Polymer waterproof coiled material and preparation method thereof

Abstract

The invention relates to the technical field of waterproof coiled materials, in particular to a macromolecular waterproof coiled material and a preparation method thereof. The waterproof roll structurally comprises the release film, the waterproof layer, the polymer layer, the aggregate layer, the polymer layer, the waterproof layer and the release film in sequence from outside to inside, and the problems that a waterproof roll is poor in waterproof effect and poor in aging resistance are solved. The polymer waterproof roll mainly comprises a release film, a waterproof layer, a polymer layer and an aggregate layer. The reaction temperature and time are adjusted by adjusting the types of cyclic siloxane in the aggregate layer and the waterproof layer; the synthetic plasticizer is added into the polymer layer; synthesizing polyarylsulfone, and adding the polyarylsulfone into the high-molecular waterproof coiled material, the component proportion of the raw materials of the polymer layer is changed; finally, bentonite is modified, and the modified bentonite is used in the waterproof layer. The prepared high-molecular waterproof coiled material is good in waterproof effect and high in peel strength after thermal aging.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to a polymer waterproof membrane and its preparation method. Background Technology

[0002] Waterproof membranes play a crucial role in building construction, and the choice of waterproof membrane material largely determines the quality of construction and the lifespan of the building. Based on the raw materials used, waterproof membranes are divided into bitumen waterproof membranes and polymer waterproof membranes.

[0003] The use of bitumen waterproof membranes has a long history. One example is Rupal A, Sharma KS, Tyagi G. "Experimental investigation on mechanical properties of polyurethane modified bituminous waterproofing membrane[J]. Materials Today: Proceedings, 2020, 27(Pt 1):467-474." This invention improves the mechanical properties of bitumen materials by adding polyurethane; however, the bitumen waterproof membrane produced by this invention mainly uses petroleum-based raw materials, which is not conducive to resource conservation. Polymer waterproof membranes can be divided into polyvinyl chloride (PVC) waterproof membranes, thermoplastic polyolefin (TPE) waterproof membranes, EPDM rubber (EPDM) waterproof membranes, and high-density polyethylene (HDPE) waterproof membranes. PVC waterproof membranes have good impermeability and good chemical stability; however, the chlorine they contain easily escapes at high temperatures, and the resulting chlorine gas is harmful to the human body. Thermoplastic polyolefin (TPE) waterproof membranes have small shrinkage and deformation, but poor flame retardant effect. EPDM rubber waterproof membranes have good heat resistance, but with increased usage time, the added plasticizers migrate, and the molecules are prone to cross-linking and degradation, leading to a decline in their mechanical properties. High-density polyethylene waterproof membranes have a regular molecular structure and high density; however, they suffer from poor aging resistance.

[0004] Polymer waterproof membranes mainly consist of a waterproof membrane base layer and an adhesive layer, achieving a waterproof effect. Patent CN110872409A discloses a TPO waterproof membrane, which improves the material's reversible deformation and waterproofing effect by adding TPO particles, rubber granules, light calcium carbonate, stearic acid, titanium dioxide, and plasticizers; however, its heat aging resistance is poor. Patent CN109910414B discloses a polymer waterproof membrane and its manufacturing process. The polymer waterproof membrane, from the outside in, consists of an outer waterproof layer, a base layer, a release film layer, and a polymer polyester inner layer. Using ethylene-vinyl acetate copolymer as the base material, its thermal insulation is improved after compatibility with stabilizers, heavy calcium powder, antistatic agents, and antioxidant graphene. The addition of carbon nanotubes to encapsulate calcium-zinc stabilizers further enhances the membrane's heat resistance. Waterproof membranes are used in building construction to resist rainwater or groundwater seepage and are easy to install; however, as the service life increases, the molecular structure is damaged and the waterproof effect decreases.

[0005] In summary, existing technologies still suffer from poor waterproofing performance and poor aging resistance of polymer waterproof membranes.

