Waterproof polymer alkali-resistant fiber cloth and preparation method thereof

Abstract

The present application relates to alkali-resistant fiber cloth technical field, specifically relates to a waterproof high molecular alkali-resistant fiber cloth and a preparation method thereof.The present application is prepared melt by modified polyvinyl chloride, PU prepolymer and modified glass fiber, then is spun, is gathered into yarn, is woven into alkali-resistant fiber cloth, the modified polyvinyl chloride is prepared by polyvinyl chloride, 4-hydroxyphenyl mercaptan, 1H, 1H, 2H, 2H-perfluorododecane mercaptan, the PU prepolymer is prepared by polyethylene glycol, hydroxyl silicone oil, toluene diisocyanate;The modified glass fiber is prepared by glass fiber modified by N, N-di (3-triethoxysilylpropyl) urea.The present application balances the flexibility and toughness of the fiber by adjusting the structure of the fiber matrix resin, including introducing silicone oil segment on the main chain of polyvinyl chloride macromolecule, introducing long fluorine side chain by in-situ polymerization, introducing urea group, improving the interface effect of glass fiber and resin matrix by introducing urea group on the surface of glass fiber.The waterproof high molecular alkali-resistant fiber cloth prepared by the present application has the effects of waterproof and strong alkali corrosion resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of alkali-resistant fiber cloth, in particular to a waterproof polymer alkali-resistant fiber cloth and a preparation method thereof, which is particularly suitable for waterproof sealing projects in strong alkaline environments. Background Art

[0002] Currently, alkali-resistant fiber cloth, a composite reinforcement material made of glass fiber and polyester fiber, is widely used in construction, road engineering, and waterproofing membranes due to its excellent mechanical properties and durability. However, in practical applications, polyester fiberglass cloth still faces challenges such as insufficient alkali resistance and poor crack resistance, limiting its long-term performance in harsh environments (especially highly alkaline ones). Therefore, there is an urgent need to overcome these technical bottlenecks through material modification or process optimization.

[0003] Currently, the industry primarily uses two approaches to improve the performance of alkali-resistant fiber cloth: first, surface modification of glass fibers, such as treatment with silane coupling agents, to enhance the interfacial bonding between the fiber and the resin; and second, the introduction of hydrophobic components (such as silicone oil) into the resin matrix to enhance water resistance. However, these methods have significant limitations: Silane coupling agents can lead to excessive crosslinking of the resin, affecting processing fluidity and increasing production energy consumption. While hydrophobically modified resins can improve water resistance, their effect on alkali resistance is limited and may reduce the material's mechanical strength. Furthermore, existing technologies often struggle to balance the material's alkali resistance, crack resistance, and processing performance.

[0004] Another major issue with existing alkali-resistant fiberglass fabrics is the mismatch in mechanical properties between the fibers and the matrix. Glass fibers are brittle and prone to fracture under dynamic loads or thermal stresses. While polyester fibers offer good toughness, their low modulus makes them ineffective in suppressing crack propagation. Furthermore, insufficient interfacial bonding between the fibers and the matrix leads to inefficient stress transfer, resulting in localized stress concentrations and accelerated cracking. While attempts have been made to improve performance through fiber blending or chemical coupling agents, these solutions are often complex or costly, making them difficult to implement on a large scale. Summary of the Invention

[0005] The purpose of the present invention is to provide a waterproof polymer alkali-resistant fiber cloth to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solution: a waterproof polymer alkali-resistant fiber cloth is made of modified polyvinyl chloride, PU prepolymer, and modified glass fiber; the mass ratio of the modified polyvinyl chloride, PU prepolymer, and modified glass fiber is 65:10~15:6~9.

[0007] Furthermore, the modified polyvinyl chloride is prepared from polyvinyl chloride, 4-hydroxythiophenol, and 1H,1H,2H,2H-perfluorododecanethiol.

[0008] Furthermore, the mass ratio of the polyvinyl chloride, 4-hydroxythiophenol, and 1H,1H,2H,2H-perfluorododecanethiol is 10:0.1-0.3:1.1-1.5.

[0009] Furthermore, the PU prepolymer is prepared from polyethylene glycol, hydroxy silicone oil, and toluene diisocyanate; the molar ratio of the total molar mass of OH in the polyethylene glycol and hydroxy silicone oil to the NCO in toluene diisocyanate is preferably 1:1.1-1.2.

[0010] Furthermore, the molar ratio of the polyethylene glycol to the hydroxy silicone oil is 6-8:1.

