Glass fiber reinforced waterproof coiled material and preparation method thereof

Abstract

The invention relates to the technical field of waterproof materials, and discloses a glass fiber reinforced waterproof roll and a preparation method thereof. The preparation method comprises the following steps: coating two surfaces of a high-density polyethylene foaming film with high-molecular waterproof layers through a film spraying process, then compounding a reinforced protective layer and the high-density polyethylene foaming film coated with the high-molecular waterproof layers, and finally drying, curing and cooling to obtain the glass fiber reinforced waterproof roll. The glass fiber reinforced waterproof roll sequentially comprises a reinforced protective layer, a high-molecular waterproof layer, a high-density polyethylene foaming film and a high-molecular waterproof layer from top to bottom, wherein the reinforced protective layer is prepared by coating polyvinyl fluoride on glass fiber cloth; the macromolecular waterproof layer is formed by blending low-density polyethylene, epoxy resin modified acrylic resin and fluorine-containing benzoxazine modified polyurethane. The glass fiber reinforced waterproof coiled material prepared by the invention has excellent mechanical properties, aging resistance and waterproof effect.

Description

Technical Field

[0001] The invention relates to the technical field of waterproof materials, in particular to a glass fiber reinforced waterproof coiled material and a preparation method thereof. Background Art

[0002] Waterproof roll is a rollable sheet-like waterproof material used in building walls, roofs, tunnels, roads, etc. to resist external rainwater and groundwater leakage. It is one of the important varieties of waterproof materials for construction projects. Polyethylene is a thermoplastic resin material with good water resistance. It is often used to make polymer waterproof rolls. The aging resistance of polyethylene materials is poor. It is easy to become brittle or even powdered when exposed to sunlight for a long time, and the mechanical properties are not good. The polyethylene composite waterproof roll published in patent CN215882882U has excellent waterproof properties by hot-pressing polyethylene staple needle-punched nonwoven fabrics on the upper and lower sides of the polyethylene film, but the mechanical properties and aging resistance of the polyethylene film are not improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a glass fiber reinforced waterproof coiled material and a preparation method thereof. The present invention has the advantages of improving the mechanical properties and aging resistance of the waterproof coiled material and having a good waterproof effect.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a glass fiber reinforced waterproof coiled material, which comprises, from top to bottom, a reinforced protective layer, a polymer waterproof layer, a high-density polyethylene foam film, and a polymer waterproof layer, wherein the reinforced protective layer is made of polyvinyl fluoride coated on a glass fiber cloth, and the polymer waterproof layer comprises the following raw materials in parts by weight: 15-20 parts by weight of low-density polyethylene, 8-10 parts by weight of epoxy resin modified acrylic resin, and 6-9 parts by weight of fluorinated benzoxazine modified polyurethane.

[0007] Preferably, the preparation method of the epoxy resin modified acrylic resin comprises the following steps:

[0008] (1) Add 12-15 g of bisphenol A epoxy resin to a reactor, heat it to 50-60° C., then add 8-10 g of β-(acryloyloxy)propionic acid, 0.02-0.04 g of a catalyst, and 0.01-0.03 g of a polymerization inhibitor, heat it to 95-100° C., react for 2-4 h, and after the reaction is complete, cool, wash, and dry to obtain an intermediate 1;

[0009] (2) adding the intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, reacting at 28-30° C. for 1-3 hours, filtering, washing and drying after the reaction to obtain an epoxy resin modified with alkenyl silane;

[0010] (3) Add 9-13 g of acrylic acid, 7-10 g of methyl methacrylate, 4-6 g of hydroxypropyl methacrylate, 5-8 g of alkenyl silane-modified epoxy resin, and 0.01-0.03 g of emulsifier to deionized water, stir and mix to obtain a pre-emulsion, add deionized water and 0.02-0.05 g of emulsifier to a reactor, heat to 75-85° C., add 0.02-0.04 g of initiator and 10% of the pre-emulsion, react at constant temperature for 20-40 min, then add the remaining pre-emulsion, continue the constant temperature reaction for 2-3 h, cool and filter after the reaction is completed to obtain epoxy resin modified acrylic resin.

