Waterproof material for waterproof roll material

Abstract

The present invention relates to the technical field of waterproof roll materials, specifically to a waterproof material for waterproof roll materials. The waterproof material produced by the present invention is used to prepare waterproof roll materials, which overcomes the problems of poor temperature resistance and poor waterproof effect of waterproof roll materials. By adjusting the types and amounts of dithiol and alkenylmethylsiloxane of a raw material for a synthetic waterproof layer; modifying hollow glass microspheres, and mixing the modified silane-maleic anhydride-hollow glass microspheres with maleic anhydride grafted high-density polyethylene to obtain a waterproof outer layer raw material; adjusting the material composition of nanofiltration raw materials one, two and post-treatment liquid to obtain a nanofiltration composite layer raw material; at the same time, changing the amount and proportion of the microcapsule layer raw material, and changing the preparation method of the adhesive layer raw material; the waterproof roll material prepared from the above raw materials has good temperature resistance and waterproof effect, and the waterproof roll material has an intuitive display effect of water erosion by the naked eye.

Description

Technical Field

[0001] The invention relates to the technical field of waterproof coiled materials, in particular to a waterproof material for waterproof coiled materials. Background Art

[0002] Waterproof membrane is a building material with waterproof function, usually composed of one or more layers of materials. It blocks moisture, thus protecting the building and extending the building's protective life. According to the different synthetic raw materials, waterproof membrane can be divided into rubber-based, modified asphalt-based, polyvinyl chloride (PVC)-based, glass fiber-based and polymer materials. Among them, modified asphalt-based waterproof membrane accounts for a large share of the market, but with the gradual increase in environmental protection requirements, the advantages of polymer waterproof membrane are becoming increasingly prominent.

[0003] PVC waterproofing membrane is composed of PVC resin, plasticizer, stabilizer, etc. It has good water resistance, chemical resistance, UV resistance and high temperature resistance, but the strength of the material itself is low. In addition, the compatibility of additives with PVC is poor, and plasticizers are easy to migrate; polyethylene (HDPE) waterproofing membrane is suitable for high-pressure environments, but its own flame retardant effect is poor and its application range is small; ethylene propylene diene monomer (EPDM) waterproofing membrane has good elasticity, weather resistance, UV resistance and chemical resistance; thermoplastic polyolefin (TPO) waterproofing membrane is a waterproof material made of polyolefin polymers, which has good UV resistance, weather resistance and heat reflectivity. However, the use of the above materials requires the use of welding technology, including hot air welding and infrared welding, etc., to improve the sealing effect, but the construction is complicated. Therefore, self-adhesive waterproofing membranes have emerged, which do not require hot welding during construction, and are simple to construct and low in cost. However, self-adhesive waterproof membranes are easily affected by the construction environment during the construction process. As the temperature rises, the fluidity of the self-adhesive layer increases. When constructed in a low-temperature environment, the membrane shrinks, which increases the difficulty of construction. The waterproof membrane bonded during construction is also prone to reduced viscosity under the influence of the external ambient temperature, resulting in bulging and reduced peel strength.

[0004] To overcome the above problems, plasticizers, UV inhibitors and high-performance fillers are added to waterproof membranes, but these substances have poor compatibility with the polymer raw materials of waterproof membranes, and the above additives have poor dispersibility, which in turn reduces the performance of waterproof membranes and reduces the waterproof effect of waterproof membranes. In addition, the waterproof performance of waterproof membranes that have been used for a long time has declined, and the decline in performance cannot be directly observed with the naked eye.

[0005] Therefore, a waterproof material for waterproof membrane is proposed. Summary of the invention

[0006] The object of the present invention is to provide a waterproof material for waterproof roll materials. By adjusting the types and amounts of dithiol and alkenylmethylsiloxane of a raw material for a synthetic waterproof layer, the obtained waterproof roll material has good temperature resistance, high tensile strength and high elongation at break at a corresponding temperature; the hollow glass microspheres are modified, and the modified silane-maleic anhydride-hollow glass microspheres are mixed with maleic anhydride grafted high-density polyethylene, and finally an anti-aging agent, an antioxidant, aromatic oil, PP wax and a leveling agent are added to obtain a waterproof outer layer raw material, and the heat resistance effect of the obtained waterproof roll material is further improved; by adjusting the material composition of nanofiltration raw materials one, two and a post-treatment liquid; at the same time, the amount and proportion of the raw material of the microcapsule layer are changed, and the preparation method of the raw material of the adhesive layer is changed, the nanofiltration composite layer formed after the water body passes through the waterproof outer layer plays a filtering and blocking role on the water again, the water body is colored after reaching the microcapsule layer, and solidifies to form a new waterproof layer; the waterproof roll material prepared from the above raw materials has good temperature resistance and waterproof effect.

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

[0008] A waterproof material for waterproof coiled material, the waterproof material for waterproof coiled material comprising: waterproof outer layer raw material, nanofiltration composite layer raw material, microcapsule layer raw material, waterproof inner layer raw material, polymer layer raw material and adhesive layer raw material;

[0009] The preparation method of a raw material for a waterproof layer is as follows: 30 parts of polyethylene TPO, 9.3-15.8 parts of alkenyl methyl siloxane, 6.0-8.0 parts of dithiol and 1.3 parts of benzoin dimethyl ether are mixed by weight, and the mixture is heated and cured by ultraviolet irradiation to obtain a precursor for a waterproof layer; a precursor for a waterproof layer, THF, potassium persulfate composite salt and deionized water are mixed in a weight ratio of 1:6:6-7:2-4, the temperature is increased to 60°C, and the mixture is stirred and reacted for 10 hours under nitrogen protection to obtain an intermediate for a waterproof layer; then 5 parts of potassium persulfate composite salt, 20 parts of deionized water and 20 parts of THF are added, the reaction is continued for 12 hours, and then the raw material for a waterproof layer is obtained by extraction with dichloromethane, washing with deionized water and rotary evaporation;

[0010] The preparation method of the waterproof outer layer material is as follows: 10 parts of alkaline hollow glass microspheres and 10 parts of 5% by mass maleic anhydride aqueous solution are mixed, and stirred at 50°C for 15 minutes to obtain maleic anhydride grafted hollow glass microspheres; KH550, 0.1 parts of EDC and 0.1 parts of Tween 80 are added to the maleic anhydride grafted hollow glass microspheres, and the stirring reaction is continued for 1.5 hours to obtain silane-maleic anhydride-hollow glass microspheres; then 90 parts of maleic anhydride are added to the hollow glass microspheres; Grafting high-density polyethylene with acid anhydride, raising the temperature to 120-135°C, stirring and reacting for 30 minutes under nitrogen protection to obtain modified high-density polyethylene; mixing the modified high-density polyethylene, a raw material for a waterproof layer, an anti-aging agent, an antioxidant, aromatic oil, PP wax and a leveling agent in a ratio of 1-11: 1-8: 0.5-0.8: 0.2-0.4: 1.5-2.5: 1-1.5: 0.1-0.3 to obtain a raw material for a waterproof outer layer;

