Resin glass fiber polymer anticorrosive plate and preparation method thereof
By coating the substrate surface of the resin fiberglass polymer anticorrosion board with a protective layer of a specific material, the problems of increased surface roughness and high wear rate caused by glass fiber are solved, achieving high strength and corrosion resistance of the substrate.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-13
- Publication Date
- 2026-03-20
AI Technical Summary
The addition of glass fiber to existing resin-coated fiberglass polymer anti-corrosion boards increases their surface roughness, making them prone to higher wear rates during use.
Vinyl resin and alkali-free glass fiber are used as the substrate, and a protective layer of materials such as triethanolamine borate modified Mo/S/Ce composite and isocyanate modified fibrous attapulgite is coated on the substrate surface. The surface of the substrate is modified by ethylene-vinyl acetate copolymer to reduce surface roughness and wear rate.
It effectively reduces the surface roughness of the substrate, reduces the wear rate, and improves the adhesion strength of the protective layer on the substrate surface, making the board structure more complete and stable.
Smart Images
Figure CN121699221A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of high polymer anticorrosion plate preparation and relates to a resin glass fiber high polymer anticorrosion plate and a preparation method thereof. BACKGROUND
[0002] The glass fiber resin plate is a composite material taking glass fiber as a reinforcing material and resin as a matrix, has the characteristics of high strength, corrosion resistance, fireproofness, environmental protection and the like, and is widely applied to the fields of building, medical treatment, industry and the like.
[0003] Although the addition of glass fiber can significantly strengthen the resin matrix, the fiber end part is prone to be exposed after the glass fiber is added into the resin, and the surface is prone to have glass fiber floating, which leads to rough surface of the plate and further increases the wear rate, when the anticorrosion plate is used for building as a skylight structure, the surface of the plate is frequently rubbed in the use scenes of opening and closing, sliding and the like, the wear rate is significantly increased when the surface roughness is high, and once the high surface roughness occurs, the rough surface is prone to adsorb and penetrate pollutants, which also reduces the corrosion resistance and mechanical strength. SUMMARY
[0004] The application aims to provide a resin glass fiber high polymer anticorrosion plate and a preparation method thereof, and solve the problem that the surface roughness of the existing resin glass fiber high polymer anticorrosion plate is increased due to the addition of glass fiber, and a high wear rate is prone to occur in the use process.
[0005] The technical scheme adopted by the application is as follows. A resin glass fiber high polymer anticorrosion plate comprises a base material and a protective layer on the surface of the base material. The base material comprises vinyl resin, alkali-free glass fiber and curing agent, and the surface of the base material is subjected to polarity modification by ethylene-vinyl acetate copolymer, wherein the addition amount of the alkali-free glass fiber is 25-28% of the mass of the vinyl resin, and the addition amount of the curing agent is 1.2-1.5% of the mass of the vinyl resin. The component ratio of the protective layer is calculated separately, and the protective layer comprises isophthalic acid / neopentyl glycol type unsaturated polyester gel coat resin, triethanolamine borate modified Mo / S / Ce composite, isocyanate modified fibrous attapulgite, silane coupling agent, initiator and crosslinking agent; wherein the mass ratio of the triethanolamine borate modified Mo / S / Ce composite is 6-8%, the mass ratio of the isocyanate modified fibrous attapulgite is 10-12%, the mass ratio of the silane coupling agent is 1.5-2%, the mass ratio of the initiator is 1-1.2%, the mass ratio of the crosslinking agent is 2-2.5%, and the rest is isophthalic acid / neopentyl glycol type unsaturated polyester gel coat resin.
[0006] Further, the ethylene-vinyl acetate copolymer-modified substrate is prepared by the following method: vinyl resin, alkali-free glass fiber and curing agent are mixed in proportion, stirred evenly and poured into a preset mold, and a substrate blank is obtained by closed molding method; the ethylene-vinyl acetate copolymer is dissolved in toluene to prepare an ethylene-vinyl acetate copolymer solution with a mass fraction of 10-12%; the surface of the substrate blank is roughened by sandpaper, and then the ethylene-vinyl acetate copolymer solution is uniformly coated on the surface of the substrate blank, the amount of ethylene-vinyl acetate copolymer is 6-7% of the total mass of the substrate blank, and dried to obtain the ethylene-vinyl acetate copolymer-modified substrate.
[0007] Furthermore, the alkali-free glass fiber is modified with a silane coupling agent and obtained by the following preparation method: alkali-free glass fiber is cut into short fibers of 3-5 mm, placed in an ethanol-water solution, and ultrasonically dispersed evenly; then, silane coupling agent KH550 is added, the amount of silane coupling agent KH550 being 2-2.5% of the mass of the alkali-free glass fiber; after stirring evenly, the pH value of the reaction system is adjusted to 4.5-5.0 with dilute hydrochloric acid, and stirred at a constant temperature of 55-60℃ for 2.5-3 h; after stirring, the fiber is filtered and separated, washed with deionized water until neutral, and then dried to obtain alkali-free glass fiber modified with silane coupling agent.