[0011] Preferably, in step (1), the catalyst is dimethylaniline and the inhibitor is 4-methoxyphenol.

[0012] Preferably, in the step (2), the mass ratio of the intermediate 1, 3-(N-allylamino)propyltrimethoxysilane, and sodium ethoxide is 1:1.3-1.4:0.02-0.05.

[0013] Preferably, in step (3), the emulsifier is sodium dodecyl sulfate and the initiator is benzoyl peroxide.

[0014] Preferably, the method for preparing the fluorinated benzoxazine-modified polyurethane comprises the following steps:

[0015] S1. Add 7-10 g of 4-mercapto-2-methylphenol, 6-9 g of 3-aminotrifluorotoluene, and 12-18 g of paraformaldehyde to a toluene solvent, stir and mix, and heat to react for 4-5 hours. After the reaction is completed, filter, wash and dry to obtain a fluorinated benzoxazine;

[0016] S2. Add 8-12 g of divinyl glycol and 6-9 g of fluorinated benzoxazine to N,N-dimethylformamide solvent, stir and mix, then add 0.03-0.05 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 36-40 ° C, after the reaction is completed, centrifuge, wash and dry to obtain a fluorinated benzoxazine modified chain extender;

[0017] S3. Add 5-7g of diphenylmethane diisocyanate, 10-12g of polycaprolactone diol, and 0.04-0.06g of dibutyltin dilaurate into the reactor, introduce nitrogen protection, and carry out prepolymerization at 72-80°C. After reacting for 1.5-2.5h, cool to 62-68°C, add 3-6g of fluorinated benzoxazine modified chain extender to carry out chain extension reaction, and the reaction time is 4-5h. After the reaction is completed, cool, wash and dry to obtain fluorinated benzoxazine modified polyurethane.

[0018] Preferably, the reaction temperature in S1 is 90-100°C.

[0019] Preferably, the ultraviolet light irradiation time in S2 is 45-60 min.

[0020] Preferably, the preparation method of the glass fiber reinforced waterproof membrane is: low-density polyethylene, epoxy resin modified acrylic resin, and fluorinated benzoxazine modified polyurethane are mixed and melted to obtain a liquid film of a polymer waterproof layer, and then the liquid film is evenly coated on both sides of a high-density polyethylene foam film through a laminating process, and then the reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer are compounded, and finally dried and solidified, and cooled to obtain a glass fiber reinforced waterproof membrane.

[0021] (III) Beneficial technical effects

[0022] The present invention prepares a liquid film of a polymer waterproof layer by mixing and melting low-density polyethylene, epoxy resin-modified acrylic resin and fluorinated benzoxazine-modified polyurethane, and then uniformly coats the liquid film on both sides of a high-density polyethylene foam film through a laminating process, and then composites a reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer, and finally dries, solidifies and cools to obtain a glass fiber reinforced waterproof coiled material.

[0023] The epoxy group in the bisphenol A epoxy resin and the carboxyl group in β-(acryloxy) propionic acid undergo a ring-opening esterification reaction to obtain an intermediate 1, the alkenyl group in the intermediate 1 and the secondary amine group in 3-(N-allylamino)propyltrimethoxysilane undergo a Michael addition reaction to obtain an alkenyl-containing silane-modified epoxy resin, the alkenyl group in the alkenyl-containing silane-modified epoxy resin undergoes a polymerization reaction with acrylic acid, methyl methacrylate, and hydroxypropyl methacrylate to obtain an epoxy resin-modified acrylic resin. 4-Mercapto-2-methylphenol undergoes a Mannich condensation reaction with 3-aminotrifluorotoluene and polyformaldehyde to obtain a fluorinated benzoxazine, the mercapto group in the fluorinated benzoxazine and the alkenyl group in divinyl glycol undergo a click reaction to obtain a fluorinated benzoxazine-modified chain extender, diphenylmethane diisocyanate and polycaprolactone diol are prepolymerized and then subjected to a chain extension reaction with the fluorinated benzoxazine-modified chain extender to obtain a fluorinated benzoxazine-modified polyurethane.

