Glass fiber reinforced polyurethane door and window material and preparation method thereof

Abstract

The present invention relates to a glass fiber reinforced polyurethane door and window material and a preparation method thereof. The glass fiber reinforced polyurethane door and window material comprises the following raw material components by weight: 30-50 parts of polyurethane material, 20-40 parts of modified glass fiber, 2-5 parts of attapulgite, and 1-3 parts of a processing aid. The present invention introduces modified glass fiber into the glass fiber reinforced polyurethane door and window material, thereby improving the dispersibility of the glass fiber in the polyurethane matrix, effectively reducing agglomeration, and enhancing the interfacial bonding force between the glass fiber and the polyurethane matrix. Furthermore, the mechanical properties of the material are significantly improved by combining the inherent high tensile strength and high elastic modulus of the glass fiber itself. At the same time, the polyurethane material in the raw material composition can enhance the flame retardant properties of the material while reducing the negative impact on the mechanical properties of the material.

Description

Technical Field

[0001] The present invention relates to the field of polyurethane materials, in particular to a glass fiber reinforced polyurethane door and window material and a preparation method thereof. Background Art

[0002] With the improvement of modern living standards and the international demand for energy conservation and emission reduction, the demand for energy-saving and environmentally friendly doors and windows is increasing. Existing door and window materials, such as aluminum alloy doors and windows and stainless steel doors and windows, have high heat transfer coefficients, resulting in poor thermal insulation performance, poor energy conservation, and poor impact resistance, which cannot meet the current energy conservation and emission reduction requirements.

[0003] Polyurethane materials have been widely praised for their excellent comprehensive performance, becoming a focus of attention in the field of building energy conservation and widely used in the construction industry. They not only provide significant sound insulation and thermal insulation, but also possess tear resistance, abrasion resistance, and waterproof and moisture-proof properties. Glass fiber-reinforced polyurethane is a high-performance composite material composed of a polyurethane matrix and glass fiber reinforcement. It possesses excellent mechanical properties such as strength, stiffness, toughness, and durability, as well as corrosion resistance, waterproofness, and thermal insulation.

[0004] Currently, flame retardants are often added to existing polyurethane door and window materials to improve their flame retardancy. However, due to the poor compatibility of flame retardants with the polyurethane matrix, this can increase internal structural defects and reduce the material's mechanical properties. Therefore, further research is needed on the flame retardancy and mechanical properties of glass fiber reinforced polyurethane door and window materials. Summary of the Invention

[0005] In order to overcome the deficiencies of the prior art, one of the objectives of the present invention is to provide a glass fiber reinforced polyurethane door and window material.

[0006] A second object of the present invention is to provide a method for preparing glass fiber reinforced polyurethane door and window materials.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] The present invention provides a glass fiber reinforced polyurethane door and window material, which comprises the following raw material components by weight: 30-50 parts of polyurethane material, 20-40 parts of modified glass fiber, 2-5 parts of attapulgite and 1-3 parts of processing aid;

[0009] The preparation process of the modified glass fiber is as follows:

[0010] (1) Immersing the glass fiber in an acetone solution for ultrasonic treatment, filtering and drying, adding a mixture of concentrated sulfuric acid and hydrogen peroxide solution and stirring; filtering, washing, and drying to obtain pretreated glass fiber;

[0011] (2) Dispersing the pretreated glass fiber in N,N-dimethylformamide, adding 2-chloroethanethiol and potassium carbonate, reacting at room temperature, filtering, washing, and drying to obtain mercaptolated glass fiber;

[0012] (3) Add mercaptolated glass fiber, esculetin and benzoin dimethyl ether into tetrahydrofuran, react, filter, wash and dry to obtain the product.

