorine gas. Then reflux and react at 42 °C for 5.5 h to obtain a product. The product is distilled at 0.046 kPa and 63 °C, and the oily mixture is collected, which is the prepared coupling agent mixture solution.

[0064] B3. Mix 15 g of the coupling agent mixture solution and 100 mL of deionized water to prepare a coupling agent hydrolysis solution. Immerse the pretreated glass fiber cloth in the coupling agent hydrolysis solution, with the immersion temperature at 30 °C and the immersion duration of 3 h. Then take it out and heat it to 73 °C for drying to obtain the modified glass fiber cloth.

[0065] Example 7

[0066] This example provides a method for preparing a modified glass fiber cloth for a highly uniform glass fiber cloth, including the following steps:

[0067] B1. Place the glass fiber cloth woven in Example 1 in a muffle furnace, set the power of the muffle furnace to 15 KW; set the decarburization parameters of the muffle furnace, with a heating rate of 20 °C / min until the temperature rises to 600 °C, and keep it warm for 30 h. After decarburization, the pretreated glass fiber cloth is obtained.

[0068] B2. Add 22 g of n - hexyltrichlorosilane and 100 g of diethyl ether to a 250 - mL three - necked flask by weight, and stir evenly at 200 r / min. Then transfer the three - necked flask to a water bath, keep the temperature at 5 °C. Then introduce 50 mL of sulfur dioxide gas and 30 mL of chlorine gas. Then reflux and react at 45 °C for 6 h to obtain a product. The product is distilled at 0.047 kPa and 65 °C, and the oily mixture is collected, which is the prepared coupling agent mixture solution.

[0069] B3. Mix 25 g of the coupling agent mixture solution and 100 mL of deionized water to prepare a coupling agent hydrolysis solution. Immerse the pretreated glass fiber cloth in the coupling agent hydrolysis solution, with the immersion temperature at 35 °C and the immersion duration of 4 h. Then take it out and heat it to 80 °C for drying to obtain the modified glass fiber cloth.

[0070] Example 8

[0071] This example provides a method for weaving a highly uniform glass fiber cloth, including the following steps:

[0072] S1. Use a spray gun to coat both the front and back sides of the modified glass fiber cloth prepared in Example 5 with the modified polymerization resin prepared in Example 2, with a spraying thickness of 0.2 mm, to obtain the sprayed modified glass fiber cloth. The sprayed modified glass fiber cloth serves as the intermediate layer; then, a layer of modified glass fiber cloth is laminated on both its front and back sides to form a composite fiber cloth.

[0073] S2. Transfer the composite fiber cloth to a constant-temperature forced-air drying oven and dry and cure it at 75 °C for 4 h to synthesize a highly uniform glass fiber cloth.

[0074] Example 9

[0075] This example provides a method for weaving a highly uniform glass fiber cloth, including the following steps:

[0076] S1. Use a spray gun to coat both the front and back sides of the modified glass fiber cloth prepared in Example 6 with the modified polymerization resin prepared in Example 3, with a spraying thickness of 0.3 mm, to obtain the sprayed modified glass fiber cloth. The sprayed modified glass fiber cloth serves as the intermediate layer; then, a layer of modified glass fiber cloth is laminated on both its front and back sides to form a composite fiber cloth.

[0077] S2. Transfer the composite fiber cloth to a constant-temperature forced-air drying oven and dry and cure it at 80 °C for 5 h to synthesize a highly uniform glass fiber cloth.

[0078] Example 10

[0079] This example provides a method for weaving a highly uniform glass fiber cloth, including the following steps:

[0080] S1. Use a spray gun to coat both the front and back sides of the modified glass fiber cloth prepared in Example 7 with the modified polymerization resin prepared in Example 4, with a spraying thickness of 0.4 mm, to obtain the sprayed modified glass fiber cloth. The sprayed modified glass fiber cloth serves as the intermediate layer; then, a layer of modified glass fiber cloth is laminated on both its front and back sides to form a composite fiber cloth.

[0081] S2. Transfer the composite fiber cloth to a constant-temperature forced-air drying oven and dry and cure it at 85 °C for 6 h to synthesize a highly uniform glass fiber cloth.

[0082] Comparative Example 1

[0083] The difference between this comparative example and Example 10 is that when preparing the modified glass fiber cloth, step B2 is cancelled, and an equivalent mass of silane coupling agent KH-550 is used to replace the coupling agent mixture.

[0084] Comparative Example 2

[0085] The difference between this comparative example and Example 10 is that when preparing the modified polymeric resin, step A1 was cancelled, and diphenylmethane diisocyanate of the same mass was used to replace the multi-epoxy chain extender.