[0011] The nanofiltration composite layer raw material is prepared from a nanofiltration raw material 1, a nanofiltration raw material 2 and a post-treatment liquid; the nanofiltration raw material 1 is obtained by mixing p-phenylenediamine, triethylamine, an organic mixed acid and deionized water; the mass percentage of p-phenylenediamine in the nanofiltration raw material 1 is 3.0%-3.8%; the nanofiltration raw material 2 is obtained by mixing terephthaloyl chloride and 1-hexene; the mass percentage of terephthaloyl chloride in the nanofiltration raw material 2 is 5.5%-9.3%; the post-treatment liquid is obtained by mixing nanocellulose, triethylamine and deionized water; the mass percentage of nanocellulose is 2.0%-3.5%;

[0012] The organic mixed acid includes an organic mixed acid 1 and an organic mixed acid 2; the organic mixed acid 1 is one of fumaric acid and polyacrylic acid; the organic mixed acid 2 is one of polyacrylic acid and polystyrene sulfonic acid; the mass mixing ratio of the organic mixed acid 1 to the organic mixed acid 2 is 1:1-3;

[0013] The preparation method of the microcapsule layer raw material is as follows: 50 parts of polylactic acid-glycolic acid copolymer and 7.5-10 parts of hydroxy cage silane are mixed, the temperature is raised to 120-150° C., and the mixture is added dropwise to the capsule shell material in a molten state; the microcapsule layer raw material with an average particle size of 280nm-600nm is obtained by grinding; the molar ratio of polylactic acid to glycolic acid in the polylactic acid-glycolic acid copolymer is 1-4:1-2;

[0014] The preparation method of the raw material of the adhesive layer is as follows: 7.0 parts of methyl methacrylate, 7.0 parts of ethyl acrylate, 21.0 parts of tripropylene glycol diacrylate, 11.9 parts of diacetone acrylamide, 17.8 parts of fluorinated acrylate, 0.5 parts of alkylphenol polyoxyethylene ether, 18.0 parts of deionized water, 0.4 parts of sodium bicarbonate and 0.8 parts of ammonium persulfate are uniformly mixed to obtain a solution to be polymerized; the solution to be polymerized is heated to 70°C, stirred for reaction for 30 minutes, then heated to 80°C, reacted for 1 hour, then cooled to 60°C and kept warm for 2.5 hours to obtain a polymerized solution; the pH of the polymerized solution is adjusted to 9.0, diacetyl adipic acid dihydrazide is added, reacted at 80°C for 10 minutes, then an acid raw material, hydroxy cage silane and 0.5 parts of phosphoric acid are added thereto, reacted for 3 hours, and then dried to obtain the raw material of the adhesive layer.

[0015] Preferably, the alkenylmethylsiloxane is one of 1,7-divinyl-octamethyltetrasiloxane, tetramethyldivinyldisiloxane and 1,5-divinyl-hexamethyltrisiloxane; and the dithiol is one of 1,4-butanedithiol, 1,5-pentanedithiol and 1,2-benzenedithiol.

[0016] Preferably, the preparation method of alkaline hollow glass microspheres is as follows: hollow glass microspheres and stearic acid are mixed in a mass ratio of 50:1 to obtain 10 parts of a hollow glass microsphere mixture; then, a 10% by mass sodium hydroxide aqueous solution is added to the hollow glass microsphere mixture, and the mixture is ground and dried to obtain alkaline hollow glass microspheres; the alkalinity of the alkaline hollow glass microspheres is 0.2-1.2 equivalents / g; and the average particle size of the alkaline hollow glass microspheres is 37µm.

[0017] Preferably, the preparation method of the raw material of the waterproof outer layer is as follows: after mixing polyethylene TPO, 14.5-15.8 parts of alkenyl methyl siloxane, 6.8-8.0 parts of dithiol and benzoin dimethyl ether, the temperature is raised to 180°C, and a homogeneous phase is obtained after melting; 10 parts of the homogeneous phase are stirred and reacted under 100W ultraviolet light with a wavelength of 365nm for 10 minutes, then cooled to room temperature, dissolved with 80 parts of THF, and precipitated with 300 parts of methanol again, and the methanol is removed to obtain a precursor of the waterproof layer;

[0018] The modified high-density polyethylene, the first raw material of the waterproof layer, the anti-aging agent, the antioxidant, the aromatic oil, the PP wax and the leveling agent are mixed at 135° C. for 10 minutes to obtain the raw material of the waterproof outer layer; the alkalinity of the alkaline hollow glass microspheres is 0.4-1.2 equivalents / gram;

[0019] The anti-aging agent is obtained by mixing phenylbenzotriazole and 1,2,3,4-tetrahydroquinoline in a ratio of 1:1; the antioxidant is BHT; the aromatic oil is Aromatic 200; and the leveling agent is an organic silicone leveling agent.

[0020] Preferably, the preparation method of the microcapsule layer raw material is as follows: MDI and quicklime, anhydrous ferrous sulfate and diethylenetriamine are mixed in a mass ratio of 10-18:32-40:10-14:1-5, and ball-milled in a ball mill at 30°C for 2 hours, and then cooled to room temperature to obtain a capsule shell material with a particle size of 100nm; polylactic acid-glycolic acid copolymer, methanol and hydroxyl cage silane are mixed, and then the temperature is increased to 120-130°C, and the mixture is stirred and melted to obtain a polylactic acid-glycolic acid copolymer melt; in a molten state at 120°C, 75 parts of the polylactic acid-glycolic acid copolymer melt are added dropwise to 25 parts of the capsule shell material, and the mixture is stirred at 1000rpm, and then dried, cooled and solidified to obtain a microcapsule layer raw material with an average particle size of 280nm-450nm.

[0021] Preferably, the fluorine-based acrylate is one of 2,2,3,3,4,4,4-heptafluorobutyl acrylate, hexafluorobutyl acrylate and 1H,1H-perfluorooctyl acrylate; and the acid raw material is one of citric acid, oxalic acid and boric acid.

[0022] Preferably, the waterproof coiled material is prepared from a waterproof material; the structure of the waterproof coiled material from top to bottom is a waterproof outer layer, a nanofiltration composite layer, a microcapsule layer, a waterproof inner layer, a polymer layer and an adhesive layer.