[0006] To address this, a polymer waterproof membrane and its preparation method are proposed. Summary of the Invention

[0007] The purpose of this invention is to provide a polymer waterproof membrane and its preparation method. The polymer waterproof membrane structure, from the outside to the inside, consists of a release film, a waterproof layer, a polymer layer, an aggregate layer, another polymer layer, a waterproof layer, and a release film. The method involves adjusting the types of siloxanes in the aggregate layer and the waterproof layer, changing the amount of hydroxyl-terminated polydimethylsiloxane, and adjusting the reaction temperature and time. A synthesized plasticizer is added to the polymer layer, using linoleic acid as the starting material and adding itaconic anhydride, 1,3,5-tris(4-hydroxyphenyl)benzene, and diethylphosphorylethyltriethoxysilane to obtain a plasticizer with good compatibility with the polymer layer raw materials. Polyarylsulfone is also synthesized, with variations in the types and amounts of synthetic raw materials, and added to the polymer waterproof membrane. The composition ratio of the polymer layer raw materials is also modified. Finally, bentonite is modified by screening its expansion index and adding modified nanocellulose and KH550 to obtain modified bentonite, which is then used in the waterproof layer. The resulting polymer waterproof membrane has good waterproof performance and high peel strength after heat aging.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] This invention provides a method for preparing a polymer waterproof membrane, the method of which is as follows:

[0010] A cyclic siloxane was ring-opened for 2-7.5 h to obtain a hydroxyl-terminated polydimethylsiloxane; 2-3.1 parts of 2-sulfonic acid terephthalic acid, 1.5-4.0 parts of the hydroxyl-terminated polydimethylsiloxane, and 1.4-1.9 parts of biphenyl were mixed and reacted to obtain the reactant; 3.5-4.0 parts of hydroxyfluorene and 5.2-8.7 parts of 4,4'-difluorodiphenyl sulfone were dissolved in sulfolane to obtain a mixed solution; the mixed solution and 2.8-5 parts of dimethyl sulfoxide were added to the reactant, the organic solvent was removed after the reaction, and the temperature was raised to 180-250℃ to obtain the product;

[0011] Modified polyethylene is obtained by melting and mixing high-density polyethylene, linear low-density polyethylene, 4-5 parts of bisphenol A epoxy resin and 1.5-2.5 parts of 4,4'-diaminodiphenyl sulfone.

[0012] The product and modified polyethylene were mixed in a ratio of 4-9:1-3 to obtain the aggregate layer;

[0013] Modified polyethylene, EPDM rubber and thermoplastic polyolefin are melt-mixed in a ratio of 5-7:2-4:1-2, hydroxide and plasticizer are added, and after stirring, the mixture is extruded to obtain a polymer layer.

[0014] The product is melted, extruded, and then immersed in an acrylic acid solution containing 0.1-0.3 parts of 1-hydroxycyclohexanebenzophenone. It is then irradiated with ultraviolet light to obtain a waterproof layer intermediate. 1.5-3 parts of modified bentonite are coated on one side of the waterproof layer intermediate, and the mixture is then hot-pressed to obtain a waterproof layer.

[0015] The release membrane, waterproof layer, polymer layer, aggregate layer, and release membrane are stacked and hot-pressed, then cut and rolled up to obtain a polymer waterproof membrane.

[0016] Preferably, the ring-opening reaction is as follows: cyclic siloxane is added to a three-necked flask and the temperature is raised; preheated potassium hydroxide aqueous solution is added to the cyclic siloxane, and the mixture is stirred and reacted for 5-7.5 h to obtain a hydroxyl-terminated polydimethylsiloxane solution; anhydrous sodium sulfate is added to the hydroxyl-terminated polydimethylsiloxane solution to remove water, and the filtered liquid is dried under vacuum to obtain hydroxyl-terminated polydimethylsiloxane; the cyclic siloxane is one of octamethylcyclotetrasiloxane, dodecylcyclohexasiloxane, hexadecylcyclooctasiloxane, octadecylcyclononasiloxane, icosylcyclodecasiloxane, and tetradecylcyclododecylsiloxane.