[0011] Furthermore, the modified glass fiber is prepared by modifying glass fiber with N,N-bis(3-triethoxysilylpropyl)urea.

[0012] Furthermore, the glass fiber is glass fiber powder with a mesh size of 1250-1500.

[0013] The preparation steps of the above-mentioned alkali-resistant fiber cloth are as follows:

[0014] S11 Preparation of PU prepolymer: Toluene diisocyanate is mixed with polyethylene glycol and hydroxy silicone oil for addition reaction to obtain a PU prepolymer;

[0015] S12 melt blending: adding modified polyvinyl chloride, PU prepolymer and catalyst into a twin-screw extruder for melt blending, then adding modified glass fiber and mixing evenly to obtain a melt;

[0016] S13 Spinning: After the melt is extruded through the spinneret, it solidifies into fibers, and the fiber surface is treated with plasma to generate a micron-scale rough structure;

[0017] S14 Bunch drawing: three-level gradient hot drawing to make yarn;

[0018] S15 weaves the yarn into alkali-resistant fiber cloth.

[0019] Furthermore, the addition reaction described in step S11 is carried out in a N2 atmosphere, the reaction temperature is 70-80°C, and the time is 5-8h.

[0020] Furthermore, the melt blending temperature in step S12 is 160-180° C., and the time is 24-48 hours.

[0021] Furthermore, the catalyst in step S12 is selected from one or more of stannous isooctanoate, dibutyltin dilaurate, dimethyltin diacetate, dibutyltin maleate, dimethyltin dichloride, zinc naphthenate, zinc octoate, and bismuth octoate.

[0022] Furthermore, the method for preparing the modified polyvinyl chloride in step S12 comprises the following steps:

[0023] Polyvinyl chloride and tetrahydrofuran are mixed, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, and potassium carbonate are added, and the mixture is kept at 60-67°C for 4-5 hours. Insoluble matter is filtered, and the solution is precipitated with a 10% by mass methanol aqueous solution. The precipitate is washed and dried to obtain modified polyvinyl chloride.

[0024] Furthermore, the mass ratio of the polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, and potassium carbonate is 10:0.1-0.3:1.1-1.5:0.6-0.9.

[0025] Furthermore, the specific preparation steps of the modified glass fiber in step S12 are as follows:

[0026] S21 Prepare a Tris-HCl buffer solution and adjust the pH to 8-10;

[0027] S22 adding the glass fiber to the Tris-HCl buffer solution and stirring and ultrasonically dispersing the solution;

[0028] S23: adding N,N-bis(3-triethoxysilylpropyl)urea and performing ultrasonic treatment with stirring to obtain a dispersion; wherein the concentration of N,N-bis(3-triethoxysilylpropyl)urea in the dispersion is 0.1-4 mg / mL; and the mass ratio of the glass fiber to the N,N-bis(3-triethoxysilylpropyl)urea is 1:0.1-0.4;

[0029] S24 placing the dispersion on a shaker and reacting under shaking for 6 to 12 hours;

[0030] S25: filtering, washing, and drying the dispersion after the reaction to obtain modified glass fiber.

[0031] Furthermore, the spinneret aperture in step S13 is 0.2-0.4 mm.

[0032] Furthermore, the curing in step S13 is achieved through a cooling air duct with a wind speed of 5-8 m / s.

[0033] Furthermore, the power of the plasma treatment in step S13 is 100 W, and the gas is Ar gas.

[0034] Furthermore, the temperature of the three-level gradient thermal stretching in step S14 is 80°C → 120°C → 150°C in sequence, and the stretching ratio is 4 to 5 times.

[0035] A composite fabric comprising the above-mentioned waterproof polymer alkali-resistant fiber cloth comprises at least one layer of polyvinyl chloride non-woven fabric and waterproof polymer alkali-resistant fiber cloth; the polyvinyl chloride non-woven fabric and the waterproof polymer alkali-resistant fiber cloth are bonded by EVA-based hot melt adhesive.

[0036] Furthermore, the polyvinyl chloride non-woven fabric has a gram weight of 30-50 g / m².

[0037] Furthermore, the waterproof polymer alkali-resistant fiber cloth is subjected to surface functionalization treatment; the surface functionalization treatment includes at least one of hydrophobic treatment and irradiation treatment.

[0038] Furthermore, the hydrophobic treatment comprises the following specific steps: immersing the alkali-resistant fiber cloth in an acetone solution containing 2 wt% polyvinylidene fluoride (PVDF) and 1 wt% nano-silica, and rolling and drying the solution to form a microporous coating having a thickness of 3-5 μm;

[0039] Furthermore, the irradiation treatment specifically comprises the following steps: subjecting the hydrophobic treated alkali-resistant fiber cloth to electron beam irradiation (dose 50-70 kGy) to crosslink the fluorine-containing chain segments with the modified polyvinyl chloride.