[0008] Further, the Mo / S / Ce composite was prepared by the following method: using ammonium molybdate as the molybdenum source, thiourea as the sulfur source, and cerium nitrate as the cerium source, the raw materials were added sequentially to deionized water according to a molar ratio of Mo:S:Ce of 1:2:(0.2-0.25), and ultrasonically dispersed until a uniform mixture was formed; the mixture was transferred to a hydrothermal reactor, sealed, and placed in an oven, and reacted at a constant temperature of 200℃ for 14-16 h. After the reaction was completed, the mixture was naturally cooled to room temperature, centrifuged to obtain the precipitate, washed alternately with deionized water and anhydrous ethanol, and finally dried to obtain the Mo / S / Ce composite.
[0009] Further, the triethanolamine borate-modified Mo / S / Ce composite was prepared by the following method: using anhydrous ethanol as a solvent, the Mo / S / Ce composite was added and ultrasonically dispersed for 25-30 min to form a suspension with a mass fraction of 5-8%; triethanolamine borate was added at a mass ratio of 1:7-8 to the Mo / S / Ce composite, and then 0.7% by mass of p-toluenesulfonic acid was added; nitrogen gas was introduced for protection, and the mixture was stirred at a constant temperature of 65-70℃ for 3.5-4 h; after the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and dried to obtain the triethanolamine borate-modified Mo / S / Ce composite.
[0010] Further, the isocyanate-modified fibrous attapulgite is prepared by the following method: the fibrous attapulgite is dried in a drying oven; the dried fibrous attapulgite is added to anhydrous toluene and ultrasonically dispersed to form a suspension; toluene diisocyanate is added at a mass ratio of 1:8-9 to attapulgite, and the mixture is heated to 75-80℃ under nitrogen protection and stirred at a constant temperature for 4.5-5 hours; after the reaction is completed, the mixture is filtered and separated, washed with anhydrous toluene, and then dried to obtain the isocyanate-modified fibrous attapulgite.
[0011] Further, the preparation method of the protective layer is as follows: isophthalic acid / neoprene glycol type unsaturated polyester gel coat resin is poured into a mixing tank, a silane coupling agent is added and stirred at low speed until uniform, then isocyanate-modified fibrous attapulgite is added, stirred at low speed for 20 min and then at high speed for 30 min; subsequently, triethanolamine borate-modified Mo / S / Ce composite is added, stirred at high speed for 30 min and then ultrasonically dispersed for 25 min; finally, an initiator and crosslinking agent are added, and stirred at low speed until uniformly dispersed to obtain a protective layer slurry; the protective layer slurry is sprayed onto the surface of an ethylene-vinyl acetate copolymer modified substrate, pre-cured at room temperature for 2.5-3 h and then cured at a constant temperature of 75-80℃ for 3-3.5 h to obtain a protective layer, the thickness of which is 100-200 μm.
[0012] Furthermore, the vinyl resin in the substrate is a bisphenol A type vinyl ester resin, and the curing agent is methyl ethyl ketone peroxide; the silane coupling agent in the protective layer is γ-aminopropyltriethoxysilane, the initiator is benzoyl peroxide, and the crosslinking agent is divinylbenzene.
[0013] Furthermore, the ethylene-vinyl acetate copolymer is obtained by copolymerizing ethylene and vinyl acetate monomers at a mass ratio of 7:3.
[0014] The method for preparing a resin-glass fiber polymer anti-corrosion board includes the following steps: S1. A substrate is prepared by using vinyl resin, alkali-free glass fiber, and curing agent, and then the surface of the substrate is modified with ethylene-vinyl acetate copolymer to obtain a substrate with surface modification by ethylene-vinyl acetate copolymer. S2. Prepare a protective layer slurry by mixing isophthalic acid / neopulinic glycol type unsaturated polyester gel coat resin, triethanolamine borate modified Mo / S / Ce composite, isocyanate modified fibrous attapulgite, silane coupling agent, initiator, and crosslinking agent. Then spray the protective layer slurry onto the surface of the substrate modified with ethylene-vinyl acetate copolymer. After curing, a resin glass fiber polymer anti-corrosion board is obtained.
[0015] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. In this invention, the substrate uses vinyl ester resin and alkali-free glass fiber as the core materials. Based on the mechanism of fiber-reinforced resin, a high-strength and corrosion-resistant substrate is obtained. A protective layer is coated on the surface of the substrate, with triethanolamine borate-modified Mo / S / Ce composite and isocyanate-modified fibrous attapulgite as the core materials. The protective layer lubricates and smooths the surface of the substrate, reducing surface roughness and wear rate. This solves the problem that the addition of glass fiber increases the surface roughness of the substrate and easily leads to a high wear rate during use. 2. In this invention, the surface of the substrate is polarized, which helps to strengthen the adhesion of the protective layer to the substrate surface, making the entire board structure intact and stable. Attached Figure Description
[0016] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort, wherein: Figure 1 This is a physical image of the substrate prepared in Example 2 of the present invention; Figure 2 This is a picture of the finished anti-corrosion board prepared according to Example 2 of the present invention; Figure 3 This is a physical image of the side wall of the anti-corrosion plate prepared in Example 2 of the present invention; Figure 4 This is a microscopic image of the Mo / S / Ce composite of the present invention. Detailed Implementation
[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments. The components of the embodiments of the invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.
[0018] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.