[0017] Preferably, the preparation method of the product is as follows: 2-sulfonic acid terephthalic acid is added to hydroxyl-terminated polydimethylsiloxane, sulfolane is added to it, and after uniform dissolution, phosphoric acid is added, and the temperature is raised. The reaction is stirred in a reactor to obtain the precursor of the reactant; biphenyl is added to the precursor of the reactant, sulfolane is added, and the reaction is continued to be stirred to obtain the reactant; hydroxyfluorene and 4,4'-difluorodiphenyl sulfone are dissolved in sulfolane to obtain a mixed solution; the mixed solution and dimethyl sulfoxide are added to the reactant, and the reaction is continued to be stirred to obtain the reactant; hydroxyfluorene and 4,4'-difluorodiphenyl sulfone are dissolved in sulfolane to obtain a mixed solution; the mixed solution and dimethyl sulfoxide are added to the reactant, and the reaction is continued to be stirred in a reactor to obtain the reactant. Nitrogen gas was introduced into the reactor, and after the air was purged, the temperature of the reactor was raised and the reaction was stirred to obtain the product precursor. After removing the organic solvent from the product precursor, the temperature was raised to 180-210℃, and after the reaction, the temperature was lowered to obtain the product intermediate. The product intermediate was added to deionized water to obtain a fibrous white precipitate. The fibrous white precipitate was crushed and washed repeatedly with water and anhydrous ethanol, and then dried under vacuum to obtain the product. The hydroxyfluorene is one of bisphenol fluorene, dihydroxyfluorene, and 2,7-dihydroxy-9,9-dimethylfluorene.

[0018] Preferably, the preparation method of the aggregate layer is as follows: high-density polyethylene and linear low-density polyethylene are melted in a reactor, and then bisphenol A epoxy resin, itaconic anhydride and 4,4'-diaminodiphenyl sulfone are added to it. After melting and mixing, a mixture is obtained. 2,2'-azobisisobutyronitrile and boron trifluoride complex are added to the mixture, and after stirring and reacting, concentrated sulfuric acid is added to it. The reaction is continued, and after cooling to room temperature, modified polyethylene is obtained.

[0019] The product and modified polyethylene are mixed to obtain a spinning raw material; the spinning raw material is dissolved in DMF and stirred to obtain a spinning solution; the spinning solution is electrospun, woven, and dried to obtain an aggregate layer.

[0020] Preferably, the preparation method of the polymer layer is as follows: modified polyethylene, EPDM rubber and thermoplastic polyolefin are mixed in a ratio of 5-7:2-4:1-2, and then co-melted and mixed evenly to obtain a polymer layer precursor; the polymer layer precursor and hydroxide are mixed and stirred to obtain a polymer layer intermediate; a plasticizer is added to the polymer layer intermediate, stirring is continued, and then the polymer layer is extruded.

[0021] Preferably, the hydroxide is two of aluminum hydroxide, magnesium hydroxide, and tungsten hydroxide.

[0022] Preferably, the preparation method of the plasticizer is as follows: 2.0-2.8 parts of linoleic acid and toluene are placed in a four-necked round-bottom flask equipped with a Dean-Stark water separator. The temperature is raised, and a phosphotungsten heteropoly acid quaternary ammonium salt catalyst and an aqueous solution of hydrogen peroxide are added. The mixture is refluxed until the epoxy value no longer changes, yielding a plasticizer precursor. 0.5-1.5 parts of 1,3,5-tris(4-hydroxyphenyl)benzene are dissolved in toluene to obtain a 1,3,5-tris(4-hydroxyphenyl)benzene solution. 0.3-0.5 parts of itaconic anhydride and phosphoric acid are added to the plasticizer precursor, followed by the 1,3,5-tris(4-hydroxyphenyl)benzene solution. The temperature is raised and the mixture is refluxed. Phosphoric acid and 1.0-4.0 parts of diethylphosphonylethyltriethoxysilane are then added, and the mixture is refluxed again. During this process, water generated is removed through a Dean-Stark water separator, and then toluene is removed to obtain the plasticizer.