[0040] Furthermore, the polyester non-woven fabric, waterproof high molecular alkali-resistant fiber fabric, and EVA-based hot melt adhesive are stacked and reinforced, with a lamination temperature of 140-160° C. and a pressure of 5-8 MPa.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The present invention prepares a waterproof polymer alkali-resistant fiber cloth having waterproof and strong alkali-resistant effects by (1) adjusting the structure of the fiber matrix resin, including introducing silicone oil segments, long fluorine side chains, and urea groups into the main chain of the polyvinyl chloride macromolecule, and (2) introducing urea groups onto the surface of the glass fiber.

[0043] Silicone oil segments and long fluorine side chains are introduced into the main chain of polyvinyl chloride macromolecules. The silicone oil segments on the main chain of the fiber macromolecule enhance the hydrophobicity of the fiber and improve the dispersion of the glass fiber in the fiber resin matrix. The introduction of long fluorine side chains can enhance the fiber's resistance to strong alkali. The rigidity of the fluorine side chains can enhance the modulus of polyvinyl chloride, and synergistically inhibit the expansion of cracks between the glass fiber and the fiber matrix resin together with the elastic effect brought by the soft and hard segments of the PU prepolymer.

[0044] Introducing urea groups on the surface of glass fibers can, on the one hand, avoid chemical bonding between the glass fibers and the fiber resin matrix, which would result in excessive cross-linking of the fiber resin matrix and affect the molding of the fibers. On the other hand, after the fibers are molded, the urea groups in the glass fibers can combine with the urea groups in the PU prepolymer through hydrogen bonds, and the urea groups in the PU prepolymer can also form a physical locking effect on the glass fibers through hydrogen bonds. The two can synergistically improve the interface between the chopped glass fibers and the resin matrix. DETAILED DESCRIPTION

[0045] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0046] In order to more clearly illustrate the method provided by the present invention, the following examples are described in detail. Example 1

[0047] (1) Preparation of modified glass fiber:

[0048] Prepare 1.5 M Tris-HCl buffer solution and adjust the pH to 8;

[0049] Add glass fiber (Fucai glass fiber powder 1250 mesh) into the Tris-HCl buffer solution and stir and disperse with ultrasound;

[0050] Add N,N-bis(3-triethoxysilylpropyl)urea and perform ultrasonic treatment with stirring to obtain a dispersion; wherein, in the dispersion, the concentration of N,N-bis(3-triethoxysilylpropyl)urea is 0.1 mg / mL, and the mass ratio of glass fiber to N,N-bis(3-triethoxysilylpropyl)urea is 1:0.1; place the dispersion in a shaker and react for 12 hours under shaking;

[0051] The dispersion after the reaction is completed is filtered, washed and dried to obtain modified glass fiber.

[0052] (2) Preparation of modified polyvinyl chloride: polyvinyl chloride (Jiyesheng JYS14715) and tetrahydrofuran were mixed, and 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, and potassium carbonate were added, and the mixture was kept at 60°C for 4 hours; insoluble matter was filtered, and the solution was precipitated with a 10% methanol aqueous solution, and the precipitate was washed and dried to obtain modified polyvinyl chloride, wherein the mass ratio of the polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, potassium carbonate, and tetrahydrofuran was 10:0.1:1.5:0.8:100.

[0053] (3) Alkali-resistant fiber cloth

[0054] Toluene diisocyanate was mixed with polyethylene glycol (PEG400 from Kehui Chemical) and hydroxy silicone oil (107# silicone oil, industrial grade, produced by Zaoyang Sihai Chemical Co., Ltd.) for an addition reaction. The addition reaction was carried out in a nitrogen atmosphere at a temperature of 70°C for 8 hours to obtain a PU prepolymer. The molar ratio of the total molar mass of OH in the polyethylene glycol and hydroxy silicone oil to the NCO in the toluene diisocyanate was 1:1.1, and the molar ratio of the polyethylene glycol to the hydroxy silicone oil was 8:1.