[0013] Preferably, in step (1), the amount ratio of glass fiber to acetone solution is 2.0 g:50-75 mL; the amount ratio of glass fiber to mixture is 2.0 g:50-75 mL; the volume ratio of concentrated sulfuric acid to hydrogen peroxide solution in the mixture is 7:3; the mass concentration of concentrated sulfuric acid is 98%; the mass concentration of hydrogen peroxide solution is 20%; the ultrasonic treatment time is 10-12 h; and the stirring time is 10-12 h.

[0014] Preferably, in step (2), the ratio of the amount of pretreated glass fiber, 2-chloroethanethiol, potassium carbonate and N,N-dimethylformamide is 0.5g: 0.6-1.2g: 0.8-1.6g: 30-45mL; the reaction time is 10-12h;

[0015] Preferably, in step (3), the usage ratio of thiolated glass fiber, esculetin, benzoin dimethyl ether and tetrahydrofuran is 1 g: 0.8-2.0 g: 0.015-0.03 g: 50-75 mL; and the reaction time is 5-10 h.

[0016] The present invention introduces modified glass fiber into glass fiber reinforced polyurethane door and window materials, introduces sulfhydryl group by 2-chloroethanethiol, and then obtains modified glass fiber by the double bond reaction of sulfhydryl group and esculetin. The phenolic hydroxyl group, ester group and thioether bond in esculetin can form hydrogen bond interactions with the urethane group in polyurethane. This interaction not only improves the dispersibility of glass fiber in polyurethane matrix, effectively reduces agglomeration, but also strengthens the interfacial bonding force between glass fiber and polyurethane matrix, further combines the inherent high tensile strength and high elastic modulus of glass fiber itself, and significantly improves the mechanical properties of the material.

[0017] At the same time, the modified glass fiber used in the present invention has corrosion resistance: ① the glass fiber itself is resistant to acid and alkali corrosion; ② the esculetin modified on the surface of the modified glass fiber can reduce the penetration of water molecules and corrosive media through its hydrophobic aromatic structure, thereby delaying the hydrolysis and swelling of polyurethane; ③ the esculetin modified on the surface of the modified glass fiber has an inhibitory effect on bacteria and mold, and can inactivate microorganisms and bacteria in the use environment of polyurethane door and window materials, thereby reducing the direct corrosion damage of microorganisms to the material and reducing the erosion of the material by acidic and alkaline liquids generated by their metabolism.

[0018] Preferably, the polyurethane material is prepared as follows: polyether polyol, modified diisocyanate, chain extender and dibutyltin dilaurate are mixed, and stirred at 75-80° C. for 3-5 hours to obtain the polyurethane material.

[0019] Preferably, the mass ratio of the polyether polyol, modified diisocyanate, chain extender and dibutyltin dilaurate is 100:(100-120):(3-10):(0.5-3); the polyether polyol is any one of polypropylene oxide ether diol, polyethylene oxide ether diol and polytetramethylene oxide ether diol, and the molar mass is 200-1000 g / mol; the chain extender is any one of ethylene glycol, 1,4-butanediol and triethanolamine.

[0020] Preferably, the preparation process of the modified diisocyanate is as follows:

[0021] S1. Under nitrogen protection and reflux conditions, triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine, and anhydrous potassium carbonate were added to N,N-dimethylformamide and fully dissolved. The mixture was reacted at 105-125°C for 8-12 h, and then filtered, washed, and dried to obtain intermediate 1.

[0022] S2. Dissolve toluene-2,4-diisocyanate in dioxane A, heat to 35-40°C, add dioxane B containing intermediate 1, maintain the temperature at 35-40°C for 2-4 hours, and then pulp, filter, and dry to obtain the product.

[0023] Preferably, in step S1, the molar ratio of triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine and anhydrous potassium carbonate is (2-2.2):1:(2-3), and the concentration of triphenylsilanol in N,N-dimethylformamide is 0.2-0.4 mol / L;

[0024] Preferably, in step S2, the molar ratio of intermediate 1 to toluene-2,4-diisocyanate is 1:(2-2.2), the concentration of toluene-2,4-diisocyanate in dioxane A is 1.5-2.5 mol / L, and the concentration of intermediate 1 in dioxane B is 0.5-1.5 mol / L.