[0024] In the enhanced protective layer, the high-strength glass fiber cloth is not easy to break when subjected to external force and has good tensile strength, which improves the mechanical properties of the waterproof membrane. By coating polyvinyl fluoride on the glass fiber cloth, the glass fiber cloth is shaped so that it will not be dislocated by drawing, further increasing the strength of the waterproof membrane; the high-density polyethylene foam film ensures the thickness of the product while having excellent waterproof performance, which can effectively prevent the penetration of water and has a certain thermal insulation ability, which plays a role in improving the temperature comfort of the building and reducing energy consumption; in the polymer waterproof layer, the silicon-oxygen bond in the epoxy resin-modified acrylic resin has a high bond energy, which makes the waterproof membrane containing silicon-oxygen bonds more stable at high temperatures, not easy to decompose or deform, and improves the aging resistance of the waterproof membrane; acrylic resin will swell and shrink in water to form a waterproof coating with high strength, flexibility and durability, which enhances The mechanical properties and waterproof effect of the waterproof membrane are improved; the epoxy resin molecule contains epoxy groups, benzene ring groups, hydroxyl groups and ether bonds, which make the waterproof layer have excellent strength and thermal stability, thereby improving the mechanical properties and aging resistance of the waterproof membrane; the carbon-fluorine bonds in the fluorinated benzoxazine-modified polyurethane have high bond energy and low surface tension, and can form a protective film with extremely low surface energy on the surface of the waterproof layer, thereby enhancing the waterproof effect of the waterproof membrane; the six-membered ring structure in the benzoxazine molecule increases the rigidity of the molecule, and this rigid structure is not easy to deform or decompose at high temperatures, thereby improving the mechanical properties and aging resistance of the waterproof membrane; the urethane bonds in the polyurethane have high chemical stability and water resistance, and these bonds can form a dense network structure to effectively prevent the penetration of water. The polyurethane also has good adhesion and can be firmly combined with the substrate, further enhancing the waterproof effect of the waterproof membrane. DETAILED DESCRIPTION

[0025] Example 1

[0026] (1) Add 12 g of bisphenol A epoxy resin to a reactor, heat it to 50° C., then add 8 g of β-(acryloyloxy)propionic acid, 0.02 g of dimethylaniline catalyst, and 0.01 g of 4-methoxyphenol inhibitor, heat it to 95° C. and react for 2 h. After the reaction is completed, cool, wash and dry to obtain intermediate 1;

[0027] (2) adding intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide is 1:1.3:0.02, reacting at 28°C for 1 hour, filtering, washing and drying after the reaction to obtain an epoxy resin modified with alkenyl silane;

[0028] (3) Add 9 g of acrylic acid, 7 g of methyl methacrylate, 4 g of hydroxypropyl methacrylate, 5 g of alkenyl silane-modified epoxy resin, and 0.01 g of sodium dodecyl sulfate emulsifier to deionized water, stir and mix to obtain a pre-emulsion, add deionized water and 0.02 g of sodium dodecyl sulfate emulsifier to a reactor, heat to 75° C., add 0.02 g of benzoyl peroxide initiator and 10% of the pre-emulsion, react at constant temperature for 20 min, then add the remaining pre-emulsion, continue the constant temperature reaction for 2-3 h, cool and filter after the reaction is completed to obtain an epoxy resin modified acrylic resin;

[0029] (4) adding 7 g of 4-mercapto-2-methylphenol, 6 g of 3-aminotrifluorotoluene, and 12 g of polyformaldehyde to a toluene solvent, stirring and mixing, heating to 90° C. to react for 4 h, and after the reaction is completed, filtering, washing, and drying to obtain a fluorinated benzoxazine;

[0030] (5) adding 8 g of divinyl glycol and 6 g of fluorinated benzoxazine to N,N-dimethylformamide solvent, stirring and mixing, adding 0.03 g of benzoin dimethyl ether photoinitiator thereto, irradiating with 365 nm ultraviolet light at 36° C. for 45 min, and after the reaction is completed, centrifuging, washing and drying to obtain a fluorinated benzoxazine modified chain extender;