[0055] The modified polyvinyl chloride, PU prepolymer and zinc naphthenate were added into a twin-screw extruder and melt-blended at a temperature of 180°C for 30 hours; then the modified glass fiber was added and mixed evenly to obtain a melt; wherein the mass ratio of the modified polyvinyl chloride, PU prepolymer and modified glass fiber was 65:10:6;

[0056] The melt was extruded through a spinneret (0.4 mm aperture) and solidified through a cooling air duct (wind speed 7-8 m / s). The fiber surface was treated with plasma to generate a micron-scale rough structure. The plasma treatment power was 100 W, the gas was Ar, and the treatment time was 20 s.

[0057] The yarns are bundled (6 filaments) and subjected to three-level gradient hot drawing, where the temperatures of the three-level gradient hot drawing are 80°C → 120°C → 150°C in sequence and the drawing ratio is 5 times, to form yarns; the yarns are woven into plain alkali-resistant fiber cloth with a plain weave, a warp density of 80 strands / inch and a weft density of 60 strands / inch. Example 2

[0058] (1) Preparation of modified glass fiber:

[0059] Prepare 1.5 M Tris-HCl buffer solution and adjust the pH to 10;

[0060] Add glass fiber (Fucai glass fiber powder 2000 mesh) into the Tris-HCl buffer solution and disperse by stirring and ultrasonication;

[0061] Add N,N-bis(3-triethoxysilylpropyl)urea and perform stirring and ultrasonic treatment to obtain a dispersion; wherein, in the dispersion, the concentration of N,N-bis(3-triethoxysilylpropyl)urea is 2 mg / mL, and the mass ratio of glass fiber to N,N-bis(3-triethoxysilylpropyl)urea is 1:2;

[0062] The dispersion was placed in a shaker and reacted for 6 h under shaking;

[0063] The dispersion after the reaction is completed is filtered, washed and dried to obtain modified glass fiber.

[0064] (2) Preparation of modified polyvinyl chloride: polyvinyl chloride (Jiyesheng JYS14715) and tetrahydrofuran were mixed, and 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, and potassium carbonate were added, and the mixture was kept at 60°C for 4 hours; insoluble matter was filtered, and the solution was precipitated with a 10% methanol aqueous solution, and the precipitate was washed and dried to obtain modified polyvinyl chloride, wherein the mass ratio of the polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, potassium carbonate, and tetrahydrofuran was 10:0.1:1.1:0.6:100.

[0065] (3) Alkali-resistant fiber cloth

[0066] Toluene diisocyanate was mixed with polyethylene glycol (PEG600 from Kehui Chemical) and hydroxy silicone oil (107# silicone oil, industrial grade, produced by Zaoyang Sihai Chemical Co., Ltd.) for an addition reaction. The addition reaction was carried out in a nitrogen atmosphere at a temperature of 80°C for 5 hours to obtain a PU prepolymer. The molar ratio of the total molar mass of OH in the polyethylene glycol and hydroxy silicone oil to the NCO in the toluene diisocyanate was preferably 1:1.2, and the molar ratio of the polyethylene glycol to the hydroxy silicone oil was 6:1.

[0067] Modified polyvinyl chloride, PU prepolymer, and dibutyltin dilaurate were added to a twin-screw extruder and melt-blended at 160°C for 24 hours; then modified glass fiber was added and mixed evenly to obtain a melt; wherein the mass ratio of modified polyvinyl chloride, PU prepolymer, and modified glass fiber was 65:15:9;

[0068] The melt was extruded through a spinneret (aperture size 0.4 mm) and solidified through a cooling air duct (wind speed 7-8 m / s). The fiber surface was treated with plasma to generate a micron-scale rough structure. The plasma treatment power was 100 W, the gas was Ar, and the treatment time was 10 s.

[0069] The yarns are bundled (6 filaments) and subjected to three-level gradient hot drawing, where the temperatures of the three-level gradient hot drawing are 80°C → 120°C → 150°C in sequence and the drawing ratio is 4 times to form yarns; the yarns are woven into plain alkali-resistant fiber cloth with a plain weave, a warp density of 80 strands / inch and a weft density of 60 strands / inch. Example 3

[0070] (1) Preparation of modified glass fiber:

[0071] Prepare 1.5 M Tris-HCl buffer solution and adjust the pH to 9;

[0072] Add glass fiber (Fucai glass fiber powder 1500 mesh) into the Tris-HCl buffer solution and stir and disperse with ultrasonication;

[0073] Add N,N-bis(3-triethoxysilylpropyl)urea and perform ultrasonic treatment with stirring to obtain a dispersion; wherein, in the dispersion, the concentration of N,N-bis(3-triethoxysilylpropyl)urea is 4 mg / mL, and the mass ratio of glass fiber to N,N-bis(3-triethoxysilylpropyl)urea is 1:0.4;

[0074] The dispersion was placed in a shaker and reacted for 10 h under shaking;

[0075] The dispersion after the reaction is completed is filtered, washed and dried to obtain modified glass fiber.