[0086] Comparative Example 3

[0087] The difference between this comparative example and Example 10 is that when preparing the modified polymeric resin, step A1 was cancelled, and 2,3-epoxy-1-propanol of the same mass was used to replace the multi-epoxy chain extender.

[0088] Comparative Example 4

[0089] The difference between this comparative example and Example 10 is that when preparing the modified polymeric resin, the multi-epoxy chain extender was not added during the polymerization reaction in step A3; the synthesized polymer melt was blended with the multi-epoxy chain extender and volatiles were removed under vacuum conditions to synthesize the modified polymeric resin.

[0090] Performance test:

[0091] 1. The dynamic contact angle values of the modified glass fiber cloths prepared in Examples 5-7 and Comparative Example 1 were detected using a dynamic contact angle tester; the tangent method was used, and the contact angle values of the modified glass fiber cloths were detected after 30 s.

[0092]

[0093] Data analysis: After being modified with the coupling agent hydrolysis solution, the modified glass fiber cloths prepared in Examples 5-7 of the present invention all had good hydrophilicity, and the water contact angle degrees were all not more than 20°. However, in Comparative Example 1, when preparing the modified glass fiber cloth, silane coupling agent KH-550 of the same mass was used to replace the coupling agent mixture. The synthesized coupling agent mixture contained isomers with multiple acyl chloride groups, which were more polar and hydrophilic, so the water contact angle value of the modified glass fiber cloth prepared in Comparative Example 1 became larger.

[0094] 2. According to ASTM D3518-13 "Standard Test Method for In-Plane Shear Response of Polymer Matrix Composites Using ±45° Laminate Tensile Tests", the interlaminar shear strength of the highly uniform glass fiber cloths prepared in Examples 8-10 and Comparative Examples 2-4 was detected; according to ASTM D3039-14 "Standard Test Method for Tensile Properties of Polymer Matrix Composites", the tensile strength of the highly uniform glass fiber cloths prepared in Examples 8-10 and Comparative Examples 2-4 was detected; according to ASTM D7264-07 "Flexural Properties of Polymer Matrix Composites", the flexural strength of the highly uniform glass fiber cloths prepared in Examples 8-10 and Comparative Examples 2-4 was detected. The specific test results are shown in the following table:

[0095] Table 1. Test data of sample properties

[0096]

[0097] Data analysis: By comparing and analyzing the data in the above table, the fiberglass cloths prepared in Examples 8-10 of the present invention all have excellent mechanical properties, specifically manifested as good shear strength, tensile strength, and flexural strength values of the prepared fiberglass cloths.

[0098] However, in Comparative Example 2, when preparing the modified polymeric resin, diphenylmethane diisocyanate of the same mass was used to replace the polyepoxy chain extender, thereby reducing its own crosslinking density; in Comparative Example 3, 2,3-epoxy-1-propanol of the same mass was used to replace the polyepoxy chain extender, thereby reducing the molecular weight of the prepared modified polymeric resin, resulting in a decrease in the mechanical properties of the fiberglass cloths prepared in Comparative Example 2 and Comparative Example 3, that is, a decrease in the shear strength value, tensile strength value, and flexural strength value.

[0099] In Comparative Example 4, when preparing the modified polymeric resin, the polyepoxy chain extender was not added during the synthesis of the lactic acid prepolymer, but was added during the synthesis of the polymer melt from the polylactic acid prepolymer. At this time, the polyepoxy chain extender did not participate in the synthesis of the prepolymer, but served as a capping agent; compared with the modified polymeric resin prepared in Comparative Example 4, the modified polymeric resin prepared in Examples 7-9 contains more functional groups and has a higher crosslinking density of the polyester adhesive, manifested as a decrease in the shear strength, tensile strength, and flexural strength values of the fiberglass cloth prepared in Comparative Example 4.

[0100] The above content is only an example and illustration of the structure of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

[0101] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0102] 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 invention to the specific embodiments only. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art 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 weaving process of a highly uniform fiberglass cloth, characterized in that, It includes the following steps: S1. Coat both the front and back sides of the modified glass fiber cloth with a modified polymer resin to obtain the sprayed modified glass fiber cloth; The sprayed modified glass fiber cloth serves as the intermediate layer, and a layer of modified glass fiber cloth is laminated on both its front and back sides to form a composite fiber cloth; S2. Dry and cure the composite fiber cloth to synthesize a highly uniform glass fiber cloth.