[0031] (6) Add 5 g of diphenylmethane diisocyanate, 10 g of polycaprolactone diol, and 0.04 g of dibutyltin dilaurate to the reactor, introduce nitrogen protection, and perform a prepolymerization reaction at 72° C. After reacting for 1.5 hours, cool to 62° C., add 3 g of fluorinated benzoxazine modified chain extender to perform a chain extension reaction, and the reaction time is 4 hours. After the reaction is completed, cool, wash and dry to obtain a fluorinated benzoxazine modified polyurethane;

[0032] (7) 15 parts by weight of low-density polyethylene, 8 parts by weight of epoxy resin-modified acrylic resin, and 6 parts by weight of fluorinated benzoxazine-modified polyurethane are mixed and melted to obtain a liquid film of a polymer waterproof layer. The liquid film is then evenly coated on both sides of a high-density polyethylene foam film through a laminating process. The reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer are then compounded. Finally, the film is dried and solidified, and cooled to obtain a glass fiber reinforced waterproof membrane.

[0033] Example 2

[0034] (1) Add 15 g of bisphenol A epoxy resin to a reactor, heat it to 60° C., then add 10 g of β-(acryloyloxy)propionic acid, 0.04 g of dimethylaniline catalyst, and 0.03 g of 4-methoxyphenol inhibitor, heat it to 100° C. and react for 4 h. After the reaction is completed, cool, wash and dry to obtain intermediate 1;

[0035] (2) adding intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide is 1:1.4:0.05, reacting at 30° C. for 3 h, filtering, washing and drying after the reaction to obtain an epoxy resin modified with alkenyl silane;

[0036] (3) Add 13 g of acrylic acid, 10 g of methyl methacrylate, 6 g of hydroxypropyl methacrylate, 8 g of alkenyl silane-modified epoxy resin, and 0.03 g of sodium dodecyl sulfate emulsifier to deionized water, stir and mix to obtain a pre-emulsion, add deionized water and 0.05 g of sodium dodecyl sulfate emulsifier to a reactor, heat to 85° C., add 0.04 g of benzoyl peroxide initiator and 10% of the pre-emulsion, react at constant temperature for 40 min, then add the remaining pre-emulsion, continue the constant temperature reaction for 3 h, cool and filter after the reaction is completed to obtain an epoxy resin-modified acrylic resin;

[0037] (4) adding 10 g of 4-mercapto-2-methylphenol, 9 g of 3-aminotrifluorotoluene, and 18 g of polyformaldehyde to a toluene solvent, stirring and mixing, heating to 100° C. for reaction for 5 h, filtering, washing, and drying after the reaction to obtain a fluorinated benzoxazine;

[0038] (5) adding 12 g of divinyl glycol and 9 g of fluorinated benzoxazine to N,N-dimethylformamide solvent, stirring and mixing, adding 0.05 g of benzoin dimethyl ether photoinitiator thereto, irradiating with 365 nm ultraviolet light at 40° C. for 60 min, and after the reaction is completed, centrifuging, washing and drying to obtain a fluorinated benzoxazine modified chain extender;

[0039] (6) 7 g of diphenylmethane diisocyanate, 12 g of polycaprolactone diol, and 0.06 g of dibutyltin dilaurate were added to the reactor, nitrogen was introduced for protection, and a prepolymerization reaction was carried out at 80° C. After reacting for 2.5 hours, the temperature was lowered to 68° C., and 6 g of a fluorinated benzoxazine modified chain extender was added to carry out a chain extension reaction. The reaction time was 5 hours. After the reaction was completed, the reaction was cooled, washed, and dried to obtain a fluorinated benzoxazine modified polyurethane;

[0040] (7) 20 parts by weight of low-density polyethylene, 10 parts by weight of epoxy resin-modified acrylic resin, and 9 parts by weight of fluorinated benzoxazine-modified polyurethane are mixed and melted to obtain a liquid film of a polymer waterproof layer. The liquid film is then evenly coated on both sides of a high-density polyethylene foam film through a laminating process. The reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer are then compounded. Finally, the film is dried and solidified, and cooled to obtain a glass fiber reinforced waterproof membrane.