[0076] (2) Preparation of modified polyvinyl chloride: polyvinyl chloride (Jiyesheng JYS14715) and tetrahydrofuran were mixed, and 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, and potassium carbonate were added, and the mixture was kept at 60°C for 4 hours; insoluble matter was filtered, and the solution was precipitated with a 10% methanol aqueous solution, and the precipitate was washed and dried to obtain modified polyvinyl chloride, wherein the mass ratio of the polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, potassium carbonate, and tetrahydrofuran was 10:0.1:1.3:0.7:100.

[0077] (3) Alkali-resistant fiber cloth

[0078] Toluene diisocyanate was mixed with polyethylene glycol (PEG400 from Kehui Chemical) and hydroxy silicone oil (107# silicone oil, industrial grade, from Zaoyang Sihai Chemical Co., Ltd.) for an addition reaction. The addition reaction was carried out in a nitrogen atmosphere at a temperature of 77°C for 6 hours to obtain a PU prepolymer. The molar ratio of the total molar mass of OH in the polyethylene glycol and hydroxy silicone oil to the NCO in the toluene diisocyanate was preferably 1:1.1, and the molar ratio of the polyethylene glycol to the hydroxy silicone oil was 7:1.

[0079] The modified polyvinyl chloride, PU prepolymer and stannous isooctanoate were added to a twin-screw extruder for melt blending at 160°C for 48 hours; then the modified glass fiber was added and mixed evenly to obtain a melt; wherein the mass ratio of the modified polyvinyl chloride, PU prepolymer and modified glass fiber was 65:13:7;

[0080] The melt was extruded through a spinneret (0.4 mm aperture) and solidified through a cooling air duct (wind speed 6-7 m / s). The fiber surface was treated with plasma to generate a micron-scale rough structure. The plasma treatment power was 100 W, the gas was Ar, and the treatment time was 13 s.

[0081] The yarns are bundled (6 filaments) and subjected to three-level gradient hot drawing, where the temperatures of the three-level gradient hot drawing are 80°C → 120°C → 150°C in sequence and the drawing ratio is 4 times to form yarns; the yarns are woven into plain alkali-resistant fiber cloth with a plain weave, a warp density of 80 strands / inch and a weft density of 60 strands / inch. Example 4

[0082] The difference between Example 4 and Example 3 is that the mass ratio of polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, potassium carbonate, and tetrahydrofuran in step (2) is 10:0.1:1.1:0.7:100, and the rest is the same as Example 3. Example 5

[0083] The difference between Example 5 and Example 3 is that the mass ratio of polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, potassium carbonate, and tetrahydrofuran in step (2) is 10:0.1:1.5:0.7:100, and the rest is the same as Example 3. Comparative Example 1

[0084] (1) Preparation of modified glass fiber: same as Example 3.

[0085] (2) Preparation of modified polyvinyl chloride: same as Example 3.

[0086] (3) Alkali-resistant fiber cloth

[0087] Toluene diisocyanate and polyethylene glycol (PEG400, Kehui Chemical) were mixed to carry out an addition reaction. The addition reaction was carried out in a nitrogen atmosphere at a temperature of 77°C for 6 hours to obtain a PU prepolymer. The molar ratio of OH in the polyethylene glycol to NCO in the toluene diisocyanate was preferably 3:1.

[0088] The modified polyvinyl chloride, PU prepolymer and stannous isooctanoate were added to a twin-screw extruder for melt blending at 160°C for 48 hours; then the modified glass fiber was added and mixed evenly to obtain a melt; wherein the mass ratio of the modified polyvinyl chloride, PU prepolymer and modified glass fiber was 65:13:7;

[0089] The melt was extruded through a spinneret and solidified through a cooling air duct (wind speed 6-7 m / s). The fiber surface was treated with plasma to generate a micron-scale rough structure. The plasma treatment power was 100 W, the gas was Ar, and the treatment time was 13 s.

[0090] The yarns are bundled (6 filaments) and subjected to three-level gradient hot drawing, where the temperatures of the three-level gradient hot drawing are 80°C → 120°C → 150°C in sequence and the drawing ratio is 4 times to form yarns; the yarns are woven into plain alkali-resistant fiber cloth with a plain weave, a warp density of 80 strands / inch and a weft density of 60 strands / inch. Comparative Example 2

[0091] Preparation of modified polyvinyl chloride: same as step (2) of Example 3.