[0025] The present invention utilizes modified diisocyanates and polyether polyols to prepare polyurethane materials. The flame retardancy of the modified diisocyanate stems primarily from the synergistic effect of the silicon group (triphenylsiloxy) and the aromatic group (benzene ring) in its molecular structure. Under high temperature conditions, the silicon group forms a dense silicon dioxide ceramic layer in situ, while the aromatic group carbonizes to form a polycyclic carbon structure. Together, the two create a physical barrier that effectively blocks the transfer of oxygen and heat. Simultaneously, the silicon and aromatic groups chemically interrupt the combustion process by capturing active free radicals in the combustion chain reaction. Furthermore, the urea group in the molecule decomposes upon heating to produce non-combustible gases such as CO2 and NH3, which dilute the concentration of combustibles, forming a gas-phase flame suppression effect and synergistically enhancing the flame retardant effect.

[0026] Preferably, the processing aids are sodium lauryl sulfate and sodium polyacrylate, and the mass ratio of sodium lauryl sulfate to sodium polyacrylate is 1:(0.5-1).

[0027] The present invention provides a preparation method of the glass fiber reinforced polyurethane door and window material, comprising the following steps: weighing various raw material components according to a proportion, firstly uniformly mixing the polyurethane material, attapulgite, and a processing aid to obtain a mixture; then passing the modified glass fiber through a mold, injecting the mixture through a glue injection machine, heating and curing, pultruding, and cooling to obtain the material.

[0028] Preferably, the temperature of the heating and curing is 180-200°C.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The present invention provides a glass fiber-reinforced polyurethane door and window material. Modified glass fiber is added as a reinforcing agent to the raw material composition. The modified treatment enhances the dispersibility and compatibility of the glass fiber in the polyurethane door and window material, significantly improving the mechanical properties and corrosion resistance of the polyurethane door and window material. The polyurethane material is prepared using a modified diisocyanate and a polyether polyol. The modified diisocyanate significantly enhances the material's flame retardancy through a synergistic mechanism of condensed phase carbonization for thermal insulation and gas phase dilution for flame suppression, while simultaneously reducing negative effects on the material's mechanical properties.

[0031] The invention provides a method for preparing a glass fiber reinforced polyurethane door and window material. The process is simple and suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a scanning electron microscope image of the modified glass fiber obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0033] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be noted that, without conflict, the embodiments described below or the technical features can be arbitrarily combined to form new embodiments. Specific conditions not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. All reagents or instruments used are conventional products obtained from commercial channels unless otherwise specified.

[0034] Example 1

[0035] This embodiment provides a glass fiber reinforced polyurethane door and window material, which includes the following raw material components, by weight: 40 parts of polyurethane material, 30 parts of modified glass fiber, 2 parts of attapulgite, and 2 parts of a processing aid; wherein the processing aid is a mixture of sodium lauryl sulfate and sodium polyacrylate in a mass ratio of 1:0.8.

[0036] The preparation process of the modified glass fiber in this embodiment is as follows:

[0037] (1) Immerse glass fiber (3-10 μm in diameter) in an acetone solution and ultrasonically treat for 12 h. After filtering and vacuum drying, add a mixture of 98 wt% concentrated sulfuric acid and 20 wt% hydrogen peroxide solution (volume ratio of 7:3) and stir for 12 h to completely expose the silanol groups. The ratio of glass fiber, acetone solution, and mixture is 2.0 g:60 mL:60 mL. Then filter, wash with deionized water, and vacuum dry to obtain pretreated glass fiber.