[0041] Example 3

[0042] (1) Add 13.5 g of bisphenol A epoxy resin to a reactor, heat it to 55° C., then add 9 g of β-(acryloyloxy)propionic acid, 0.03 g of dimethylaniline catalyst, and 0.02 g of 4-methoxyphenol inhibitor, heat it to 98° C. and react for 3 h. After the reaction is completed, cool, wash and dry to obtain intermediate 1;

[0043] (2) adding intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide is 1:1.35:0.03, reacting at 29° C. for 2 h, filtering, washing and drying after the reaction to obtain an epoxy resin modified with alkenyl silane;

[0044] (3) Add 11 g of acrylic acid, 8.5 g of methyl methacrylate, 5 g of hydroxypropyl methacrylate, 6.5 g of alkenyl silane-modified epoxy resin, and 0.02 g of sodium dodecyl sulfate emulsifier to deionized water, stir and mix to obtain a pre-emulsion, add deionized water and 0.04 g of sodium dodecyl sulfate emulsifier to a reactor, heat to 80° C., add 0.03 g of benzoyl peroxide initiator and 10% of the pre-emulsion, react at constant temperature for 30 min, then add the remaining pre-emulsion, continue the constant temperature reaction for 2.5 h, cool and filter after the reaction to obtain an epoxy resin-modified acrylic resin;

[0045] (4) adding 8.5 g of 4-mercapto-2-methylphenol, 7.5 g of 3-aminotrifluorotoluene, and 15 g of polyformaldehyde to a toluene solvent, stirring and mixing, heating to 95° C. and reacting for 4.5 h. After the reaction is completed, filtering, washing, and drying to obtain a fluorinated benzoxazine;

[0046] (5) adding 10 g of divinyl glycol and 7.5 g of fluorinated benzoxazine to N,N-dimethylformamide solvent, stirring and mixing, adding 0.04 g of benzoin dimethyl ether photoinitiator thereto, irradiating with 365 nm ultraviolet light at 38° C. for 52 min, and after the reaction is completed, centrifuging, washing and drying to obtain a fluorinated benzoxazine modified chain extender;

[0047] (6) Add 6 g of diphenylmethane diisocyanate, 11 g of polycaprolactone diol, and 0.05 g of dibutyltin dilaurate to the reactor, introduce nitrogen protection, and perform a prepolymerization reaction at 76° C. After reacting for 2 hours, cool to 64° C., add 4.5 g of fluorinated benzoxazine modified chain extender to perform a chain extension reaction, and the reaction time is 4.5 hours. After the reaction is completed, cool, wash and dry to obtain a fluorinated benzoxazine modified polyurethane;

[0048] (7) 17 parts by weight of low-density polyethylene, 9 parts by weight of epoxy resin-modified acrylic resin, and 8 parts by weight of fluorinated benzoxazine-modified polyurethane are mixed and melted to obtain a liquid film of a polymer waterproof layer. The liquid film is then evenly coated on both sides of a high-density polyethylene foam film through a laminating process. The reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer are then compounded. Finally, the film is dried and solidified, and cooled to obtain a glass fiber reinforced waterproof membrane.

[0049] Example 4

[0050] (1) Add 12 g of bisphenol A epoxy resin to a reactor, heat it to 50° C., then add 8 g of β-(acryloyloxy)propionic acid, 0.02 g of dimethylaniline catalyst, and 0.01 g of 4-methoxyphenol inhibitor, heat it to 95° C. and react for 2 h. After the reaction is completed, cool, wash and dry to obtain intermediate 1;

[0051] (2) adding intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide is 1:1.3:0.02, reacting at 28°C for 1 hour, filtering, washing and drying after the reaction to obtain an epoxy resin modified with alkenyl silane;

[0052] (3) Add 13 g of acrylic acid, 10 g of methyl methacrylate, 6 g of hydroxypropyl methacrylate, 8 g of alkenyl silane-modified epoxy resin, and 0.03 g of sodium dodecyl sulfate emulsifier to deionized water, stir and mix to obtain a pre-emulsion, add deionized water and 0.05 g of sodium dodecyl sulfate emulsifier to a reactor, heat to 85° C., add 0.04 g of benzoyl peroxide initiator and 10% of the pre-emulsion, react at constant temperature for 40 min, then add the remaining pre-emulsion, continue the constant temperature reaction for 3 h, cool and filter after the reaction is completed to obtain an epoxy resin-modified acrylic resin;