[0023] The preferred method for preparing modified bentonite is as follows: First, the bentonite is dried in a vacuum drying oven. Then, the bentonite and 2-2.5 parts of nano zinc oxide are mixed evenly with deionized water to obtain a mixture. Nanocellulose crystals and glycine are dispersed in deionized water, then concentrated sulfuric acid is added, the temperature is raised, the mixture is stirred and reacted, filtered and dried to obtain modified nanocellulose. 0.3-0.5 parts of modified nanocellulose are added to the mixture, the temperature is raised, and the mixture is ball-milled using a star ball mill and dried. Then, 1.5-3.6 parts of KH550 are added, and the mixture is ball-milled again to obtain modified bentonite.

[0024] Preferably, the bentonite is one of calcium-based bentonite and sodium-based bentonite; the swelling index of the bentonite is 7.0-31.4 mL / 2g.

[0025] On the other hand, the present invention provides a polymer waterproof membrane, the structure of which, from the outside to the inside, consists of a release film, a waterproof layer, a polymer layer, an aggregate layer, a polymer layer, a waterproof layer, and a release film; the polymer waterproof membrane is prepared by any of the above preparation methods.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] 1. By adjusting the types of raw materials used to synthesize hydroxyl-terminated polydimethylsiloxane and changing the hydrolysis time of the siloxane, the resulting hydroxyl-terminated polydimethylsiloxane reacts with the functional group of 2-sulfonic acid terephthalic acid through chemical bonds. By changing the amount of hydroxyl-terminated polydimethylsiloxane, a polyarylsulfone structure intermediate is obtained. The repeating units of the polyarylsulfone structure contain alternating polydimethylsiloxane structures. In addition, by adjusting the amount of dimethyl sulfoxide added, the water generated during the reaction is absorbed by the dimethyl sulfoxide. At the same time, by reasonably adjusting the reaction temperature, the polymer waterproof membrane has a good waterproof effect.

[0028] 2. Using linoleic acid as the initial reactant, the unsaturated double bonds are epoxidized to obtain modified linoleic acid containing epoxy groups. Itaconic anhydride is then added; after ring-opening, itaconic anhydride reacts with the hydroxyl groups of the opened epoxy groups, thus incorporating itaconic anhydride into the reaction system. Next, 1,3,5-tris(4-hydroxyphenyl)benzene is added; the ring-opened itaconic anhydride reacts with the hydroxyl groups in 1,3,5-tris(4-hydroxyphenyl)benzene, thus linking 1,3,5-tris(4-hydroxyphenyl)benzene to itaconic anhydride. Then, diethylphosphorylethyltriethoxysilane is added; the phosphoryl group hydrolyzes under heating conditions and reacts with the hydroxyl groups in 1,3,5-tris(4-hydroxyphenyl)benzene to obtain a plasticizer containing phosphate ester groups. Using the prepared plasticizer further improves the waterproof effect and mechanical strength of the polymer waterproof membrane.

[0029] 3. The carboxyl group at one end of 3-sulfonic acid terephthalic acid reacts with hydroxyl-terminated polydimethylsiloxane, while the carboxyl group at the other end reacts with the phenolic hydroxyl group of biphenyl hydroquinone, thus yielding a reactant with 2-sulfonic acid terephthalic acid in the middle and hydroxyl-terminated polydimethylsiloxane and biphenyl hydroquinone at both ends. Subsequently, two molecules of 4,4'-difluorodiphenyl sulfone react with bisphenol fluorene and the reactant, respectively, with fluorine being replaced by oxygen atoms, ultimately yielding the final product. This product is used in the aggregate layer and waterproofing layer, improving the thermal aging performance of the polymer waterproof membrane.

[0030] 4. High-density polyethylene and linear low-density polyethylene are used as reactants and polymerized with the unsaturated double bonds of itaconic anhydride under high-temperature conditions. Under the action of a catalyst, the ring-opening itaconic anhydride crosslinks with bisphenol A epoxy resin and 4,4'-diaminodiphenyl sulfone to obtain modified polyethylene. During the spinning process, the amino groups in the modified polyethylene crosslink with the sulfonic acid groups of the product to form an aggregate layer. Simultaneously, modified polyethylene, EPDM rubber, and thermoplastic polyolefins are mixed in appropriate proportions, and hydroxides are added. The resulting polymer waterproof membrane exhibits improved adaptability to high-temperature and hot environments, and its heat resistance is further enhanced.