[0038] (2) Dispersing the pretreated glass fiber in N,N-dimethylformamide, adding 2-chloroethanethiol and potassium carbonate, wherein the amount ratio of the pretreated glass fiber, 2-chloroethanethiol, potassium carbonate and N,N-dimethylformamide is 0.5g:1g:1g:40mL; stirring at room temperature for 12h, adding 6mol / L hydrochloric acid to quench the reaction, filtering, washing with distilled water and saturated brine in turn, and vacuum drying to obtain thiolated glass fiber;

[0039] (3) Add mercaptolated glass fiber, esculetin and photoinitiator benzoin dimethyl ether into tetrahydrofuran, wherein the amount ratio of mercaptolated glass fiber, esculetin, benzoin dimethyl ether and tetrahydrofuran is 1g:1.5g:0.02g:60mL; react under nitrogen protection and ultraviolet light for 8 hours, filter, wash with tetrahydrofuran and ethanol in turn, and vacuum dry to obtain modified glass fiber. The scanning electron microscope image of the obtained modified glass fiber is shown in FIG. Figure 1 shown.

[0040]

[0041] The polyurethane material of this embodiment is prepared as follows: polyether polyol (polypropylene oxide ether diol, molar mass 400g / mol), modified diisocyanate, chain extender (ethylene glycol) and dibutyltin dilaurate are mixed, and stirred at 80°C for 4h to obtain the obtained material.

[0042] The preparation process of the modified diisocyanate in this embodiment is as follows:

[0043] (1) Under nitrogen protection and reflux conditions, triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine and anhydrous potassium carbonate were added to N,N-dimethylformamide and fully dissolved, wherein the molar ratio of triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine and anhydrous potassium carbonate was 2.1:1:2.5, and the concentration of triphenylsilanol in N,N-dimethylformamide was 0.3 mol / L; after reacting at 115°C for 10 h, the mixture was filtered, and part of the solvent was removed by vacuum distillation. The product was precipitated with 5 wt% hydrochloric acid solution, and the solid product was filtered to obtain the solid product, which was washed with deionized water and dried under vacuum to obtain intermediate 1 (yield 73.8%). 1 HNMR: (C 50 H 44 N2O2Si2, 400MHz, DMSO-d6) δ: 4.24 (s, 2H), 6.82-6.86 (dd, 4H), 7.03-7.07 (dd, 4H), 7.35-7.39 (m, 18H), 7.44-7.48 (m, 12H), 8.62 (s, 4H). MS (ESI) m / z=760.29 [M].

[0044] (2) Dissolve toluene-2,4-diisocyanate in dioxane A, heat to 35-40°C, and slowly add dioxane B containing intermediate 1, wherein the molar ratio of intermediate 1 to toluene-2,4-diisocyanate is 1:2.1, the concentration of toluene-2,4-diisocyanate in dioxane A is 2 mol / L, and the concentration of intermediate 1 in dioxane B is 1 mol / L; continue stirring and reacting at 40°C for 3 hours, precipitate the product with deionized water, filter to obtain a crude product, and beat with 2 wt% dilute hydrochloric acid and 90 v / v% ethanol in turn, filter, and vacuum dry to obtain a modified diisocyanate (yield 90.3%). 1 HNMR: (C 68 H 56N6O6Si2, 400MHz, DMSO-d6) δ: 2.31 (s, 6H), 5.88 (s, 2H), 6.46 (s, 2H), 6.82-6.86 (dd, 4H) , 7.03-7.07 (dd, 4H), 7.35-7.39 (m, 18H), 7.44-7.52 (m, 16H), 7.61 (s, 2H), 8.26 (s, 2H). MS (ESI) m / z=1108.38 [M].

[0045]

[0046] The preparation method of the glass fiber reinforced polyurethane door and window material in this embodiment includes the following steps: weighing the raw material components according to the ratio, first mixing the polyurethane material, attapulgite, and processing aid uniformly to obtain a mixture; then passing the modified glass fiber through a mold, injecting the mixture through a glue injection machine, heating at 190°C to cure, pultruding, and cooling to obtain the material.