[0053] (4) adding 10 g of 4-mercapto-2-methylphenol, 9 g of 3-aminotrifluorotoluene, and 18 g of polyformaldehyde to a toluene solvent, stirring and mixing, heating to 100° C. for reaction for 5 h, filtering, washing, and drying after the reaction to obtain a fluorinated benzoxazine;

[0054] (5) adding 10 g of divinyl glycol and 7.5 g of fluorinated benzoxazine to N,N-dimethylformamide solvent, stirring and mixing, adding 0.04 g of benzoin dimethyl ether photoinitiator thereto, irradiating with 365 nm ultraviolet light at 38° C. for 52 min, and after the reaction is completed, centrifuging, washing and drying to obtain a fluorinated benzoxazine modified chain extender;

[0055] (6) Add 6 g of diphenylmethane diisocyanate, 11 g of polycaprolactone diol, and 0.05 g of dibutyltin dilaurate to the reactor, introduce nitrogen protection, and perform a prepolymerization reaction at 76° C. After reacting for 2 hours, cool to 64° C., add 4.5 g of fluorinated benzoxazine modified chain extender to perform a chain extension reaction, and the reaction time is 4.5 hours. After the reaction is completed, cool, wash and dry to obtain a fluorinated benzoxazine modified polyurethane;

[0056] (7) 17 parts by weight of low-density polyethylene, 9 parts by weight of epoxy resin-modified acrylic resin, and 8 parts by weight of fluorinated benzoxazine-modified polyurethane are mixed and melted to obtain a liquid film of a polymer waterproof layer. The liquid film is then evenly coated on both sides of a high-density polyethylene foam film through a laminating process. The reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer are then compounded. Finally, the film is dried and solidified, and cooled to obtain a glass fiber reinforced waterproof membrane.

[0057] Example 5

[0058] (1) Add 13.5 g of bisphenol A epoxy resin to a reactor, heat it to 55° C., then add 9 g of β-(acryloyloxy)propionic acid, 0.03 g of dimethylaniline catalyst, and 0.02 g of 4-methoxyphenol inhibitor, heat it to 98° C. and react for 3 h. After the reaction is completed, cool, wash and dry to obtain intermediate 1;

[0059] (2) adding intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, wherein the mass ratio of intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide is 1:1.35:0.03, reacting at 29° C. for 2 h, filtering, washing and drying after the reaction to obtain an epoxy resin modified with alkenyl silane;

[0060] (3) Add 9 g of acrylic acid, 7 g of methyl methacrylate, 4 g of hydroxypropyl methacrylate, 5 g of alkenyl silane-modified epoxy resin, and 0.01 g of sodium dodecyl sulfate emulsifier to deionized water, stir and mix to obtain a pre-emulsion, add deionized water and 0.02 g of sodium dodecyl sulfate emulsifier to a reactor, heat to 75° C., add 0.02 g of benzoyl peroxide initiator and 10% of the pre-emulsion, react at constant temperature for 20 min, then add the remaining pre-emulsion, continue the constant temperature reaction for 2-3 h, cool and filter after the reaction is completed to obtain an epoxy resin modified acrylic resin;

[0061] (4) adding 7 g of 4-mercapto-2-methylphenol, 6 g of 3-aminotrifluorotoluene, and 12 g of polyformaldehyde to a toluene solvent, stirring and mixing, heating to 90° C. to react for 4 h, and after the reaction is completed, filtering, washing, and drying to obtain a fluorinated benzoxazine;

[0062] (5) adding 12 g of divinyl glycol and 9 g of fluorinated benzoxazine to N,N-dimethylformamide solvent, stirring and mixing, adding 0.05 g of benzoin dimethyl ether photoinitiator thereto, irradiating with 365 nm ultraviolet light at 40° C. for 60 min, and after the reaction is completed, centrifuging, washing and drying to obtain a fluorinated benzoxazine modified chain extender;