[0031] 5. Bentonite is modified by first screening its expansion index, then mixing it with nano-zinc oxide, followed by the addition of modified nano-cellulose crystals. After introducing amino groups onto the surface of the nano-cellulose crystals, they are intercalated into the mixture under ball milling conditions. KH550 is then introduced to obtain modified bentonite. After carboxylating the surface of the waterproof layer, the amino groups of the modified bentonite react with the carboxyl groups, thus bonding the modified bentonite to the surface of the waterproof layer. The polymer waterproof membrane prepared with modified bentonite exhibits excellent waterproofing and heat aging resistance. Attached Figure Description

[0032] Figure 1The image shows the test results of the waterproof and heat aging resistance of the polymer waterproof membrane of this invention. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Please see Figure 1 This invention provides a polymer waterproof membrane and its preparation method, the technical solution of which is as follows:

[0035] The material information involved in this invention is as follows:

[0036] Bisphenol fluorene CAS: 3236-71-3; Dihydroxyfluorene CAS: 73100-16-0; 2,7-Dihydroxy-9,9-Dimethylfluorene CAS: 221010-68-0; 2-Sulfonic acid terephthalic acid CAS: 4991-22-4; Biphenyl hydroquinone CAS: 92-88-6; 4,4'-Difluorodiphenyl sulfone CAS: 383-29-9; Octamethylcyclotetrasiloxane (D4) CAS: 556-67-2; Dodecylcyclohexasiloxane (D6) CAS: 540-97-6; Hexadecylcyclooctasiloxane (D8) CAS: 556-68-3; Eicosylcyclodecasiloxane (D10) CAS: 18772-3 6-6; Tetramethylcyclododecylsiloxane (D12) CAS: 18919-94-3; Octadecylcyclononasiloxane (D9) CAS: 556-71-8; Linoleic acid CAS: 60-33-3; 1,3,5-Tris(4-hydroxyphenyl)benzene CAS: 15797-52-1; Itaconic anhydride CAS: 2170-03-8; Diethylphosphorylethyltriethoxysilane CAS: 757-44-8; 1-Hydroxycyclohexanebenzophenone CAS: 947-19-3; 3-Aminopropyltriethoxysilane (KH550) CAS: 919-30-2; DMF is a dimethylformamide solvent, CAS: 68-12-2. Dean-Stark water separators are Dean-Stark water separators.

[0037] Nano zinc oxide was purchased from Xianfeng Nanotechnology Co., Ltd.; EPDM rubber was purchased from PetroChina Jilin Chemical Co., Ltd.; thermoplastic polyolefins were purchased from Dow Chemical (China) Co., Ltd.; and high-density polyethylene and low-density polyethylene were purchased from Dushanzi Petrochemical Co., Ltd.

[0038] Example 1

[0039] 5.0 parts of octamethylcyclotetrasiloxane were added to a three-necked flask and the temperature was raised to 60°C. 2 parts of a 10% (w / w) potassium hydroxide aqueous solution preheated to 60°C were added to the octamethylcyclotetrasiloxane. The mixture was stirred at 800 rpm. Starting from 2 hours, 0.01 parts of the octamethylcyclotetrasiloxane reaction solution were taken out every hour and tested with potassium hydroxide until the amount of potassium hydroxide no longer changed. After reacting for 5 hours, a hydroxyl-terminated polydimethylsiloxane solution was obtained. 1.0 part of anhydrous sodium sulfate was added to the hydroxyl-terminated polydimethylsiloxane solution to remove water. The filtered liquid was then vacuum dried to obtain hydroxyl-terminated polydimethylsiloxane.