[0047] Example 2

[0048] This embodiment provides a glass fiber reinforced polyurethane door and window material, which includes the following raw material components, calculated by weight: 30 parts of polyurethane material, 20 parts of modified glass fiber, 3 parts of attapulgite, and 1 part of a processing aid; wherein the processing aid is a mixture of sodium lauryl sulfate and sodium polyacrylate in a mass ratio of 1:0.5.

[0049] The preparation process of the modified glass fiber in this embodiment is as follows:

[0050] (1) Immerse the glass fiber in an acetone solution and ultrasonically treat it for 10 hours. After filtering and vacuum drying, add a mixture of 98 wt% concentrated sulfuric acid and 20 wt% hydrogen peroxide solution (volume ratio of 7:3) and stir for 10 hours to completely expose the silanol groups. The ratio of glass fiber, acetone solution, and mixture is 2.0 g:50 mL:50 mL. Then filter, wash with deionized water, and vacuum dry to obtain pretreated glass fiber.

[0051] (2) Dispersing the pretreated glass fiber in N,N-dimethylformamide, adding 2-chloroethanethiol and potassium carbonate, wherein the amount ratio of the pretreated glass fiber, 2-chloroethanethiol, potassium carbonate and N,N-dimethylformamide is 0.5g:0.6g:0.8g:30mL; stirring at room temperature for 10h, adding 6mol / L hydrochloric acid to quench the reaction, filtering, washing with distilled water and saturated brine in turn, and vacuum drying to obtain thiolated glass fiber;

[0052] (3) Add mercaptolated glass fiber, esculetin and photoinitiator benzoin dimethyl ether into tetrahydrofuran, wherein the amount ratio of mercaptolated glass fiber, esculetin, benzoin dimethyl ether and tetrahydrofuran is 1g:0.8g:0.015g:50mL; after reacting for 5h under nitrogen protection and ultraviolet light irradiation, the modified glass fiber is filtered, washed with tetrahydrofuran and ethanol in turn, and vacuum dried to obtain the modified glass fiber.

[0053] The preparation steps of the polyurethane material in this embodiment are as follows: polyether polyol (polytetramethylene ether diol, molar mass of 1000 g / mol), modified diisocyanate, chain extender (1,4-butanediol) and dibutyltin dilaurate are mixed, and stirred at 80°C for 3 hours to obtain the polyurethane material.

[0054] The preparation process of the modified diisocyanate in this embodiment is as follows:

[0055] (1) Under nitrogen protection and reflux conditions, triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine and anhydrous potassium carbonate were added to N,N-dimethylformamide and fully dissolved, wherein the molar ratio of triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine and anhydrous potassium carbonate was 2:1:2, and the concentration of triphenylsilanol in N,N-dimethylformamide was 0.2 mol / L; after reacting at 125°C for 8 hours, the mixture was filtered, and part of the solvent was removed by vacuum distillation. The product was precipitated with 5wt% hydrochloric acid solution, and the solid product was filtered to obtain the solid product, which was washed with deionized water and dried under vacuum to obtain intermediate 1 (yield 71.4%). 1 HNMR was the same as in Example 1.

[0056] (2) Dissolve toluene-2,4-diisocyanate in dioxane A, heat to 40°C, and slowly add dioxane B containing intermediate 1, wherein the molar ratio of intermediate 1 to toluene-2,4-diisocyanate is 1:2, the concentration of toluene-2,4-diisocyanate in dioxane A is 1.5 mol / L, and the concentration of intermediate 1 in dioxane B is 0.5 mol / L; continue stirring and reacting at 40°C for 2 hours, precipitate the product with deionized water, filter to obtain a crude product, beat with 2wt% dilute hydrochloric acid and 90v / v% ethanol in turn, filter, and vacuum dry to obtain a modified diisocyanate (yield 88.6%). 1 HNMR was the same as in Example 1.