[0019] It should be noted that relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0020] The features and performance of the present invention will be further described in detail below with reference to embodiments.
[0021] This invention provides a resin-glass fiber polymer anti-corrosion board, including a substrate and a protective layer on the surface of the substrate; The substrate comprises vinyl ester resin, alkali-free glass fiber, and a curing agent, and the surface of the substrate is polar-modified by ethylene-vinyl acetate copolymer, wherein the amount of alkali-free glass fiber added is 25-28% of the mass of vinyl ester resin, and the amount of curing agent added is 1.2-1.5% of the mass of vinyl ester resin; The composition ratio of the protective layer is calculated separately. The protective layer includes isophthalic acid / neoplastic glycol type unsaturated polyester gel coat resin, triethanolamine borate modified Mo / S / Ce composite, isocyanate modified fibrous attapulgite, silane coupling agent, initiator, and crosslinking agent. Among them, the mass percentage of triethanolamine borate modified Mo / S / Ce composite is 6-8%, the mass percentage of isocyanate modified fibrous attapulgite is 10-12%, the mass percentage of silane coupling is 1.5-2%, the mass percentage of initiator is 1-1.2%, the mass percentage of crosslinking agent is 2-2.5%, and the balance is isophthalic acid / neoplastic glycol type unsaturated polyester gel coat resin.
[0022] The ethylene-vinyl acetate copolymer-modified substrate is prepared by the following method: vinyl ester resin, alkali-free glass fiber, and curing agent are mixed in proportion, stirred evenly, and poured into a preset mold. A substrate preform is obtained by closed-loop molding. The ethylene-vinyl acetate copolymer is dissolved in toluene to prepare an ethylene-vinyl acetate copolymer solution with a mass fraction of 10-12%. The surface of the substrate preform is roughened by sandpaper, and then the ethylene-vinyl acetate copolymer solution is uniformly coated on the surface of the substrate preform. The amount of ethylene-vinyl acetate copolymer is 6-7% of the total mass of the substrate preform. The substrate is dried to obtain the ethylene-vinyl acetate copolymer-modified substrate.
[0023] The alkali-free glass fiber is modified with a silane coupling agent and prepared by the following method: alkali-free glass fiber is cut into short fibers of 3-5 mm and placed in an ethanol-water solution (ethanol to water volume ratio 3:1), and ultrasonically dispersed evenly (15 min); then, silane coupling agent KH550 is added, the amount of silane coupling agent KH550 being 2-2.5% of the mass of the alkali-free glass fiber. After stirring evenly, the pH value of the reaction system is adjusted to 4.5-5.0 with dilute hydrochloric acid, and stirred at a constant temperature of 55-60℃ for 2.5-3 h; after stirring, the fiber is filtered and separated, washed with deionized water until neutral, and then dried to obtain silane coupling agent modified alkali-free glass fiber.
[0024] The Mo / S / Ce composite was prepared by the following method: using ammonium molybdate as the molybdenum source, thiourea as the sulfur source, and cerium nitrate as the cerium source, the raw materials were added sequentially to deionized water according to a molar ratio of Mo:S:Ce of 1:2:(0.2-0.25), and ultrasonically dispersed until a uniform mixture was formed. The mixture was transferred to a hydrothermal reactor, sealed, and placed in an oven. The reaction was carried out at 200°C for 14-16 hours. After the reaction was completed, the mixture was naturally cooled to room temperature, centrifuged to obtain the precipitate, washed alternately with deionized water and anhydrous ethanol, and finally dried to obtain the Mo / S / Ce composite.
[0025] The triethanolamine borate-modified Mo / S / Ce composite was prepared by the following method: Anhydrous ethanol was used as the solvent; the Mo / S / Ce composite was added and ultrasonically dispersed for 25-30 min to form a suspension with a mass fraction of 5-8%; triethanolamine borate was added at a mass ratio of 1:7-8 to the Mo / S / Ce composite, followed by 0.7% (by mass) of p-toluenesulfonic acid; nitrogen gas was introduced for protection, and the mixture was stirred at a constant temperature of 65-70℃ for 3.5-4 h; after the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and dried to obtain the triethanolamine borate-modified Mo / S / Ce composite.
[0026] The isocyanate-modified fibrous attapulgite was prepared by the following method: the fibrous attapulgite was placed in a vacuum drying oven at 110°C and dried for 6-8 hours to remove surface adsorbed water; the dried fibrous attapulgite was added to anhydrous toluene and ultrasonically dispersed for 30 minutes to form a suspension; toluene diisocyanate was added at a mass ratio of 1:8-9 to attapulgite, and the mixture was heated to 75-80°C under nitrogen protection and stirred at a constant temperature for 4.5-5 hours; after the reaction was completed, the mixture was filtered and separated, washed with anhydrous toluene, and dried to obtain the isocyanate-modified fibrous attapulgite.