[0092] Alkali-resistant fiber cloth: Toluene diisocyanate was mixed with polyethylene glycol (PEG400 from Kehui Chemical) and hydroxy silicone oil (107# silicone oil, industrial grade, produced by Zaoyang Sihai Chemical Co., Ltd.) for an addition reaction. The addition reaction was carried out in a nitrogen atmosphere at a temperature of 77°C for 6 hours to obtain a PU prepolymer. The molar ratio of the total molar mass of OH in the polyethylene glycol and hydroxy silicone oil to the NCO in the toluene diisocyanate was preferably 1:1.2, and the molar ratio of polyethylene glycol to hydroxy silicone oil was 7:1.

[0093] Modified polyvinyl chloride, PU prepolymer, and stannous isooctanoate were added to a twin-screw extruder and melt-blended at 160°C for 48 hours. Glass fiber (Fucai glass fiber powder 1500 mesh) was then added and mixed uniformly to obtain a melt. The mass ratio of modified polyvinyl chloride, PU prepolymer, and glass fiber was 65:13:7.

[0094] The melt was extruded through a spinneret and solidified through a cooling air duct (wind speed 6-7 m / s). The fiber surface was treated with plasma to generate a micron-scale rough structure. The plasma treatment power was 100 W, the gas was Ar, and the treatment time was 13 s.

[0095] The yarns are bundled (6 filaments) and subjected to three-level gradient hot drawing, where the temperatures of the three-level gradient hot drawing are 80°C → 120°C → 150°C in sequence and the drawing ratio is 4 times to form yarns; the yarns are woven into plain alkali-resistant fiber cloth with a plain weave, a warp density of 80 strands / inch and a weft density of 60 strands / inch. Comparative Example 3

[0096] (1) Preparation of modified glass fiber:

[0097] Prepare 1.5 M Tris-HCl buffer solution and adjust the pH to 9;

[0098] Add glass fiber (Fucai glass fiber powder 1500 mesh) into the Tris-HCl buffer solution and stir and disperse with ultrasonication;

[0099] KH550 was added and subjected to stirring and ultrasonic treatment to obtain a dispersion; wherein, in the dispersion, the concentration of KH550 was 4 mg / mL, and the mass ratio of glass fiber to KH550 was 1:0.4;

[0100] The dispersion was placed in a shaker and reacted for 10 h under shaking;

[0101] The dispersion after the reaction is completed is filtered, washed and dried to obtain modified glass fiber.

[0102] (2) Preparation of modified polyvinyl chloride: same as Example 3.

[0103] (3) Alkali-resistant fiber cloth

[0104] Toluene diisocyanate was mixed with polyethylene glycol (PEG400 from Kehui Chemical) and hydroxy silicone oil (107# silicone oil, industrial grade, produced by Zaoyang Sihai Chemical Co., Ltd.) for an addition reaction. The addition reaction was carried out in a nitrogen atmosphere at a temperature of 77°C for 6 hours to obtain a PU prepolymer. The molar ratio of the total molar mass of OH in the polyethylene glycol and hydroxy silicone oil to the NCO in the toluene diisocyanate was 1:1.2, and the molar ratio of the polyethylene glycol to the hydroxy silicone oil was 7:1.

[0105] The modified polyvinyl chloride, PU prepolymer and stannous isooctanoate were added to a twin-screw extruder and melt-blended at a temperature of 190°C for 48 hours; then the modified glass fiber was added and mixed evenly to obtain a melt; wherein the mass ratio of the modified polyvinyl chloride, PU prepolymer and modified glass fiber was 65:13:9:7;

[0106] The melt was extruded through a spinneret and solidified through a cooling air duct (wind speed 6-7 m / s). The fiber surface was treated with plasma to generate a micron-scale rough structure. The plasma treatment power was 100 W, the gas was Ar, and the treatment time was 13 s.

[0107] The yarns are bundled (6 filaments) and subjected to three-level gradient hot drawing, where the temperatures of the three-level gradient hot drawing are 80°C → 120°C → 150°C in sequence and the drawing ratio is 3 times to form yarns; the yarns are woven into plain alkali-resistant fiber cloth with a plain weave, a warp density of 80 strands / inch and a weft density of 60 strands / inch.