[0057] The preparation method of the glass fiber reinforced polyurethane door and window material in this embodiment includes the following steps: weighing the raw material components according to the ratio, first mixing the polyurethane material, attapulgite, and processing aid uniformly to obtain a mixture; then passing the modified glass fiber through a mold, injecting the mixture through a glue injection machine, heating at 200°C to cure, pultruding, and cooling to obtain the material.

[0058] Example 3

[0059] This embodiment provides a glass fiber reinforced polyurethane door and window material, which includes the following raw material components, by weight: 50 parts of polyurethane material, 40 parts of modified glass fiber, 5 parts of attapulgite and 3 parts of processing aid; wherein the processing aid is a mixture of sodium lauryl sulfate and sodium polyacrylate in a mass ratio of 1:1.

[0060] The preparation process of the modified glass fiber in this embodiment is as follows:

[0061] (1) Immerse the glass fiber in an acetone solution and ultrasonically treat it for 12 hours. After filtering and vacuum drying, add a mixture of 98 wt% concentrated sulfuric acid and 20 wt% hydrogen peroxide solution (volume ratio of 7:3) and stir for 12 hours to completely expose the silanol groups. The ratio of glass fiber, acetone solution, and mixture is 2.0 g:75 mL:75 mL. Then filter, wash with deionized water, and vacuum dry to obtain pretreated glass fiber.

[0062] (2) Dispersing the pretreated glass fiber in N,N-dimethylformamide, adding 2-chloroethanethiol and potassium carbonate, wherein the amount ratio of the pretreated glass fiber, 2-chloroethanethiol, potassium carbonate and N,N-dimethylformamide is 0.5g:1.2g:1.6g:45mL; stirring at room temperature for 12h, adding 6mol / L hydrochloric acid to quench the reaction, filtering, washing with distilled water and saturated brine in turn, and vacuum drying to obtain thiolated glass fiber;

[0063] (3) Add mercaptolated glass fiber, esculetin and photoinitiator benzoin dimethyl ether into tetrahydrofuran, wherein the amount ratio of mercaptolated glass fiber, esculetin, benzoin dimethyl ether and tetrahydrofuran is 1g:2.0g:0.03g:75mL; after reacting for 10 hours under nitrogen protection and ultraviolet light irradiation, the modified glass fiber is filtered, washed with tetrahydrofuran and ethanol in turn, and vacuum dried to obtain the modified glass fiber.

[0064] The polyurethane material of this embodiment is prepared by mixing polyether polyol (polyethylene oxide ether diol, molar mass of 1000 g / mol), modified diisocyanate, chain extender (triethanolamine) and dibutyltin dilaurate, and stirring the mixture at 75° C. for 5 hours to obtain the polyurethane material.

[0065] The preparation process of the modified diisocyanate in this embodiment is as follows:

[0066] (1) Under nitrogen protection and reflux conditions, triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine and anhydrous potassium carbonate were added to N,N-dimethylformamide and fully dissolved, wherein the molar ratio of triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine and anhydrous potassium carbonate was 2.2:1:3, and the concentration of triphenylsilanol in N,N-dimethylformamide was 0.4 mol / L; after reacting at 105°C for 12 h, the mixture was filtered, and part of the solvent was removed by vacuum distillation. The product was precipitated with 5 wt% hydrochloric acid solution, and the solid product was filtered to obtain the solid product, which was washed with deionized water and dried under vacuum to obtain intermediate 1 (yield 72.1%). 1 HNMR was the same as in Example 1.

[0067] (2) Dissolve toluene-2,4-diisocyanate in dioxane A, heat to 35°C, and slowly add dioxane B containing intermediate 1, wherein the molar ratio of intermediate 1 to toluene-2,4-diisocyanate is 1:2.2, the concentration of toluene-2,4-diisocyanate in dioxane A is 2.5 mol / L, and the concentration of intermediate 1 in dioxane B is 1.5 mol / L; continue to stir the reaction at 35°C for 4 hours, precipitate the product with deionized water, filter to obtain a crude product, beat with 2wt% dilute hydrochloric acid and 90v / v% ethanol in turn, filter, and vacuum dry to obtain a modified diisocyanate (yield 89.4%). 1 HNMR was the same as in Example 1.