[0023] Preferably, the preparation method of the nanofiltration composite layer is as follows: the waterproof outer layer raw material is melt-extruded at 150°C to obtain a sheet, the surface of the sheet is immersed in the solution of nanofiltration raw material one, and after soaking for 1 minute, it is purged with nitrogen to make its surface free of obvious droplets, and then the solution of nanofiltration raw material two is poured on the surface of the above material, and after soaking for 1 minute, it is purged with nitrogen again, and then treated at 80°C for 8 minutes to obtain a sheet and a nanofiltration composite layer precursor; the post-treatment liquid is coated on a single surface of the nanofiltration composite layer precursor, and then vacuum dried at 60°C to obtain the nanofiltration composite layer.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. By using polyethylene TPO, alkenyl methyl siloxane, dithiol, benzoin dimethyl ether and potassium persulfate complex salt as basic components of a raw material for synthesizing a waterproof layer, adjusting their dosage to form a raw material containing a polysulfone polysilane structure and a TPO cross-linked structure, and adjusting the dosage of the raw material for the waterproof layer and the modified high-density polyethylene component, the waterproof roll material obtained by the waterproof raw material has good temperature resistance.

[0026] 2. By introducing hollow glass microspheres, the borosilicate glass contained therein can improve the heat resistance of the waterproofing membrane. By modifying its surface, alkaline hollow glass microspheres are obtained, and the alkalinity of the alkaline hollow glass microspheres is adjusted. Then, maleic anhydride is introduced into the alkaline hollow glass microspheres. The carboxyl group after the ring opening of maleic anhydride is neutralized with the alkalinity of the alkaline hollow glass microspheres, thereby introducing maleic anhydride into the alkaline hollow glass microspheres. Then, the unreacted carboxyl group in the maleic anhydride molecule is condensed with the amino group of KH550. The modified silane-maleic anhydride-hollow glass microspheres are mixed with maleic anhydride grafted high-density polyethylene. In the molten state, the hydroxyl groups in the silane-maleic anhydride-hollow glass microspheres react and cross-link with the maleic anhydride in the maleic anhydride grafted high-density polyethylene. At the same time, the dosage ratio of the anti-aging agent, the antioxidant, the aromatic oil, the PP wax and the leveling agent is controlled, and the obtained waterproofing membrane has further improved heat resistance.

[0027] 3. By adjusting the composition and proportion of p-phenylenediamine and organic mixed acid in the nanofiltration raw material 1, the surface of the sheet obtained from the waterproof outer layer raw material is treated, and then the nanofiltration raw material 1 and the post-treatment liquid are used for treatment, so that a layer of reverse osmosis nanofiltration membrane structure with a certain strength is formed between the waterproof outer layer and the microcapsule layer. After the external water passes through the waterproof outer layer, it is further blocked in the nanofiltration structure layer, and a small part of the water enters the microcapsule layer, thereby changing the color of the waterproof coiled material. The waterproof performance is improved, and the waterproof effect of the waterproof coiled material is more intuitive.

[0028] 4. By adjusting the amount of alkenylmethylsiloxane used to prepare the raw materials for the waterproof outer layer; by changing the method for preparing the raw materials for the microcapsule layer, wherein the amount ratio of MDI to quicklime, anhydrous ferrous sulfate and diethylenetriamine is adjusted, wherein MDI, on the one hand, forms a solidified urea-based compound when it comes into contact with water, and releases a large amount of heat at the same time; on the other hand, anhydrous ferrous sulfate plays a role as a color indicator in the waterproof coiled material, and turns light green when it comes into contact with water, and the change in color can directly reflect the water-resistant effect of its waterproof outer layer; in addition, quicklime releases heat when it comes into contact with water, and under the action of diethylenetriamine, MDI reacts with the hydroxyl group or part of the hydroxyl cage silane of the nanocellulose in the nanofiltration composite layer structure to form a compound containing an amide structure, and the cross-linked substance formed by the curing of the microcapsule layer forms a new protective layer again; at the same time, the molar ratio of polylactic acid and glycolic acid, the amount of hydroxyl cage silane, the reaction temperature and the particle size of the raw materials for the microcapsule layer are adjusted, thereby further improving the waterproof effect of the waterproof coiled material.

[0029] 5. By rationally selecting the type of fluorine-based acrylate in the raw material of the adhesive layer, the acrylate containing unsaturated double bonds is polymerized under the action of an initiator, and then the amount of diacetyl adipic acid dihydrazide added is adjusted, the type of acid is changed, and finally the amount of hydroxy cage silane is adjusted, thereby improving the waterproof effect of the adhesive layer in the waterproof membrane and the bonding peel strength to cement. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a schematic diagram of the waterproof membrane structure of the present invention;

[0031] Figure 2 This is a graph showing the tensile strength results of the waterproof membranes of Examples 9, 12-20 of the present invention and Comparative Examples 3-7.

[0032] In the figure: 1-waterproof outer layer, 2-nanofiltration composite layer, 3-microcapsule layer, 4-waterproof inner layer, 5-polymer layer, 6-adhesive layer. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] See also Figure 1 to Figure 2 The present invention provides a waterproof material for waterproof roll material, and the technical solution is as follows:

[0035] The material information used in the present invention is as follows: 1,7-divinyl-octamethyltetrasiloxane CAS: 13315-13-4; tetramethyldivinyldisiloxane CAS: 2627-95-4; 1,5-divinyl-hexamethyltrisiloxane CAS: 17980-39-1; 1,4-butanedithiol CAS: 1191-08-8; 1,5-pentanedithiol CAS: 928-98-3; 1,2-benzenedithiol CAS: 17534-15-5; benzoin dimethyl ether CAS: 24650-42-8; p-phenylenediamine CAS: 106-50-3; triethylamine CAS: 121-44-8; fumaric acid CAS: 110-17-8; 1,3,5-benzenetricarboxylic acid chloride CAS: 4422-95-1; polystyrene sulfonic acid CAS: 28210-41-5; polypropylene Oleic acid CAS: 9003-01-4; methyl methacrylate CAS: 80-62-6; ethyl acrylate CAS: 140-88-5; tripropylene glycol diacrylate CAS: 42978-66-5; diacetone acrylamide CAS: 2873-97-4; 2,2,3,3,4,4,4-heptafluorobutyl acrylate CAS: 424-64-6; hexafluorobutyl acrylate CAS: 54052-90-3; 1H,1H-perfluorooctyl acrylate CAS: 307-98-2; phenylbenzotriazole CAS: 2240-22-4; 1,2,3,4-tetrahydroquinoline CAS: 635-46-1; antioxidant 264 (BHT) CAS: 128-37-0; 4,4'-diphenylmethane diisocyanate (MDI) CAS: 101-68-8.

[0036] Aromatic 200, a aromatic solvent oil, was purchased from Jiangsu Hualun Chemical Co., Ltd.; the organosilicon leveling agent was purchased from Kramar Reagent Company, model BYK-349; and the maleic anhydride grafted high-density polyethylene was purchased from DuPont, USA, model E100.