2. The weaving process of a highly uniform fiberglass cloth according to claim 1, characterized in that, In step S1, the preparation method of the modified glass fiber cloth includes the following steps: B1. Place the glass fiber cloth in a muffle furnace, heat up the muffle furnace, and then keep it warm to remove carbon to obtain the pretreated glass fiber cloth; B2. Mix n-hexyltrichlorosilane and ether, at 2 - 5 °C, introduce sulfur dioxide gas and chlorine gas, and then reflux and react at 40 - 45 °C for 5 - 6 h to obtain a product; the product is distilled at 63 - 65 °C under 0.045 - 0.047 kPa, and the oily mixture is collected, which is the prepared coupling agent mixture solution; B3. Mix the coupling agent mixture solution and deionized water to obtain a coupling agent hydrolysis solution; immerse the pretreated glass fiber cloth in the coupling agent hydrolysis solution, then take it out, heat up and dry it to obtain the modified glass fiber cloth.

3. The weaving process of a highly uniform fiberglass cloth according to claim 2, characterized in that, In step B1, the heating rate is 10 - 20 °C / min, the temperature for keeping warm to remove carbon is 500 - 600 °C, and the duration for keeping warm to remove carbon is 20 - 30 h; in step B2, the dosage ratio of n-hexyltrichlorosilane, ether, sulfur dioxide gas and chlorine gas is 11 - 22 g:100 g:30 - 50 mL:20 - 30 mL; the immersion temperature is 25 - 35 °C, the immersion duration is 2 - 4 h, and the drying temperature is 70 - 80 °C.

4. The weaving process of a highly uniform fiberglass cloth according to claim 1, characterized in that In step S1, the preparation method of the modified polymer resin includes the following steps: A1. Dissolve hexachlorocyclotriphosphazene in tetrahydrofuran, then add triethylamine to obtain a mixed solution; add 2,3-epoxy-1-propanol to the mixed solution and react at 25 - 30 °C for 40 - 45 h to obtain a product; the product is subjected to post-process treatment to prepare a multi-epoxy group chain extender; A2. Transfer an 88 - 95% wt aqueous lactic acid solution to a prepolymerization reactor for oligomerization reaction to generate a lactic acid prepolymer; add the lactic acid prepolymer to a static mixing tank, and then add stannous dioxide and react to generate lactide; A3. Transfer lactide to two series-connected continuous stirred tank reactors, add a catalyst, a stabilizer and a multi-epoxy group chain extender to polymerize in the above-mentioned series-connected continuous stirred tank reactors to synthesize a polymer melt; the polymer melt is vacuum-devolatilized to synthesize a modified polymer resin.

5. The weaving process of a highly uniform fiberglass cloth according to claim 4, characterized in that, In step A1, the dosage ratio of hexachlorocyclotriphosphazene, tetrahydrofuran and triethylamine is 8.7 - 17.4 g:100 mL:1.2 - 1.5 g; the post-process treatment steps include: filtering the product to remove triethylamine hydrochloride, rotary evaporating to remove the tetrahydrofuran solvent at 35 - 45 °C to obtain a solid; dissolving the solid in dichloromethane, where the mass ratio of the solid to dichloromethane is 1:8 - 10; then washing with water, drying with sodium sulfate, and removing dichloromethane at 40 - 45 °C to obtain a multi-epoxy group chain extender.

6. The weaving process of a highly uniform fiberglass cloth according to claim 4, characterized in that, In step A2, the temperature of the oligomerization reaction is 155 - 175 °C, the pressure of the oligomerization reaction is 2.5 - 2.8 kPa, and the duration of the oligomerization reaction is 6 - 8 h; the dosage ratio of the lactic acid aqueous solution to tin dioxide is 200 - 300 mL: 0.1 - 0.2 g, the temperature of the reaction is 210 - 220 °C, the pressure of the reaction is 1.33 - 1.35 kPa, and the duration of the reaction is 1 - 2 h.

7. The weaving process of a highly uniform fiberglass cloth according to claim 4, characterized in that, In step A3, the dosage ratio of lactide, catalyst, stabilizer, and polyepoxy chain extender is 100 mL: 0.5 - 1 g: 1 - 2 g: 5 - 10 g; the temperature of the polymerization reaction is 170 - 180 °C, the residence time in the first continuous tank reactor is 0.5 - 1 h, and the residence time in the second continuous tank reactor is 3.3 - 3.5 h; the temperature of the vacuum devolatilization is 70 - 80 °C.

8. The weaving process of a highly uniform fiberglass cloth according to claim 1, characterized in that, In step S1, the spraying thickness on both the front and back sides is 0.2 - 0.4 mm; in step S2, the temperature of the drying and curing is 75 - 85 °C, and the duration of the drying and curing is 4 - 6 h.

9. A high-uniformity fiberglass cloth, characterized in that, It is prepared by using a weaving process of a highly uniform fiberglass cloth as described in any one of claims 1 - 8.

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