[0068] The preparation method of the glass fiber reinforced polyurethane door and window material in this embodiment includes the following steps: weighing the raw material components according to the ratio, first mixing the polyurethane material, attapulgite, and processing aid uniformly to obtain a mixture; then passing the modified glass fiber through a mold, injecting the mixture through a glue injection machine, heating at 180°C to cure, pultruding, and cooling to obtain the material.

[0069] Comparative Example 1

[0070] The difference between this comparative example and Example 1 is that the modified diisocyanate is replaced by toluene-2,4-diisocyanate in the preparation of the polyurethane material.

[0071] Comparative Example 2

[0072] The difference between this comparative example and Example 1 is that the modified glass fiber is replaced by glass fiber.

[0073] Test example

[0074] 1. According to GB / T 1449-2005 “Test method for bending properties of fiber reinforced plastics”, the bending strength of the glass fiber reinforced polyurethane door and window materials obtained in Examples 1-3 and Comparative Examples 1-2 was measured. The results are shown in Table 1.

[0075] 2. According to GB / T 1450-2005 “Test method for interlaminar shear strength of fiber reinforced plastics”, the shear strength of the glass fiber reinforced polyurethane door and window materials obtained in Examples 1-3 and Comparative Examples 1-2 was measured. The results are shown in Table 1.

[0076] 3. According to GB / T 2406.2-2009 “Determination of Combustion Behavior of Plastics by Oxygen Index Method”, the oxygen index of the glass fiber reinforced polyurethane door and window materials obtained in Examples 1-3 and Comparative Examples 1-2 was measured. The results are shown in Table 1.

[0077] Table 1

[0078]

[0079] As shown in Table 1, the mechanical properties and flame retardancy of the glass fiber-reinforced polyurethane door and window materials obtained in Examples 1-3 are superior to those of Comparative Examples 1-2. Specifically, the present invention utilizes modified diisocyanates and polyether polyols to prepare the polyurethane materials. The modified diisocyanates significantly enhance the flame retardancy of the materials through a synergistic mechanism of condensed phase carbonization for insulation and gas phase dilution for flame suppression, while simultaneously reducing the negative impact on the mechanical properties of the materials. The present invention also incorporates modified glass fiber as a reinforcing agent. This modification enhances the dispersibility and compatibility of the glass fiber in the polyurethane door and window materials, significantly improving the mechanical properties of the polyurethane door and window materials.

[0080] The above embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and replacements made by technicians in this field on the basis of the present invention fall within the scope of protection required by the present invention.

Claims

1. A glass fiber reinforced polyurethane door and window material, characterized in that: The raw material components include, by weight: 30-50 parts of polyurethane material, 20-40 parts of modified glass fiber, 2-5 parts of attapulgite and 1-3 parts of processing aid; The preparation process of the modified glass fiber is as follows: (1) Immersing the glass fiber in an acetone solution for ultrasonic treatment, filtering and drying, adding a mixture of concentrated sulfuric acid and hydrogen peroxide solution and stirring; filtering, washing, and drying to obtain pretreated glass fiber; (2) Dispersing the pretreated glass fiber in N,N-dimethylformamide, adding 2-chloroethanethiol and potassium carbonate, reacting at room temperature, filtering, washing, and drying to obtain mercaptolated glass fiber; (3) Add mercaptolated glass fiber, esculetin and benzoin dimethyl ether into tetrahydrofuran, react, filter, wash and dry to obtain the product.