[0037] Example 1

[0038] After mixing 30 parts of polyethylene TPO, 14.5 parts of alkenyl methyl siloxane, 7.1 parts of dithiol and 1.3 parts of benzoin dimethyl ether, the temperature was raised to 180°C, and a homogeneous phase was obtained after melting; 10 parts of the homogeneous phase were stirred and reacted under 100W ultraviolet light (wavelength 365nm) for 10 minutes, then cooled to room temperature, dissolved with 80 parts of THF, precipitated with 300 parts of methanol again, and the methanol was removed to obtain a waterproof layer precursor; a waterproof layer precursor, THF, potassium persulfate composite salt and deionized water were mixed in a mass ratio of 5:30:30:20, the temperature was raised to 60°C, and stirred and reacted for 10 hours under nitrogen protection to obtain a waterproof layer intermediate; then 5 parts of potassium persulfate composite salt, 20 parts of deionized water and 20 parts of THF were added, and the reaction was continued for 12 hours, and then extracted with dichloromethane, washed with deionized water and rotary evaporated to obtain a waterproof layer raw material.

[0039] Hollow glass microspheres and stearic acid were mixed in a ratio of 50:1 to obtain 10 parts of a hollow glass microsphere mixture; then, a 10% by mass sodium hydroxide aqueous solution was added to the hollow glass microsphere mixture, and the mixture was ground and dried to obtain alkaline hollow glass microspheres.

[0040] 10 parts of alkaline hollow glass microspheres and 10 parts of 5% by mass maleic anhydride aqueous solution were mixed, and stirred at 50°C for 15 minutes to obtain maleic anhydride grafted hollow glass microspheres; 1.1 parts of KH550, 0.1 parts of EDC and 0.1 parts of Tween 80 were added to the maleic anhydride grafted hollow glass microspheres, and the stirring reaction was continued for 1.5 hours to obtain silane-maleic anhydride-hollow glass microspheres; then 90 parts of maleic anhydride grafted high-density polyethylene were added, the temperature was raised to 135°C, and the reaction was stirred for 30 minutes under nitrogen protection to obtain modified high-density polyethylene; the modified high-density polyethylene, waterproof layer one, anti-aging agent, antioxidant, aromatic oil, PP wax and leveling agent were mixed at a mass ratio of 40:55:0.5:0.3:2:1:0.1 at 135°C for 10 minutes to obtain the waterproof outer layer raw material.

[0041] The anti-aging agent is phenylbenzotriazole and 1,2,3,4-tetrahydroquinoline in a proportion of 1:1; the antioxidant is BHT; the aromatic solvent oil is Aromatic 200; and the leveling agent is an organic silicon leveling agent.

[0042] MDI, quicklime, anhydrous ferrous sulfate and diethylenetriamine were mixed in a mass ratio of 15:35:12:3, and the mixture was ball-milled in a ball mill at 30°C for 2 hours. After cooling to room temperature, a capsule shell material with a particle size of 100 nm was obtained. 50 parts of polylactic acid-glycolic acid copolymer (the molar ratio of polylactic acid to glycolic acid was 2:3), 100 parts of methanol and 10 parts of hydroxy cage silane were mixed, and then the temperature was raised to 120°C, and the mixture was stirred and melted to obtain a polylactic acid-glycolic acid copolymer melt. In a molten state at 120°C, 75 parts of the polylactic acid-glycolic acid copolymer melt were dropwise added to 25 parts of the capsule shell material, and the mixture was stirred at 1000 rpm, and then dried, cooled and solidified to obtain a microcapsule layer raw material with an average particle size of 280 nm-600 nm.

[0043] The raw material of the waterproof inner layer is obtained by mixing the waterproof layer 1 and the modified high-density polyethylene in a ratio of 1:9; the amount of the raw material of the waterproof inner layer is 100 parts.

[0044] The raw material of the polymer layer is a mixture of high-density polyethylene and thermoplastic polyolefin melt-mixed in a ratio of 3:1; the total weight of the high-density polyethylene and thermoplastic polyolefin is 120 parts.

[0045] 7.0 parts of methyl methacrylate, 7.0 parts of ethyl acrylate, 21.0 parts of tripropylene glycol diacrylate, 11.9 parts of diacetone acrylamide, 17.8 parts of 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 0.5 parts of alkylphenol polyoxyethylene ether, 18.0 parts of deionized water, 0.4 parts of sodium bicarbonate and 0.8 parts of ammonium persulfate are uniformly mixed to obtain a solution to be polymerized; the solution to be polymerized is heated to 70°C, stirred for reaction for 30 minutes, then heated to 80°C, reacted for 1 hour, then cooled to 60°C and kept warm for 2.5 hours to obtain a polymerizing solution; the pH of the polymerizing solution is adjusted to 9.0, 18.1 parts of diacetyl adipic acid dihydrazide are added, reacted at 80°C for 10 minutes, 6.5 parts of acid raw materials citric acid and 7 parts of hydroxy cage silane and 0.5 parts of phosphoric acid are added thereto, reacted for 3 hours, and then dried to obtain a raw material for an adhesive layer.

[0046] Embodiment 2-10

[0047] Different from Example 1, the preparation method of the waterproof layer raw material and the mixing and proportion of the waterproof layer raw material and its modified high-density polyethylene are changed, as shown in Table 1. The four substances in Table 1 are a waterproof layer precursor, THF, potassium persulfate complex salt and deionized water.

[0048] Table 1 Preparation method of waterproof layer raw materials and mixing ratio with modified high-density polyethylene

[0049]

[0050] Comparative Example 1

[0051] Different from Example 1, no modified high-density polyethylene is added to obtain the waterproof outer layer raw material.

[0052] Comparative Example 2

[0053] Different from Example 1, no raw material for the waterproof layer 1 is added to obtain the raw material for the waterproof outer layer.

[0054] Embodiment 11

[0055] The waterproof outer layer raw materials obtained in Examples 1-10 and Comparative Examples 1 and 2 were melt-extruded at 150°C to obtain a sheet, and its surface was immersed in the solution of nanofiltration raw material 1, and nitrogen was used to purge it after soaking for 1 minute to make it clear that there were no obvious droplets on the surface, and then the solution of nanofiltration raw material 2 was poured on the surface of the above materials, and nitrogen was used to purge it again after soaking for 1 minute, and then it was treated at 80°C for 8 minutes to obtain a sheet and a nanofiltration composite layer precursor. Nanocellulose crystals and deionized water were mixed in a ratio of 3:100 (post-treatment liquid) and then coated on a single surface of the nanofiltration composite layer precursor again, and then vacuum dried at 60°C to obtain a nanofiltration composite layer.

[0056] After the microcapsule layer, waterproof inner layer and polymer layer are melted, they are hot pressed with the nanofiltration composite layer and the self-adhesive layer to obtain a waterproof roll. The waterproof roll has a total of 6 layers, such as Figure 1 As shown, the structure of the waterproof roll material is, from top to bottom, a waterproof outer layer 1, a nanofiltration composite layer 2, a microcapsule layer 3, a waterproof inner layer 4, a polymer layer 5 and an adhesive layer 6.