[0063] (6) 7 g of diphenylmethane diisocyanate, 12 g of polycaprolactone diol, and 0.06 g of dibutyltin dilaurate were added to the reactor, nitrogen was introduced for protection, and a prepolymerization reaction was carried out at 80° C. After reacting for 2.5 hours, the temperature was lowered to 68° C., and 6 g of a fluorinated benzoxazine modified chain extender was added to carry out a chain extension reaction. The reaction time was 5 hours. After the reaction was completed, the reaction was cooled, washed, and dried to obtain a fluorinated benzoxazine modified polyurethane;

[0064] (7) 20 parts by weight of low-density polyethylene, 10 parts by weight of epoxy resin-modified acrylic resin, and 9 parts by weight of fluorinated benzoxazine-modified polyurethane are mixed and melted to obtain a liquid film of a polymer waterproof layer. The liquid film is then evenly coated on both sides of a high-density polyethylene foam film through a laminating process. The reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer are then compounded. Finally, the film is dried and solidified, and cooled to obtain a glass fiber reinforced waterproof membrane.

[0065] Comparative Example 1

[0066] The difference between this comparative example and Example 5 is that no epoxy resin-modified acrylic resin is added to the polymer waterproof layer of the glass fiber reinforced waterproof membrane.

[0067] Comparative Example 2

[0068] The difference between this comparative example and Example 5 is that no fluorinated benzoxazine-modified polyurethane is added to the polymer waterproof layer of the glass fiber reinforced waterproof membrane.

[0069] According to GB / T18173.1-2012, the tensile strength test of the glass fiber reinforced waterproof membranes of Examples 1-5 and Comparative Examples 1-2 was performed at a test temperature of 23° C. The test results are shown in Table 1.

[0070] Table 1: Tensile strength test.

[0071]

[0072]

[0073] The tear strength test of the glass fiber reinforced waterproof membranes of Examples 1-5 and Comparative Examples 1-2 was performed according to GB / T18173.1-2012. The test results are shown in Table 2.

[0074] Table 2: Tear strength test.

[0075]

[0076] It can be seen from Table 1 and Table 2 that Examples 1-5 have better mechanical properties than Comparative Examples 1-2.

[0077] According to GB / T3512-2014, the glass fiber reinforced waterproof membranes of Examples 1-5 and Comparative Examples 1-2 were subjected to a hot air aging test at 80°C for 168 hours, and the tensile strength retention rate of the membranes after aging was calculated. The test results are shown in Table 3.

[0078] Table 3: Aging resistance test.

[0079]

[0080]

[0081] It can be seen from Table 3 that Examples 1-5 have better aging resistance than Comparative Examples 1-2.

[0082] According to GB / T18173.1-2012, the glass fiber reinforced waterproof membranes of Examples 1-5 and Comparative Examples 1-2 were tested for water impermeability, with a test pressure of 0.3 MPa and a test time of 30 min. The test results are shown in Table 4.

[0083] Table 4: Water-tightness test.

[0084] project Water seepage Example 1 No leakage Example 2 No leakage Example 3 No leakage Example 4 No leakage Example 5 No leakage Comparative Example 1 Minor leakage Comparative Example 2 Minor leakage

[0085] According to T / CWA302-2023, the glass fiber reinforced waterproof membranes of Examples 1-5 and Comparative Examples 1-2 were tested for water resistance at a test temperature of 23° C. and a water immersion time of 14 days. The test results are shown in Table 5.

[0086] Table 5: Water resistance test.

[0087]

[0088]

[0089] It can be seen from Table 4 and Table 5 that Examples 1-5 have better waterproof effects than Comparative Examples 1-2.

[0090] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. Glass fiber reinforced waterproof membrane, characterized in that: From top to bottom, they are a reinforced protective layer, a polymer waterproof layer, a high-density polyethylene foam film, and a polymer waterproof layer. The reinforced protective layer is made of polyvinyl fluoride coated on glass fiber cloth. The polymer waterproof layer includes the following raw materials in parts by weight: 15-20 parts by weight of low-density polyethylene, 8-10 parts by weight of epoxy resin modified acrylic resin, and 6-9 parts by weight of fluorinated benzoxazine modified polyurethane.