[0027] The protective layer is prepared as follows: isophthalic acid / neopulmonol type unsaturated polyester gel coat resin is poured into a mixing tank, a silane coupling agent is added and stirred at low speed until uniform, then isocyanate-modified fibrous attapulgite is added, stirred at low speed for 20 min and then stirred at high speed (800-1000 r / min) for 30 min; then triethanolamine borate-modified Mo / S / Ce composite is added, stirred at high speed for 30 min and then ultrasonically dispersed for 25 min; finally, an initiator and crosslinking agent are added, and stirred at low speed for 15 min until uniformly dispersed to obtain a protective layer slurry; the protective layer slurry is sprayed onto the surface of an ethylene-vinyl acetate copolymer modified substrate, pre-cured at room temperature for 2.5-3 h and then cured at 75-80℃ for 3-3.5 h to obtain a protective layer with a thickness of 100-200 μm.
[0028] The vinyl resin in the substrate is bisphenol A type vinyl ester resin, and the curing agent is methyl ethyl ketone peroxide; the silane coupling agent in the protective layer is γ-aminopropyltriethoxysilane, the initiator is benzoyl peroxide, and the crosslinking agent is divinylbenzene.
[0029] The ethylene-vinyl acetate copolymer is obtained by copolymerizing ethylene and vinyl acetate monomers at a mass ratio of 7:3.
[0030] The method for preparing a resin-glass fiber polymer anti-corrosion board includes the following steps: S1. A substrate is prepared by using vinyl resin, alkali-free glass fiber, and curing agent, and then the surface of the substrate is modified with ethylene-vinyl acetate copolymer to obtain a substrate with surface modification by ethylene-vinyl acetate copolymer. S2. A protective layer slurry is prepared by mixing isophthalic acid / neoprene glycol type unsaturated polyester gel coat resin, triethanolamine borate modified Mo / S / Ce composite, isocyanate modified fibrous attapulgite, silane coupling agent, initiator, and crosslinking agent. This protective layer slurry is then sprayed onto the surface of a substrate modified with ethylene-vinyl acetate copolymer. After curing, a resin-coated glass fiber polymer anti-corrosion board is obtained. Based on the above, the specific implementation method of this application is as follows: Example 1
[0031] A preferred embodiment of the present invention provides a resin-glass fiber polymer anti-corrosion board, which is prepared by the following method: S1. Bisphenol A type vinyl ester resin, alkali-free glass fiber, and methyl ethyl ketone peroxide curing agent are mixed according to the specified ratio, stirred evenly, and poured into a pre-set mold to obtain a substrate preform by closed-loop molding. Ethylene-vinyl acetate copolymer is dissolved in toluene to prepare an 11% (w / w) ethylene-vinyl acetate copolymer solution, wherein the ethylene-vinyl acetate copolymer is obtained by copolymerizing ethylene and vinyl acetate monomers at a mass ratio of 7:3. The surface of the substrate preform is roughened with sandpaper, and then the ethylene-vinyl acetate copolymer solution is uniformly coated onto the surface of the substrate preform. The amount of ethylene-vinyl acetate copolymer used is 6.5% of the total mass of the substrate preform. The substrate modified with ethylene-vinyl acetate copolymer is obtained by drying. The amount of alkali-free glass fiber added is 25% (w / w) of the mass of bisphenol A type vinyl ester resin, and the amount of methyl ethyl ketone peroxide curing agent added is 1.2% (w / w) of the mass of bisphenol A type vinyl ester resin. S2. Pour isophthalic acid / neoprene glycol type unsaturated polyester gel coat resin into a mixing tank. First, add γ-aminopropyltriethoxysilane silane coupling agent and stir at low speed until homogeneous. Then, add isocyanate-modified fibrous attapulgite and stir at low speed (300 r / min) for 20 min, followed by high speed stirring (1000 r / min) for 30 min. Next, add triethanolamine borate-modified Mo / S / Ce composite and stir at high speed (1000 r / min) for 30 min, followed by ultrasonic dispersion for 25 min. Finally, add benzoyl peroxide initiator and divinylbenzene crosslinking agent and stir at low speed (300 r / min) for 15 min until uniformly dispersed to obtain the protective layer slurry. Spray the protective layer slurry onto ethylene... The substrate surface modified with vinyl acetate copolymer was pre-cured at room temperature for 2.5 h and then cured at 75℃ for 3.5 h to obtain a resin-glass fiber polymer anti-corrosion board. The thickness of the protective layer of the resin-glass fiber polymer anti-corrosion board is 150 μm (dry film). The composition ratio of the protective layer was calculated separately. The mass ratio of triethanolamine borate modified Mo / S / Ce composite was 7%, the mass ratio of isocyanate modified fibrous attapulgite was 11%, the mass ratio of γ-aminopropyltriethoxysilane silane coupling agent was 1.8%, the mass ratio of benzoyl peroxide initiator was 1.1%, the mass ratio of divinylbenzene crosslinking agent was 2.3%, and the balance was isophthalic acid / neopulmonol type unsaturated polyester gel coat resin.
[0032] In this embodiment, the alkali-free glass fiber is modified with a silane coupling agent and prepared by the following method: alkali-free glass fiber is cut into short fibers of 3-5 mm and placed in an ethanol-water solution (ethanol to water volume ratio 3:1), and ultrasonically dispersed evenly (15 min); then, silane coupling agent KH550 is added, with the amount of silane coupling agent KH550 being 2.3% of the mass of the alkali-free glass fiber. After stirring evenly, the pH of the reaction system is adjusted to 5.0 with dilute hydrochloric acid, and the mixture is stirred at a constant temperature of 60°C for 3 h; after stirring, the fiber is filtered and separated, washed with deionized water until neutral, and then dried to obtain alkali-free glass fiber modified with silane coupling agent.