[0108] Comparative Example 3 is similar to Example 3, but uses KH550 modified glass fiber. The melt flowability is lower than that of Example 3, and the subsequent hot drawing is more difficult to operate. The melt blending temperature needs to be increased, and the draw ratio needs to be reduced to ensure the normal operation of the entire spinning process, which increases the energy consumption and reduces the efficiency of production. Comparative Example 4

[0109] (1) Preparation of modified glass fiber:

[0110] Prepare a 1.5M Tris-HCl aqueous buffer solution, and adjust the pH value to 9;

[0111] Add glass fiber (rich color glass fiber powder 1500 mesh) to the Tris-HCl aqueous buffer solution and stir and ultrasonically disperse;

[0112] Add N,N-di(3-triethoxysilylpropyl)urea and stir and ultrasonically treat to obtain a dispersion; wherein, in the dispersion, the concentration of N,N-di(3-triethoxysilylpropyl)urea is 4 mg / mL, and the mass ratio of glass fiber to N,N-di(3-triethoxysilylpropyl)urea is 1:0.4;

[0113] Place the dispersion in a shaker and react for 10 h under shaking;

[0114] Filter, wash, and dry the dispersion after the reaction is completed to obtain modified glass fiber.

[0115] (2) Alkali-resistant fiber cloth

[0116] Mix toluene diisocyanate with polyethylene glycol (Kewei Chemical PEG400) and hydroxyl silicone oil (Jiayang Sihai Chemical Co., Ltd. 107# silicone oil, industrial grade) to perform addition reaction. The addition reaction is performed in a N2 atmosphere, the reaction temperature is 77°C, and the reaction time is 6 h to obtain a PU prepolymer; wherein, the total molar mass of ·OH in polyethylene glycol and hydroxyl silicone oil to the molar of NCO in toluene diisocyanate is 1:1.2, and the molar ratio of polyethylene glycol to hydroxyl silicone oil is 7:1.

[0117] Melt blend modified polyvinyl chloride, PU prepolymer, and isooctanoic acid stannous with a twin-screw extruder at a temperature of 160°C for 48 h; then add modified glass fiber and mix uniformly to obtain a melt; wherein, the mass ratio of modified polyvinyl chloride, PU prepolymer, and modified glass fiber is 65:13:7, and the mass ratio of BPO to modified polyvinyl chloride is 65:0.2.

[0118] The melt was extruded through a spinneret (0.4 mm aperture) and solidified through a cooling air duct (wind speed 6-7 m / s). The fiber surface was treated with plasma to generate a micron-scale rough structure. The plasma treatment power was 100 W, the gas was Ar, and the treatment time was 13 s.

[0119] The yarns are bundled (6 filaments) and subjected to three-level gradient hot drawing, where the temperatures of the three-level gradient hot drawing are 80°C → 120°C → 150°C in sequence and the drawing ratio is 4 times to form yarns; the yarns are woven into plain alkali-resistant fiber cloth with a plain weave, a warp density of 80 strands / inch and a weft density of 60 strands / inch. Comparative Example 5

[0120] The mass ratio of polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecanethiol, potassium carbonate, and tetrahydrofuran in Comparative Example 5 and step (2) of Example 3 is 10:0.1:1.7:0.7:100, and the rest is the same as Example 3.

[0121] Effect Examples

[0122] Table 1 below shows the performance test results of strong alkali resistance and water impermeability of the above examples and comparative examples.

[0123] The source of the strong alkali resistance test data is: the mass loss of cloth of the same size soaked in 10wt% NaOH solution for 30 days.

[0124] The tensile performance test is based on GB / T328.9.

[0125] Table 1

[0126]

[0127] The alkali-resistant fiber cloth prepared in Example 3 was subjected to surface functional modification and laminated with a polyester nonwoven fabric to prepare a roll. The specific steps are as follows:

[0128] (1) Hydrophobic treatment: The fiber cloths of the embodiment and the comparative example were immersed in an acetone solution containing 2 wt% polyvinylidene fluoride (PVDF) and 1 wt% nano-silica, and then rolled and dried to form a microporous coating with a thickness of 4 μm;

[0129] (2) Irradiation treatment: The hydrophobic treated fiber cloth is subjected to electron beam irradiation (dose 60 kGy) to cross-link the fluorine-containing chain segments with the resin, and the mass loss rate after immersion in 10% NaOH solution for 30 days is ≤0.5%.

[0130] (3) The fiber cloth, the EVA-based hot melt adhesive layer with a thickness of 0.4 mm, the polyester non-woven fabric (non-woven fabric with a gram weight of 30-50 g / m², and the non-woven fabric with a gram weight of 50 g / m² is selected in this preparation method), the EVA-based hot melt adhesive layer with a thickness of 0.4 mm, and the fiber cloth are stacked in sequence and laminated (temperature 160°C, pressure 8 MPa) to obtain a composite cloth.