[0057] The waterproof membranes obtained according to the methods of Examples 1-10 and Comparative Examples 1 and 2 were tested for heat resistance, with specific reference to the composite sheet test section in GBT 18173.1-2012 "Polymer Waterproof Materials Part 1: Sheet Materials". The final test results are shown in Table 2.

[0058] Table 2 Test results of temperature resistance of waterproof membrane

[0059]

[0060] The waterproof roll prepared by the waterproof material prepared by Examples 1-10 of the present invention has a tensile strength of 67.8-74.0 N / cm and 31.1-37.6 N / cm at 23°C and 60°C, respectively, and a tensile elongation at break of 450%-540% and 370%-430% at 23°C and -20°C, respectively, as shown in Table 2. By using TPO, alkenyl methyl siloxane, dithiol and benzoin dimethyl ether as starting reaction raw materials, wherein the sulfur atom in the dithiol simultaneously performs nucleophilic attack on the carbon atom of the vinyl group and the carbon atom on the unsaturated double bond in the alkenyl methyl siloxane, and forms a thioether bond, and benzoin dimethyl ether, as a compound containing a benzene ring and an ether group, cross-links with the thioether bond to promote the formation of the thioether bond and the cross-linking structure, and then promotes the generation of free radicals under the action of potassium persulfate composite salt, thereby obtaining a raw material for a waterproof layer containing a polysulfone polysilane structure and TPO cross-linking, in which the polysulfone and siloxane structures are alternately connected. In Examples 1-3, the type of alkenylmethylsiloxane was changed, and the waterproofing membrane obtained by Example 3 using 1,7-divinyl-octamethyltetrasiloxane had the highest tensile strength and elongation at break at different temperatures. As the amount of silicon atoms introduced increased, the proportion of methylsiloxane structure in the raw material of the waterproof layer increased, the tensile strength decrease value at 60°C was low, and the elongation at break was high at -20°C. The results of Examples 3 and 4 show that the temperature resistance decreases when the amount of alkenylmethylsiloxane is reduced. The results of Examples 3, 5 and 6 show that by changing the type and amount of dithiols, the sulfur in the dithiols eventually forms a sulfide structure. Example 3 uses 1,2-benzenedithiol with high tensile strength and elongation at break at 230°C, high tensile strength at 60°C, and the alternating benzene ring structure improves the temperature resistance of the waterproofing membrane. The results of Examples 3 and 7 show that increasing the amount of 1,2-benzenedithiol increases the tensile strength at 60°C, and the elongation at break at -20°C decreases. As the polysulfone and benzene ring structures formed increase, the heat resistance effect increases, but the brittleness at low temperatures also increases. The results of Examples 7-10 show that the heat resistance effect is improved by reasonably adjusting the amount of waterproof layer precursor, THF, potassium persulfate composite salt and deionized water; the heat resistance effect is further improved by mixing the waterproof layer raw material with modified high-density polyethylene in a suitable proportion. Comparative Examples 1 and 2 do not add modified high-density polyethylene and waterproof layer raw material, respectively, and the tensile strength and break productivity are lower than those of the examples, and the heat resistance performance is reduced.

[0061] Examples 12-20

[0062] Different from Example 9, the following preparation conditions are changed, as shown in Table 3.

[0063] Table 3 Preparation conditions of waterproof outer layer materials

[0064]

[0065] Comparative Example 3

[0066] Different from Example 9, the alkalinity of the alkaline hollow glass microspheres is 0.2 equivalent / g.

[0067] Comparative Example 4

[0068] Different from Example 9, KH550 was not added.

[0069] Comparative Example 5

[0070] Different from Example 9, no anti-aging agent was added.

[0071] Comparative Example 6

[0072] Different from Example 9, no aromatic oil was added.

[0073] Comparative Example 7

[0074] Different from Example 9, no PP wax was added.

[0075] Embodiment 21

[0076] The waterproof outer layer materials of Examples 12-20 and Comparative Examples 3-6 were used to prepare waterproof rolls, and the temperature resistance performance was tested. The specific preparation method and test method were carried out with reference to Example 11, and the final test results are shown in Tables 4 and Figure 2 shown.

[0077] Table 4 Elongation at break test results of Example 9, Examples 12-20 and Comparative Examples 3-7

[0078]

[0079] The waterproof outer layer raw materials prepared from Examples 9, 12-20 and Comparative Examples 3-7 of the present invention are further used to prepare waterproof rolls, such as Figure 2As shown in Table 4, the tensile strength at 23°C and 60°C is 71.9-74.8N / cm and 35.1-38.5N / cm, respectively. As shown in Table 4, the elongation at break at 23°C and -20°C is 490%-550% and 390%-450%, respectively. The results of Examples 9, 12-14 show that as the alkalinity of the alkaline hollow glass microspheres increases, the tensile strength at 23°C and 60°C gradually increases, and the elongation at break at 23°C and -20°C also shows a trend of gradually increasing. This is because the alkalinity increases, the content of reactive hydroxyl groups in the system increases, and the hydroxyl groups react with the introduced maleic anhydride and KH550 on the one hand, and esterify with maleic anhydride in polyethylene on the other hand, thereby improving the crosslinking degree of the system; the results of Comparative Example 3 show that when the alkalinity is low, the tensile strength and elongation at break at 23°C are not significantly changed compared with Example 9, but the performance at 60°C and -20°C is reduced. The results of Examples 12, 15 and 16 show that the hollow glass spheres are modified by introducing KH550, and the heat resistance gradually improves as its dosage increases. The results of Examples 16-18 show that as the temperature of the melt mixing increases, the tensile strength at 60°C and the elongation at break at -20°C both show a trend of first decreasing and then increasing. At the same time, the results of Comparative Example 4 further prove that the introduction of KH550 into the hollow glass microspheres has the effect of improving the heat resistance of the waterproof roll; controlling the temperature within a lower range has a protective effect on the raw materials of the material. The results of Examples 18-20 show that the dosage ratio of the anti-aging agent, antioxidant, aromatic oil, PP wax and leveling agent is adjusted, wherein the aromatic oil plays a role in plasticizing the waterproof roll and improving the ductility of the roll, and the use of the leveling agent improves the consistency of the raw material mixing; the PP wax mainly plays a role in improving the thermal stability of the roll, the anti-aging agent and antioxidant improve the stability of the roll in use, and the coordinated use of multiple substances further improves the heat resistance of the waterproof roll. The results of Comparative Examples 5-7 show that without adding antioxidants, aromatic oils or PP wax, the tensile strength and elongation at break at 23°C do not decrease significantly, but the tensile strength at 60°C and the elongation at break at -20°C are both lower than those in Example 9.

[0080] Examples 22-29

[0081] Different from Example 19, the dosage of nanofiltration raw material 1 and nanofiltration raw material 2 is changed, as shown in Table 5.