[0033] The Mo / S / Ce composite described in this embodiment was prepared by the following method: Ammonium molybdate was used as the molybdenum source, thiourea as the sulfur source, and cerium nitrate as the cerium source. The raw materials were sequentially added to deionized water according to a Mo:S:Ce molar ratio of 1:2:0.23, and ultrasonically dispersed until a homogeneous mixture was formed. The mixture was transferred to a hydrothermal reactor, sealed, and placed in an oven. The reactor was reacted at 200°C for 15 hours. After the reaction, the mixture was naturally cooled to room temperature, centrifuged to obtain the precipitate, and washed alternately with deionized water and anhydrous ethanol. Finally, the precipitate was dried to obtain the Mo / S / Ce composite, with the microstructure shown below. Figure 4 As shown.
[0034] The triethanolamine borate-modified Mo / S / Ce composite described in this embodiment was prepared by the following method: Anhydrous ethanol was used as the solvent, and the Mo / S / Ce composite was ultrasonically dispersed for 30 min to form a 7% (w / w) suspension; triethanolamine borate was added at a mass ratio of 1:8 to the Mo / S / Ce composite, followed by 0.7% (w / w) of p-toluenesulfonic acid from the triethanolamine borate; nitrogen gas was introduced for protection, and the mixture was stirred at 70°C for 4 h; after the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and dried to obtain the triethanolamine borate-modified Mo / S / Ce composite.
[0035] The isocyanate-modified fibrous attapulgite described in this embodiment was prepared by the following method: the fibrous attapulgite was dried in a vacuum drying oven at 110°C for 8 hours to remove surface adsorbed water; the dried fibrous attapulgite was added to anhydrous toluene and ultrasonically dispersed for 30 minutes to form a suspension; toluene diisocyanate was added at a mass ratio of 1:8.5 to toluene diisocyanate, and the mixture was heated to 80°C under nitrogen protection and stirred at a constant temperature for 5 hours; after the reaction was completed, the mixture was filtered and separated, washed with anhydrous toluene, and dried to obtain the isocyanate-modified fibrous attapulgite.
[0036] Example 2
[0037] This embodiment differs from Embodiment 1 in that, in step S1, the amount of alkali-free glass fiber added is 26.5% of the mass of bisphenol A type vinyl ester resin, and the amount of methyl ethyl ketone peroxide curing agent added is 1.3% of the mass of bisphenol A type vinyl ester resin; all other aspects remain the same. The ethylene-vinyl acetate copolymer modified substrate prepared within the scope of this embodiment (matching the actual object with the preset mold shape) is as follows: Figure 1 As shown, a distinct fibrous structure can be seen internally under light; the finished product image of the anti-corrosion board is shown below. Figure 2 , Figure 3 As shown, the surface is smooth and glossy with no delamination on the sides, and the structure is intact.
[0038] Example 3
[0039] This embodiment differs from Embodiment 1 in that, in step S1, the amount of alkali-free glass fiber added is 28% of the mass of bisphenol A type vinyl ester resin, and the amount of methyl ethyl ketone peroxide curing agent added is 1.5% of the mass of bisphenol A type vinyl ester resin; all other aspects are the same.
[0040] Example 4
[0041] This embodiment differs from Embodiment 2 in that the composition ratio of the protective layer is calculated separately. The mass percentage of the triethanolamine borate-modified Mo / S / Ce composite is 6%, the mass percentage of the isocyanate-modified fibrous attapulgite is 10%, the mass percentage of the silane coupling is 1.5%, the mass percentage of the initiator is 1%, the mass percentage of the crosslinking agent is 2%, and the balance is isophthalic acid / neoprene glycol type unsaturated polyester gel coat resin; all other components are the same.
[0042] Example 5
[0043] This embodiment differs from Embodiment 2 in that the composition ratio of the protective layer is calculated separately. The mass percentage of the triethanolamine borate-modified Mo / S / Ce composite is 8%, the mass percentage of the isocyanate-modified fibrous attapulgite is 12%, the mass percentage of the silane coupling is 2%, the mass percentage of the initiator is 1.2%, the mass percentage of the crosslinking agent is 2.5%, and the balance is isophthalic acid / neoprolol type unsaturated polyester gel coat resin; all other components are the same.
[0044] Example 6
[0045] Based on Example 2, but differing from Example 2, the Mo / S / Ce composite described in this example was prepared by the following method: using ammonium molybdate as the molybdenum source, thiourea as the sulfur source, and cerium nitrate as the cerium source, the raw materials were sequentially added to deionized water according to a molar ratio of Mo:S:Ce of 1:2:0.2, and ultrasonically dispersed until a uniform mixture was formed; the mixture was transferred to a hydrothermal reactor, sealed, and placed in an oven, where it was reacted at 200°C for 14 hours. After the reaction, it was naturally cooled to room temperature, centrifuged to obtain the precipitate, washed alternately with deionized water and anhydrous ethanol, and finally dried to obtain the Mo / S / Ce composite.