[0131] The interlayer peeling strength and water-tightness test results of the composite fabric are shown in Table 2 below.

[0132] Table 2

[0133]

[0134] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A waterproof polymer alkali-resistant fiber cloth, characterized in that: The invention is prepared from modified polyvinyl chloride, PU prepolymer and modified glass fiber; the modified polyvinyl chloride is prepared from polyvinyl chloride, 4-hydroxythiophenol and 1H,1H,2H,2H-perfluorododecanethiol; the PU prepolymer is prepared from polyethylene glycol, hydroxy silicone oil and toluene diisocyanate; the modified glass fiber is prepared from glass fiber modified by N,N-bis(3-triethoxysilylpropyl)urea; the mass ratio of the modified polyvinyl chloride, PU prepolymer and modified glass fiber is 65:10-15:6-9; The preparation method of modified polyvinyl chloride comprises the following steps: mixing polyvinyl chloride and tetrahydrofuran, adding 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecane mercaptan, and potassium carbonate, and keeping the mixture at 60-67°C for 4-5 hours; filtering insoluble matter, precipitating the solution with a methanol aqueous solution with a mass fraction of 10%, washing and drying the precipitate to obtain a modified polyvinyl chloride, wherein the mass ratio of the polyvinyl chloride, 4-hydroxythiophenol, 1H,1H,2H,2H-perfluorododecane mercaptan, and potassium carbonate is 10:0.1-0.3:1.1-1.5:0.6-0.

9.

2. The waterproof polymer alkali-resistant fiber cloth according to claim 1, characterized in that: The molar ratio of the total molar mass of ·OH in the polyethylene glycol and hydroxy silicone oil to NCO in toluene diisocyanate is 1:1.1-1.2; and the molar ratio of the polyethylene glycol to the hydroxy silicone oil is 6-8:

1.

3. The waterproof polymer alkali-resistant fiber cloth according to claim 1, characterized in that: The glass fiber is 1250-1500 mesh glass fiber powder.

4. A method for preparing the waterproof high molecular alkali-resistant fiber cloth according to any one of claims 1 to 3, characterized in that: The steps include: S11 melt blending: adding modified polyvinyl chloride, PU prepolymer and catalyst into a twin-screw extruder for melt blending, then adding modified glass fiber and mixing evenly to obtain a melt; S12 Spinning: After the melt is extruded through the spinneret, it solidifies into fibers, and the fiber surface is treated with plasma to generate a micron-scale rough structure; S13 is bundled, hot drawn and made into yarn; S14 Weave the yarn into alkali-resistant fiber cloth.

5. The method for preparing the waterproof high molecular alkali-resistant fiber cloth according to claim 4, characterized in that: The specific preparation steps of the modified glass fiber in step S11 are as follows: S21 Prepare a Tris-HCl buffer solution and adjust the pH to 8-10; S22 adding the glass fiber to the Tris-HCl buffer solution and stirring and ultrasonically dispersing the solution; S23: adding N,N-bis(3-triethoxysilylpropyl)urea and performing ultrasonic treatment with stirring to obtain a dispersion; S24 placing the dispersion on a shaker and reacting under shaking for 6 to 12 hours; S25 filtering, washing, and drying the dispersion after the reaction to obtain modified glass fiber; Wherein, the mass ratio of the glass fiber to N,N-bis(3-triethoxysilylpropyl)urea is 1:0.1-0.4; The spinneret aperture in step S13 is 0.2-0.4 mm.

6. The method for preparing the waterproof high molecular alkali-resistant fiber cloth according to claim 4, characterized in that: The PU prepolymer in step S11 is obtained by mixing toluene diisocyanate with polyethylene glycol and hydroxy silicone oil and performing an addition reaction; the addition reaction is carried out in a N2 atmosphere at a reaction temperature of 70-80°C for 5-8 hours.

7. A composite fabric comprising the waterproof high molecular alkali-resistant fiber cloth according to any one of claims 1 to 3, characterized in that: The composite fabric comprises at least one layer of polyester non-woven fabric and waterproof high molecular alkali-resistant fiber fabric; the polyester non-woven fabric and the waterproof high molecular alkali-resistant fiber fabric are bonded together by EVA-based hot melt adhesive.

8. The composite fabric according to claim 7, characterized in that: The waterproof polymer alkali-resistant fiber cloth is subjected to surface functionalization treatment; the surface functionalization treatment includes at least one of hydrophobic treatment and irradiation treatment.

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