[0082] p-phenylenediamine, triethylamine, organic mixed acid and deionized water are mixed to obtain nanofiltration raw material 1, wherein the mass percentage of p-phenylenediamine is 3.2%, the mass percentage of triethylamine is 1.7%, and the mass percentage of organic mixed acid is 3.9%. Trimethylolyl chloride and 1-hexene are mixed to obtain nanofiltration raw material 2, wherein the mass percentage of trimethylolyl chloride is 5.5%.

[0083] The nanocellulose and triethylamine are dissolved in deionized water to obtain a post-treatment solution, wherein the mass percentage of the nanocellulose is 2% and the mass percentage of the triethylamine is 1.7%.

[0084] Comparative Example 8

[0085] Different from Example 19, only fumaric acid was added.

[0086] Comparative Example 9

[0087] Different from Example 19, only polyacrylic acid was added.

[0088] Comparative Example 10

[0089] In contrast to Example 19, only polystyrene sulfonic acid was added.

[0090] Comparative Example 11

[0091] Different from Example 19, no nanocellulose was added.

[0092] Embodiment 30

[0093] The nanofiltration raw material 1, nanofiltration raw material 2 and post-treatment liquid obtained in Examples 19, 22-29 and Comparative Examples 8-11 were used to treat waterproof rolls, and the waterproof performance of the obtained waterproof rolls was tested. The waterproof performance test was carried out with reference to the physical properties of the composite sheet in GB T 18173.1-2012 "Polymer Waterproof Materials Part 1: Sheets", and the final test results are shown in Table 5.

[0094] Table 5 Changes in the amount of nanofiltration raw material 1, nanofiltration raw material 2 and nanocellulose

[0095]

[0096] The results in Table 5 show that the waterproof roll prepared by the present invention has an effective time of 60-120 minutes for the first waterproof outer layer to block water. After the waterproof outer layer is treated with nanofiltration raw material 1, the amino group in the p-phenylenediamine structure is connected with the maleic anhydride in the waterproof outer layer raw material, thereby being closely combined with the waterproof outer layer, and some organic acids react with the amino groups of p-phenylenediamine, and then nanofiltration raw material 2 is added, and trimeryl chloride is reacted with the unreacted amino group in p-phenylenediamine to obtain a polyamide structure, and the hydroxyl group of the nanocellulose in the post-treatment liquid replaces the chlorine element. The triethylamine added therein plays a role in neutralizing the pH of the system, and 1-hexene can cross-link with the permeable structure or react with the unsaturated double bonds in the TPO or high-density polyethylene in the waterproof outer layer raw material, thereby improving the percolation effect on water and the strength of the nanofiltration structure, and the cross-linked nanocellulose crystals have a certain absorption and storage effect on water.

[0097] In Examples 19, 22 and 23, as the mass percentage of p-phenylenediamine in the nanofiltration raw material 1 increases, the 0.3MPa single layer water permeability discoloration time gradually increases. This is because the benzene ring structure introduced therein improves the mechanical strength of the nanofiltration structure membrane layer, thereby increasing the waterproof time. The results of Examples 23-25 ​​show that the type of organic mixed acid is adjusted, and the discoloration time under the conditions of Example 24 is the longest. After the polystyrene sulfonic acid reacts, the permeability of the membrane to water is reduced, the water flux of the membrane is improved, and the waterproof effect is the best. The results of Examples 24 and 26 show that by adjusting the dosage ratio of the organic mixed acid, the time for water permeability to discolor is increased; the mixed use of organic acids synergistically improves the waterproof effect. In Comparative Examples 8-10, only one organic acid is added, and the time for discoloration to appear is shortened. The results of Examples 26-28 show that as the mass percentage of trimerephthaloyl chloride increases, the time for discoloration to occur increases first and then decreases. By controlling the dosage within the range shown in the examples, the water impact strength of the nanofiltration structure is improved, and the process of the reaction between nanocellulose and trimerephthaloyl chloride is also increased. The time for discoloration to occur increases, and the waterproof performance is improved. The results of Examples 28 and 29 show that the waterproof performance is good when the content of nanocellulose is adjusted; in Comparative Example 11, nanocellulose is not added, and the waterproof effect decreases. By introducing a nanofiltration structure into the waterproof coiled material, the waterproof performance of the waterproof coiled material is improved.

[0098] Examples 31-43

[0099] Different from Example 29, the preparation method of the raw materials of the microcapsule layer and the amount of alkenylmethylsiloxane in the waterproof layer are changed, as shown in Table 6. The four substances in Table 6 are MDI, quicklime, anhydrous ferrous sulfate and diethylenetriamine.

[0100] Table 6 Preparation method of microcapsule layer raw materials and amount of alkenylmethylsiloxane used

[0101]

[0102] Comparative Example 12

[0103] Different from Example 29, no microcapsule layer raw material was added.

[0104] Embodiment 44

[0105] The microcapsule layer raw materials, waterproof outer layer raw materials and other components prepared in Examples 29, 31-43 and Comparative Example 12 were used to prepare waterproof coiled materials, and the obtained waterproof coiled materials were tested for waterproof performance, wherein the test of single-layer water permeability time was carried out with reference to Example 30, and the test of watertightness time was carried out with reference to the physical properties of composite sheets in GB T 18173.1-2012 "Polymer Waterproof Materials Part 1: Sheets", and the final test results are shown in Table 7.

[0106] Table 7 Waterproof test results of waterproof membranes obtained in Examples 29, 31-45 and Comparative Example 12

[0107]