[0046] Example 7
[0047] Based on Example 2, but differing from Example 2, the Mo / S / Ce composite described in this example was prepared by the following method: using ammonium molybdate as the molybdenum source, thiourea as the sulfur source, and cerium nitrate as the cerium source, the raw materials were sequentially added to deionized water according to a molar ratio of Mo:S:Ce of 1:2:0.25, and ultrasonically dispersed until a uniform mixture was formed; the mixture was transferred to a hydrothermal reactor, sealed, and placed in an oven, where it was reacted at 200°C for 16 hours. After the reaction, it was naturally cooled to room temperature, centrifuged to obtain the precipitate, washed alternately with deionized water and anhydrous ethanol, and finally dried to obtain the Mo / S / Ce composite.
[0048] Example 8
[0049] Based on Example 2, the difference from Example 2 is that the thickness of the protective layer of the resin fiberglass polymer anticorrosion board in this example is 100μm (dry film); all other aspects are the same.
[0050] Example 9
[0051] Based on Example 2, the difference from Example 2 is that the thickness of the protective layer of the resin fiberglass polymer anticorrosion board in this example is 200μm (dry film); all other aspects are the same.
[0052] Comparative Example 1 The resin-coated glass fiber polymer anti-corrosion board (without a protective layer) provided in this comparative example is prepared by the following method: bisphenol A type vinyl ester resin, alkali-free glass fiber (3-5 mm short chopped fiber, not modified by silane coupling agent) and methyl ethyl ketone peroxide curing agent are mixed in a certain proportion, stirred evenly, and then poured into a preset mold. The resin-coated glass fiber polymer anti-corrosion board is obtained by closed-loop molding. The amount of alkali-free glass fiber added is 26.5% of the mass of bisphenol A type vinyl ester resin, and the amount of methyl ethyl ketone peroxide curing agent added is 1.3% of the mass of bisphenol A type vinyl ester resin.
[0053] Comparative Example 2 Based on Comparative Example 1, and without the protective layer, this application uses alkali-free glass fiber modified with silane coupling agent instead of the alkali-free glass fiber without silane coupling agent modification in Comparative Example 1. All other aspects are the same. The preparation method of alkali-free glass fiber modified with silane coupling agent can be referred to Example 1.
[0054] Comparative Example 3 Based on Example 2, the difference from Example 2 is that the protective layer of this comparative example does not contain the triethanolamine borate-modified Mo / S / Ce complex, but all other aspects are the same (adaptive adjustments were made to the preparation method).
[0055] Comparative Example 4 Based on Example 2, the difference from Example 2 is that the protective layer of this comparative example does not contain isocyanate-modified fibrous attapulgite, but all other aspects are the same (adaptive adjustments were made to the preparation method).
[0056] Comparative Example 5 Based on Example 2, the difference from Example 2 is that the fibrous attapulgite in the protective layer of this comparative example is not modified with isocyanate, and the fibrous attapulgite is purchased directly; all other aspects are the same.
[0057] Comparative Example 6 Based on Example 2, the difference from Example 2 is that the Mo / S / Ce composite in the protective layer of this comparative example is not modified by triethanolamine borate, and the preparation method of the Mo / S / Ce composite is the same as in Example 1.
[0058] Comparative Example 7 Based on Example 2, the difference from Example 2 is that the substrate of this comparative example is not modified by surface polarity through ethylene-vinyl acetate copolymer. Bisphenol A type vinyl ester resin, alkali-free glass fiber and methyl ethyl ketone peroxide curing agent are mixed in proportion, stirred evenly and poured into a preset mold. The substrate is obtained by closed molding method. The substrate is not modified by ethylene-vinyl acetate copolymer and is directly used to attach the protective layer. All other aspects are the same.
[0059] Comparative Example 8 Based on Example 2, the difference from Example 2 is that this comparative example uses a Mo / S composite instead of the Mo / S / Ce composite in Example 2. The preparation method is the same as the preparation method and amount of the Mo / S / Ce composite in Example 1, except that no cerium source is added.
[0060] Experimental Example 1 The appearance characteristics, surface roughness, wear rate and corrosion resistance of the resin glass fiber polymer anti-corrosion boards (with a conventional thickness of 2 mm) prepared in Examples 1-9 and Comparative Examples 1-8 were tested. The results are shown in Table 1.