2. The glass fiber reinforced waterproof coiled material according to claim 1, characterized in that: The preparation method of the epoxy resin modified acrylic resin comprises the following steps: (1) Add 12-15 g of bisphenol A epoxy resin to a reactor, heat it to 50-60° C., then add 8-10 g of β-(acryloyloxy)propionic acid, 0.02-0.04 g of a catalyst, and 0.01-0.03 g of a polymerization inhibitor, heat it to 95-100° C., react for 2-4 h, and after the reaction is complete, cool, wash, and dry to obtain an intermediate 1; (2) adding the intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide catalyst to N,N-dimethylformamide solvent, stirring and mixing, reacting at 28-30° C. for 1-3 hours, filtering, washing and drying after the reaction to obtain an epoxy resin modified with alkenyl silane; (3) Add 9-13 g of acrylic acid, 7-10 g of methyl methacrylate, 4-6 g of hydroxypropyl methacrylate, 5-8 g of alkenyl silane-modified epoxy resin, and 0.01-0.03 g of emulsifier to deionized water, stir and mix to obtain a pre-emulsion, add deionized water and 0.02-0.05 g of emulsifier to a reactor, heat to 75-85° C., add 0.02-0.04 g of initiator and 10% of the pre-emulsion, react at constant temperature for 20-40 min, then add the remaining pre-emulsion, continue the constant temperature reaction for 2-3 h, cool and filter after the reaction is completed to obtain epoxy resin modified acrylic resin.

3. The glass fiber reinforced waterproof coiled material according to claim 2, characterized in that: In the step (1), the catalyst is dimethylaniline and the inhibitor is 4-methoxyphenol.

4. The glass fiber reinforced waterproof coiled material according to claim 2, characterized in that: In the step (2), the mass ratio of the intermediate 1, 3-(N-allylamino)propyltrimethoxysilane and sodium ethoxide is 1:1.3-1.4:0.02-0.

05.

5. The glass fiber reinforced waterproof coiled material according to claim 2, characterized in that: In the step (3), the emulsifier is sodium lauryl sulfate and the initiator is benzoyl peroxide.

6. The glass fiber reinforced waterproof coiled material according to claim 1, characterized in that: The method for preparing the fluorinated benzoxazine-modified polyurethane comprises the following steps: S1. Add 7-10 g of 4-mercapto-2-methylphenol, 6-9 g of 3-aminotrifluorotoluene, and 12-18 g of paraformaldehyde to a toluene solvent, stir and mix, and heat to react for 4-5 hours. After the reaction is completed, filter, wash and dry to obtain a fluorinated benzoxazine; S2. Add 8-12 g of divinyl glycol and 6-9 g of fluorinated benzoxazine to N,N-dimethylformamide solvent, stir and mix, then add 0.03-0.05 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 36-40 ° C, after the reaction is completed, centrifuge, wash and dry to obtain a fluorinated benzoxazine modified chain extender; S3. Add 5-7g of diphenylmethane diisocyanate, 10-12g of polycaprolactone diol, and 0.04-0.06g of dibutyltin dilaurate into the reactor, introduce nitrogen protection, and carry out prepolymerization at 72-80°C. After reacting for 1.5-2.5h, cool to 62-68°C, add 3-6g of fluorinated benzoxazine modified chain extender to carry out chain extension reaction, and the reaction time is 4-5h. After the reaction is completed, cool, wash and dry to obtain fluorinated benzoxazine modified polyurethane.

7. The glass fiber reinforced waterproof coiled material according to claim 6, characterized in that: The reaction temperature in S1 is 90-100°C.

8. The glass fiber reinforced waterproof coiled material according to claim 6, characterized in that: The ultraviolet light irradiation time in S2 is 45-60 minutes.

9. The glass fiber reinforced waterproof coiled material according to claim 1, characterized in that: The preparation method of the glass fiber reinforced waterproof coiled material is as follows: low-density polyethylene, epoxy resin modified acrylic resin, and fluorinated benzoxazine modified polyurethane are mixed and melted to obtain a liquid film of a polymer waterproof layer, and then the liquid film is evenly coated on both sides of a high-density polyethylene foam film through a laminating process, and then the reinforced protective layer and the high-density polyethylene foam film coated with the polymer waterproof layer are compounded, and finally dried and solidified, and cooled to obtain the glass fiber reinforced waterproof coiled material.

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