[0108] The waterproof coiled material prepared by the present invention has a color change time of 115-155 minutes for a single layer of 0.3MPa waterproof coiled material, and a water permeability time of 130-185 minutes for a 0.3Mpa waterproof coiled material. On the one hand, MDI forms a solidified urea-based compound when it meets water, and releases a large amount of heat at the same time; on the other hand, anhydrous ferrous sulfate plays a role of indicating color in the waterproof coiled material, and turns light green when it meets water (color observation is performed after the section is cut), and the water resistance effect of its waterproof outer layer can be directly reflected by the color change; on the other hand, quicklime releases heat when it meets water, and under the action of diethylenetriamine, MDI reacts with the hydroxyl group or part of the hydroxyl cage silane of the nanocellulose in the nanofiltration structure to form a compound containing an amide structure, and the cross-linked substance formed by the curing of the microcapsule layer forms a new protective layer again; the molar ratio of polylactic acid and glycolic acid is adjusted, and in the process of heating and pressing the waterproof coiled material, the free carboxyl group reacts with the hydroxyl group of the hydroxyl cage silane to esterify, thereby introducing a strong waterproof compound into the microcapsule layer. The results of Examples 29, 31 and 32 show that with the increase in the amount of alkenylmethylsiloxane, the time for the monolayer to change color after water permeability increases first and then decreases, and the water permeability time of the waterproof roll tends to remain unchanged after the increase. The adjustment of alkenylmethylsiloxane in the waterproof outer layer has an increasing effect on the waterproof effect of the outer layer, but excessive dosage leads to increased flexibility and reduced water pressure resistance. The water permeability time of the waterproof roll is related to the waterproof effect of the nanofiltration composite layer, microcapsule layer, waterproof inner layer and adhesive layer, so the waterproof time tends to remain unchanged. The results of Examples 31, 33 and 34 show that by reasonably adjusting the amount of MDI and quicklime in the four substances, the waterproof effect is improved. The results of Examples 34-36 show that by reasonably adjusting the amount of anhydrous ferrous sulfate and diethylenetriamine, the color development effect of ferrous sulfate under the conditions of Example 34 is the best, and the waterproof effect is also the best. The results of Examples 34, 37 and 38 show that by adjusting the molar ratio of polylactic acid and glycolic acid, glycolic acid and hydroxyl cage-shaped silane react more completely, thereby increasing the time for discoloration of the monolayer permeability and the water permeability time of the waterproof roll. The results of Examples 38 and 39 show that the waterproof effect increases with the increase in the amount of hydroxyl cage-shaped silane. The results of Examples 39-41 show that with the increase in the reaction temperature, the waterproof effect first increases and then decreases, and the waterproof effect under the conditions of Example 40 is the best. The results of Examples 40, 42 and 43 show that the waterproof effect is best when the average particle size of the raw material of the microcapsule layer of Example 40 is 450nm. This is because water enters the microcapsule layer through the nanofiltration composite layer, and the average particle size of the raw material of the microcapsule layer is too low, then the water absorption effect increases, and the particle size is too high, which is not conducive to the improvement of the waterproof effect. After water enters the microcapsule layer through the nanofiltration composite layer, the components undergo cross-linking reactions to form a new cured protective layer. Comparative Example 12 does not add microcapsule layer raw materials. Compared with the comparative example, the discoloration time of the 0.3MPa single-layer water permeability and the water permeability time of the 0.3Mpa waterproof membrane are reduced.

[0109] Examples 45-52

[0110] Different from Example 40, the preparation method of the adhesive layer raw material is changed, as shown in Table 8.

[0111] Table 8 Preparation method of adhesive layer raw materials

[0112]

[0113] Embodiment 53

[0114] The waterproof membranes obtained in Examples 40 and 45-52 were tested for waterproof performance. The waterproof membranes were adhered to the surface of uncured concrete and tested for water impermeability under a water pressure of 0.3 MPa after covering for 72 hours. The examples were adhered to uncured concrete and cured for 72 hours, then immersed in water, and the 180° peel strength was tested after immersion for 48 hours. The final test results are shown in Table 8.

[0115] The peel strength of the waterproof roll prepared by the present invention after immersion in water is 2.5-4.0 N / mm. The unsaturated double bonds in methyl methacrylate, ethyl acrylate, tripropylene glycol diacrylate, diacetone acrylamide and 2,2,3,3,4,4,4-heptafluorobutyl acrylate are polymerized, and the introduced fluorine atoms improve the waterproof effect of the waterproof material; the diacetyl adipic acid dihydrazide added thereafter is cross-linked and polymerized again with the components in the polymerization liquid, and the added acid reacts with the unreacted amino groups in the diacetyl adipic acid dihydrazide, and partially reacts with the hydroxyl groups of the hydroxy cage silane for esterification, thereby improving the waterproof effect. The results of Examples 40, 45 and 46 show that the waterproof roll has the best waterproof effect under the conditions of Example 46, which is due to the increase in the introduced fluorine atoms and the increase in the resistance to water. The results of Examples 46-48 show that the waterproof effect is best when the amount of diacetyl adipic acid dihydrazide is controlled within a reasonable range. The results of Examples 47, 49 and 50 show that the peel strength is the highest when oxalic acid is used for the reaction, because oxalic acid has the strongest binding force with the substances in cement, so it is not easy to peel off; while when citric acid is used, the hydroxyl groups at both ends of its molecule connect diacetyl adipic acid dihydrazide with hydroxy cage silane. The results of Examples 49, 51 and 52 show that as the amount of hydroxy cage silane used increases, the water-blocking effect of the waterproofing membrane is enhanced.

[0116] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A waterproof material for waterproof coiled material, characterized in that: The waterproof material for the waterproof coiled material comprises: waterproof outer layer raw material, nanofiltration composite layer raw material, microcapsule layer raw material, waterproof inner layer raw material, polymer layer raw material and adhesive layer raw material; The preparation method of the waterproof outer layer material is as follows: 10 parts of alkaline hollow glass microspheres and 10 parts of 5% maleic anhydride aqueous solution are mixed, and stirred at 50° C. for 15 minutes to obtain maleic anhydride grafted hollow glass microspheres; KH550, 0.1 parts of EDC and 0.1 parts of Tween 80 are added to the maleic anhydride grafted hollow glass microspheres, and the stirring reaction is continued for 1.5 hours to obtain silane-maleic anhydride-hollow glass microspheres; then 90 parts of the Maleic anhydride is grafted onto high-density polyethylene, the temperature is raised to 120-135° C., and the reaction is stirred for 30 minutes under nitrogen protection to obtain modified high-density polyethylene; the modified high-density polyethylene, a raw material for a waterproof layer, an anti-aging agent, an antioxidant, an aromatic oil, PP wax and a leveling agent are mixed in a ratio of 1-11: 1-8: 0.5-0.8: 0.2-0.4: 1.5-2.5: 1-1.5: 0.1-0.3 to obtain the raw material for the waterproof outer layer; The preparation method of the raw material of the waterproof layer is as follows: after mixing 30 parts of polyethylene TPO, 9.3-15.8 parts of alkenyl methyl siloxane, 6.0-8.0 parts of dithiol and 1.3 parts of benzoin dimethyl ether by mass, heating and curing by ultraviolet irradiation to obtain a precursor of the waterproof layer; after mixing the precursor of the waterproof layer, THF and potassium persulfate composite salt and deionized water in a mass ratio of 1:6:6-7:2-4, the temperature is increased to 60°C, and stirred for reaction for 10 hours under nitrogen protection to obtain a waterproof layer intermediate; then 5 parts of the potassium persulfate composite salt, 20 parts of the deionized water and 20 parts of the THF are added, the reaction is continued for 12 hours, and then extracted with dichloromethane, washed with the deionized water and rotary evaporated to obtain the raw material of the waterproof layer; The nanofiltration composite layer raw material is prepared from a nanofiltration raw material 1, a nanofiltration raw material 2 and a post-treatment liquid; the nanofiltration raw material 1 is obtained by mixing p-phenylenediamine, triethylamine, an organic mixed acid and the deionized water; the mass percentage of the p-phenylenediamine in the nanofiltration raw material 1 is 3.0%-3.8%; the nanofiltration raw material 2 is obtained by mixing terephthaloyl chloride and 1-hexene; the mass percentage of terephthaloyl chloride in the nanofiltration raw material 2 is 5.5%-9.3%; the post-treatment liquid is obtained by mixing nanocellulose, triethylamine and deionized water; the mass percentage of the nanocellulose is 2.0%-3.5%; The organic mixed acid comprises an organic mixed acid 1 and an organic mixed acid 2; the organic mixed acid 1 is one of fumaric acid and polyacrylic acid; the organic mixed acid 2 is one of polyacrylic acid and polystyrene sulfonic acid; the mass mixing ratio of the organic mixed acid 1 to the organic mixed acid 2 is 1:1-3; The preparation method of the microcapsule layer raw material is as follows: 50 parts of polylactic acid-glycolic acid copolymer and 7.5-10 parts of hydroxy cage silane are mixed, the temperature is raised to 120-150° C., and the mixture is added dropwise to the capsule shell material in a molten state; the microcapsule layer raw material having an average particle size of 280nm-600nm is obtained by grinding; the molar ratio of polylactic acid to glycolic acid in the polylactic acid-glycolic acid copolymer is 1-4:1-2; The preparation method of the adhesive layer raw material is as follows: 7.0 parts of methyl methacrylate, 7.0 parts of ethyl acrylate, 21.0 parts of tripropylene glycol diacrylate, 11.9 parts of diacetone acrylamide, 17.8 parts of fluorine-based acrylate, 0.5 parts of alkylphenol polyoxyethylene ether, 18.0 parts of the deionized water, 0.4 parts of sodium bicarbonate and 0.8 parts of ammonium persulfate are uniformly mixed to obtain a liquid to be polymerized; the liquid to be polymerized is heated to 70°C, stirred for reaction for 30 minutes, then heated to 80°C, reacted for 1 hour, then cooled to 60°C and kept warm for 2.5 hours to obtain a polymerized liquid; the polymerized liquid is adjusted to pH 9.0, diacetyl adipic acid dihydrazide is added, reacted at 80°C for 10 minutes, then the acid raw material, the hydroxy cage silane and 0.5 parts of phosphoric acid are added thereto, reacted for 3 hours, and then dried to obtain the adhesive layer raw material.