[0061] Appearance characteristics: Refer to GB / T 1446-2005 "General Rules for Test Methods of Fiber Reinforced Plastics", and adapt and adjust the test method accordingly. Under natural light, observe the surface condition of the anti-corrosion board with the naked eye (whether it is smooth, whether there are bubbles, cracks, delamination, exposed fibers and other defects). Surface roughness: Referring to GB / T 1031-2009 "Product Geometric Specification (GPS) - Surface Structure Profile Method: Roughness Parameters and Values", a contact roughness tester (model: TR200) was used for testing. The testing parameters were set as follows: sampling length 0.8 mm, evaluation length 4.0 mm, and measurement speed 0.5 mm / s. Testing was conducted at different locations on each anti-corrosion plate (5 test points were randomly selected). The arithmetic mean deviation Ra of the profile at each test point was recorded, and the average value was taken as the surface roughness value of the sample. (The recorded value is the average of multiple parallel samples.) Wear rate: Based on GB / T 3960-2016 "Test Method for Sliding Friction and Wear of Plastics", adjustments were made, and a pin-disc friction and wear testing machine was used for testing; the mating part was a GCr15 steel ball (5mm diameter); load (F) 50N; rotation speed 200r / min; wear time (t) 60min; test environment: room temperature (25±2℃), relative humidity (50±5)%; before the test, the anti-corrosion plate sample was cut into 10mm×10mm×2mm blocks, the surface was wiped with anhydrous ethanol and dried, and the initial mass m1 of the block was weighed using an electronic balance; after the test, the wear debris on the surface of the block was cleaned with anhydrous ethanol, dried, and then weighed m2; wear rate calculation formula: W=(m1-m2) / (F×t), unit is mg / (N・h); F is the load, unit is N; t is the wear time, unit is h; (recorded values are the average values of multiple parallel samples) Corrosion resistance: Referring to GB / T 3857-2017 "Test Method for Chemical Resistance of Glass Fiber Reinforced Thermosetting Plastics", three corrosive media were prepared: 40% hydrochloric acid solution, 5% sodium hydroxide solution, and kerosene. The anti-corrosion plates from Examples 1-9 and Comparative Examples 1-8 were cut into 50mm × 20mm × 2mm test blocks. The test blocks were completely immersed in the corresponding corrosive media at a temperature of 25±2℃ for 72 hours. After immersion, the test blocks were removed, rinsed, and dried to constant weight. The weight change rate before and after immersion was calculated as: weight change rate = (initial weight - weight after rinsing and drying to constant weight) / initial weight × 100%. (The recorded value is the average of multiple parallel samples.) Table 1. Test results of resin-glass fiber polymer anti-corrosion board
[0062] Experimental Example 2 The bending strength, tensile strength, and Barcol hardness of the anti-corrosion plates prepared in Examples 1-9, Comparative Examples 1 and 2 were tested, and the results are shown in Table 2.
[0063] Bending strength test: The test method refers to the standard GB / T 1449-2005 "Test method for bending properties of fiber reinforced plastics". The specific steps are existing technology and can be referred to the standard. Tensile strength test: The test method refers to the standard GB / T 1447-2005 "Test Method for Tensile Properties of Fiber Reinforced Plastics". The specific steps are existing technology and can be referred to the standard. Barcol hardness: The test method refers to the standard GB / T 3854-2005 "Test method for Barcol hardness of fiber reinforced plastics". The specific steps are existing technology and can be referred to the standard. The data recorded in the table below are the range values of the results from multiple parallel samples.
[0064] Table 2 Basic Performance Testing of Anticorrosion Boards Comparative Example 1 is the prior art. Based on the data in Tables 1 and 2, compared with Comparative Example 1, after the protective layer is attached to the outer surface of the resin fiberglass polymer substrate, this application not only solves the problem of rough surface and high wear rate of the anti-corrosion board caused by the addition of glass fiber, but also improves the anti-corrosion, mechanical strength, hardness and other properties of the resin fiberglass polymer board, making it suitable for fields such as skylights (where there will be frequent sliding friction).
[0065] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A resin-glass fiber polymer anti-corrosion board, characterized in that: This includes the substrate and the protective layer on the substrate surface; The substrate comprises vinyl ester resin, alkali-free glass fiber, and a curing agent, and the surface of the substrate is polar-modified by ethylene-vinyl acetate copolymer, wherein the amount of alkali-free glass fiber added is 25-28% of the mass of vinyl ester resin, and the amount of curing agent added is 1.2-1.5% of the mass of vinyl ester resin; The composition ratio of the protective layer is calculated separately. The protective layer includes isophthalic acid / neoplastic glycol type unsaturated polyester gel coat resin, triethanolamine borate modified Mo / S / Ce composite, isocyanate modified fibrous attapulgite, silane coupling agent, initiator, and crosslinking agent. Among them, the mass percentage of triethanolamine borate modified Mo / S / Ce composite is 6-8%, the mass percentage of isocyanate modified fibrous attapulgite is 10-12%, the mass percentage of silane coupling agent is 1.5-2%, the mass percentage of initiator is 1-1.2%, the mass percentage of crosslinking agent is 2-2.5%, and the balance is isophthalic acid / neoplastic glycol type unsaturated polyester gel coat resin.
2. The resin-glass fiber polymer anti-corrosion board according to claim 1, characterized in that: The ethylene-vinyl acetate copolymer-modified substrate is prepared by the following method: vinyl ester resin, alkali-free glass fiber, and curing agent are mixed in proportion, stirred evenly, and poured into a preset mold. A substrate preform is obtained by closed-loop molding. The ethylene-vinyl acetate copolymer is dissolved in toluene to prepare an ethylene-vinyl acetate copolymer solution with a mass fraction of 10-12%. The surface of the substrate preform is roughened by sandpaper, and then the ethylene-vinyl acetate copolymer solution is uniformly coated on the surface of the substrate preform. The amount of ethylene-vinyl acetate copolymer is 6-7% of the total mass of the substrate preform. The substrate is dried to obtain the ethylene-vinyl acetate copolymer-modified substrate.