2. The glass fiber reinforced polyurethane door and window material according to claim 1, characterized in that: In step (1), the amount ratio of glass fiber to acetone solution is 2.0 g:50-75 mL; the amount ratio of glass fiber to mixture is 2.0 g:50-75 mL; the volume ratio of concentrated sulfuric acid to hydrogen peroxide solution in the mixture is 7:3; the mass concentration of the concentrated sulfuric acid is 98%; the mass concentration of the hydrogen peroxide solution is 20%; the ultrasonic treatment time is 10-12 h; and the stirring time is 10-12 h.

3. The glass fiber reinforced polyurethane door and window material according to claim 1, characterized in that: In the step (2), the ratio of the amount of pretreated glass fiber, 2-chloroethanethiol, potassium carbonate and N,N-dimethylformamide is 0.5g:0.6-1.2g:0.8-1.6g:30-45mL; the reaction time is 10-12h; In the step (3), the usage ratio of mercaptolated glass fiber, esculetin, benzoin dimethyl ether and tetrahydrofuran is 1 g: 0.8-2.0 g: 0.015-0.03 g: 50-75 mL; and the reaction time is 5-10 h.

4. The glass fiber reinforced polyurethane door and window material according to claim 1, characterized in that: The preparation steps of the polyurethane material are as follows: after mixing polyether polyol, modified diisocyanate, chain extender and dibutyltin dilaurate, stirring and reacting at 75-80° C. for 3-5 hours to obtain the polyurethane material.

5. The glass fiber reinforced polyurethane door and window material according to claim 4, characterized in that: The mass ratio of the polyether polyol, modified diisocyanate, chain extender and dibutyltin dilaurate is 100:(100-120):(3-10):(0.5-3); the polyether polyol is any one of polypropylene oxide ether diol, polyethylene oxide ether diol and polytetramethylene oxide ether diol, and the molar mass is 200-1000 g / mol; the chain extender is any one of ethylene glycol, 1,4-butanediol and triethanolamine.

6. The glass fiber reinforced polyurethane door and window material according to claim 4, characterized in that: The preparation process of the modified diisocyanate is as follows: S1. Under nitrogen protection and reflux conditions, triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine, and anhydrous potassium carbonate were added to N,N-dimethylformamide and fully dissolved. The mixture was reacted at 105-125°C for 8-12 h, and then filtered, washed, and dried to obtain intermediate 1. S2. Dissolve toluene-2,4-diisocyanate in dioxane A, heat to 35-40°C, add dioxane B containing intermediate 1, maintain the temperature at 35-40°C for 2-4 hours, and then pulp, filter, and dry to obtain the product.

7. The glass fiber reinforced polyurethane door and window material according to claim 6, characterized in that: In step S1, the molar ratio of triphenylsilanol, 1,2-bis(4-chlorophenyl)ethylenediamine, and anhydrous potassium carbonate is (2-2.2):1:(2-3), and the concentration of triphenylsilanol in N,N-dimethylformamide is 0.2-0.4 mol / L; In step S2, the molar ratio of intermediate 1 to toluene-2,4-diisocyanate is 1:(2-2.2), the concentration of toluene-2,4-diisocyanate in dioxane A is 1.5-2.5 mol / L, and the concentration of intermediate 1 in dioxane B is 0.5-1.5 mol / L.

8. The glass fiber reinforced polyurethane door and window material according to claim 1, characterized in that: The processing aids are sodium lauryl sulfate and sodium polyacrylate, and the mass ratio of sodium lauryl sulfate to sodium polyacrylate is 1:(0.5-1).

9. The method for preparing the glass fiber reinforced polyurethane door and window material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: weighing various raw material components according to a proportion, uniformly mixing the polyurethane material, attapulgite and a processing aid to obtain a mixture; passing the modified glass fiber through a mold, injecting the mixture through a glue injection machine, heating and curing, pultruding and cooling to obtain the product.

10. The preparation method according to claim 9, characterized in that The temperature of the heating and curing is 180-200°C.

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