2. The waterproof material for waterproof coiled material according to claim 1, characterized in that: The alkenylmethylsiloxane is one of 1,7-divinyl-octamethyltetrasiloxane, tetramethyldivinyldisiloxane and 1,5-divinyl-hexamethyltrisiloxane; the dithiol is one of 1,4-butanedithiol, 1,5-pentanedithiol and 1,2-benzenedithiol.

3. The waterproof material for waterproof roll material according to claim 1, characterized in that: The preparation method of the alkaline hollow glass microspheres is as follows: hollow glass microspheres and stearic acid are mixed at a mass ratio of 50:1 to obtain 10 parts of a hollow glass microsphere mixture; then a sodium hydroxide aqueous solution with a mass fraction of 10% is added to the hollow glass microsphere mixture, and the alkaline hollow glass microspheres are obtained after grinding and drying; the alkalinity of the alkaline hollow glass microspheres is 0.2-1.2 equivalents / gram; and the average particle size of the alkaline hollow glass microspheres is 37µm.

4. The waterproof material for waterproof coiled material according to claim 1, characterized in that: The preparation method of the waterproof outer layer raw material is as follows: after mixing the polyethylene TPO, 14.5-15.8 parts of the alkenyl methyl siloxane, 6.8-8.0 parts of the dithiol and the benzoin dimethyl ether, the temperature is raised to 180° C., and a homogeneous phase is obtained after melting; 10 parts of the homogeneous phase are stirred and reacted under 100W ultraviolet light with a wavelength of 365nm for 10 minutes, then cooled to room temperature, dissolved with 80 parts of THF, and precipitated with 300 parts of methanol again, and the first precursor of the waterproof layer is obtained after removing the methanol; The modified high-density polyethylene, the first raw material of the waterproof layer, the anti-aging agent, the antioxidant, the aromatic oil, the PP wax and the leveling agent are mixed at 135° C. for 10 minutes to obtain the raw material of the waterproof outer layer; the alkalinity of the alkaline hollow glass microspheres is 0.4-1.2 equivalents / gram; The anti-aging agent is obtained by mixing phenylbenzotriazole and 1,2,3,4-tetrahydroquinoline in a ratio of 1:1; the antioxidant is BHT; the aromatic oil is Aromatic 200; and the leveling agent is an organic silicon leveling agent.

5. The waterproof material for waterproof coiled material according to claim 1, characterized in that: The preparation method of the microcapsule layer raw material is as follows: MDI and quicklime, anhydrous ferrous sulfate and diethylenetriamine are mixed in a mass ratio of 10-18:32-40:10-14:1-5, and the mixture is ball-milled in a ball mill at 30°C for 2 hours, and the mixture is cooled to room temperature to obtain the capsule shell material with a particle size of 100nm; the polylactic acid-glycolic acid copolymer, methanol and the hydroxyl cage silane are mixed, and then the temperature is increased to 120-130°C, and the mixture is stirred and melted to obtain a polylactic acid-glycolic acid copolymer melt; in a molten state at 120°C, 75 parts of the polylactic acid-glycolic acid copolymer melt are added dropwise to 25 parts of the capsule shell material, and the mixture is stirred at 1000rpm, and then dried, cooled and solidified to obtain the microcapsule layer raw material with an average particle size of 280nm-450nm.

6. The waterproof material for waterproof coiled material according to claim 1, characterized in that: The fluorine-based acrylate is one of 2,2,3,3,4,4,4-heptafluorobutyl acrylate, hexafluorobutyl acrylate and 1H,1H-perfluorooctyl acrylate; the acid raw material is one of citric acid, oxalic acid and boric acid.

7. The waterproof material for waterproof coiled material according to claim 1, characterized in that: The waterproof coiled material is prepared from the waterproof material; the structure of the waterproof coiled material from top to bottom is a waterproof outer layer (1), a nanofiltration composite layer (2), a microcapsule layer (3), a waterproof inner layer (4), a polymer layer (5) and an adhesive layer (6).

8. The waterproof material for waterproof roll material according to claim 7, characterized in that: The preparation method of the nanofiltration composite layer (2) is as follows: the waterproof outer layer raw material is melt-extruded at 150°C to obtain a sheet, the surface of the sheet is immersed in the solution of the nanofiltration raw material one, and after soaking for 1 minute, it is purged with nitrogen to make the surface free of obvious droplets, and then the solution of the nanofiltration raw material two is poured on the surface of the above material, and after soaking for 1 minute, it is purged with nitrogen again, and then treated at 80°C for 8 minutes to obtain a sheet and a nanofiltration composite layer precursor; the post-treatment liquid is coated on a single surface of the nanofiltration composite layer precursor, and then vacuum dried at 60°C to obtain the nanofiltration composite layer (2).

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