3. The resin-glass fiber polymer anti-corrosion board according to claim 1, characterized in that: The alkali-free glass fiber is modified with a silane coupling agent and prepared by the following method: alkali-free glass fiber is cut into short fibers of 3-5 mm, placed in an ethanol-water solution, and ultrasonically dispersed evenly; then, silane coupling agent KH550 is added, the amount of silane coupling agent KH550 being 2-2.5% of the mass of the alkali-free glass fiber. After stirring evenly, the pH value of the reaction system is adjusted to 4.5-5.0 with dilute hydrochloric acid, and stirred at a constant temperature of 55-60℃ for 2.5-3 hours; after stirring, the fiber is filtered and separated, washed with deionized water until neutral, and then dried to obtain alkali-free glass fiber modified with silane coupling agent.
4. The resin-glass fiber polymer anti-corrosion board according to claim 1, characterized in that: The Mo / S / Ce composite was prepared by the following method: using ammonium molybdate as the molybdenum source, thiourea as the sulfur source, and cerium nitrate as the cerium source, the raw materials were added sequentially to deionized water according to a molar ratio of Mo:S:Ce of 1:2:(0.2-0.25), and ultrasonically dispersed until a uniform mixture was formed. The mixture was transferred to a hydrothermal reactor, sealed, and placed in an oven. The reaction was carried out at 200°C for 14-16 hours. After the reaction was completed, the mixture was naturally cooled to room temperature, centrifuged to obtain the precipitate, washed alternately with deionized water and anhydrous ethanol, and finally dried to obtain the Mo / S / Ce composite.
5. The resin-glass fiber polymer anti-corrosion board according to claim 4, characterized in that: The triethanolamine borate-modified Mo / S / Ce composite was prepared by the following method: Anhydrous ethanol was used as the solvent; the Mo / S / Ce composite was added and ultrasonically dispersed for 25-30 min to form a suspension with a mass fraction of 5-8%; triethanolamine borate was added at a mass ratio of 1:7-8 to the Mo / S / Ce composite, followed by the addition of 0.7% (by mass) p-toluenesulfonic acid from the triethanolamine borate; the mixture was then purged with nitrogen and stirred at a constant temperature of 65-70℃ for 3.5-4 h. After the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and dried to obtain the triethanolamine borate-modified Mo / S / Ce complex.
6. The resin-glass fiber polymer anti-corrosion board according to claim 1, characterized in that: The isocyanate-modified fibrous attapulgite was prepared by the following method: the fibrous attapulgite was dried in a drying oven; the dried fibrous attapulgite was added to anhydrous toluene and ultrasonically dispersed to form a suspension; toluene diisocyanate was added at a mass ratio of 1:8-9 to attapulgite, and the mixture was heated to 75-80℃ under nitrogen protection and stirred at a constant temperature for 4.5-5 hours; after the reaction was completed, the mixture was filtered and separated, washed with anhydrous toluene, and then dried to obtain the isocyanate-modified fibrous attapulgite.
7. The resin-glass fiber polymer anti-corrosion board according to claim 1, characterized in that: The protective layer is prepared as follows: isophthalic acid / neopulmonium glycol type unsaturated polyester gel coat resin is poured into a mixing tank, a silane coupling agent is added and stirred at low speed until uniform, then isocyanate-modified fibrous attapulgite is added, stirred at low speed for 20 min and then at high speed for 30 min; then triethanolamine borate-modified Mo / S / Ce composite is added, stirred at high speed for 30 min and then ultrasonically dispersed for 25 min; finally, an initiator and a crosslinking agent are added, and stirred at low speed until uniformly dispersed to obtain a protective layer slurry; the protective layer slurry is sprayed onto the surface of an ethylene-vinyl acetate copolymer modified substrate, pre-cured at room temperature for 2.5-3 h and then cured at 75-80℃ for 3-3.5 h to obtain a protective layer with a thickness of 100-200 μm.
8. The resin-glass fiber polymer anti-corrosion board according to claim 1, characterized in that: The vinyl resin in the substrate is bisphenol A type vinyl ester resin, and the curing agent is methyl ethyl ketone peroxide; the silane coupling agent in the protective layer is γ-aminopropyltriethoxysilane, the initiator is benzoyl peroxide, and the crosslinking agent is divinylbenzene.
9. The resin-glass fiber polymer anti-corrosion board according to claim 1, characterized in that: The ethylene-vinyl acetate copolymer is obtained by copolymerizing ethylene and vinyl acetate monomers at a mass ratio of 7:
3.
10. A method for preparing a resin-glass fiber polymer anti-corrosion board according to any one of claims 1-9, characterized in that: Includes the following steps: S1. A substrate is prepared by using vinyl resin, alkali-free glass fiber, and curing agent, and then the surface of the substrate is modified with ethylene-vinyl acetate copolymer to obtain a substrate with surface modification by ethylene-vinyl acetate copolymer. S2. Prepare a protective layer slurry by mixing isophthalic acid / neopulinic glycol type unsaturated polyester gel coat resin, triethanolamine borate modified Mo / S / Ce composite, isocyanate modified fibrous attapulgite, silane coupling agent, initiator, and crosslinking agent. Then spray the protective layer slurry onto the surface of the substrate modified with ethylene-vinyl acetate copolymer. After curing, a resin glass fiber polymer anti-corrosion board is obtained.