[0040] 2.5 parts of 2-sulfonic acid terephthalic acid were added to 3.0 parts of hydroxyl-terminated polydimethylsiloxane, followed by 20 parts of sulfolane. After dissolving evenly, 0.1 parts of phosphoric acid were added, and the temperature was raised to 60°C. The mixture was stirred in a reactor for 4 hours to obtain the precursor of the reactant. 1.9 parts of biphenyl hydroquinone were added to the precursor of the reactant, followed by 20 parts of sulfolane. The mixture was stirred for another 5 hours to obtain the reactant. 3.5 parts of bisphenol fluorene and 5.2 parts of 4,4'-difluorodiphenyl sulfone were dissolved in 30 parts of sulfolane to obtain a mixed solution. The mixed solution was... 0.3 parts potassium carbonate and 5 parts dimethyl sulfoxide were added to the reactants. Nitrogen gas was introduced into the reactor, and after the air was purged, the temperature of the reactor was raised to 180°C. After stirring for 3 hours, the product precursor was obtained. After removing the organic solvent from the product precursor, the temperature was raised to 210°C and reacted for 10 hours. Then, the temperature was lowered to 80°C to obtain the product intermediate. The product intermediate was added to deionized water at 80°C to obtain a fibrous white precipitate. The fibrous white precipitate was crushed and washed repeatedly with water at 100°C and anhydrous ethanol at 60°C. Then, it was dried under vacuum to obtain the product.

[0041] Eight parts of high-density polyethylene and two parts of linear low-density polyethylene were melted in a reactor, and then four parts of bisphenol A epoxy resin, 1.2 parts of itaconic anhydride and 2.5 parts of 4,4'-diaminodiphenyl sulfone were added to the mixture. After melting and mixing, a mixture was obtained. Then, 0.3 parts of 2,2'-azobisisobutyronitrile and 0.2 parts of boron trifluoride complex were added to the mixture. The mixture was then stirred at 160°C for 10 min, and then 0.3 parts of concentrated sulfuric acid were added. The reaction was continued for 30 min, and after cooling to room temperature, modified polyethylene was obtained.

[0042] The product and modified polyethylene were mixed at a ratio of 9:1 to obtain a spinning raw material; the amount of the spinning raw material was 3 parts; the spinning raw material was dissolved in 14.5 parts of DMF solvent and stirred at 600 rpm for 12 h to obtain a spinning solution; the spinning solution was electrospun and then woven, and dried at 60℃ for 48 h to obtain an aggregate layer;

[0043] Modified polyethylene, EPDM rubber, and thermoplastic polyolefin were mixed in a ratio of 6:4:1 and then co-melted to obtain a polymer layer precursor. 10 parts of the polymer layer precursor, 0.15 parts of aluminum hydroxide, and 0.15 parts of magnesium hydroxide (totaling 0.3 parts of hydroxides) were mixed and stirred at 160°C for 30 minutes to obtain a polymer layer intermediate. 0.4 parts of DEHP plasticizer were added to the polymer layer intermediate, and stirring was continued for 5 minutes, followed by extrusion to obtain the polymer layer.

[0044] The preparation method of the waterproof layer is as follows: 5 parts of the product are melted and extruded to obtain the waterproof layer precursor; the waterproof layer precursor is immersed in an acrylic solution and irradiated with ultraviolet light for 10 minutes to obtain the waterproof layer intermediate; the acrylic solution contains 0.3 parts of 1-hydroxycyclohexanebenzophenone; 3 parts of modified bentonite and 0.3 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride are uniformly coated on one side of the waterproof layer intermediate, and hot-pressed to obtain the waterproof layer;

[0045] The preparation method of modified bentonite is as follows:

[0046] First, bentonite was dried in a vacuum drying oven at 60℃ for 72 hours. Then, 5 parts of calcium-based bentonite and 2 parts of nano-zinc oxide were mixed evenly with 20 parts of deionized water to obtain a mixture. 0.5 parts of nano-cellulose crystals and 0.2 parts of glycine were dispersed in deionized water, followed by the addition of 0.01 parts of concentrated sulfuric acid. The temperature was raised to 55℃, and the mixture was stirred for 5 hours. After filtration and drying, modified nano-cellulose was obtained. 0.5 parts of modified nano-cellulose were added to the mixture, the temperature was raised to 40℃, and the mixture was ball-milled using a star ball mill for 2 hours. After drying, 1.5 parts of KH550 were added, and the mixture was ball-milled for another 1.5 hours to obtain modified bentonite.

[0047] The release membrane, waterproof layer, polymer layer, aggregate layer, polymer layer, waterproof layer, and release membrane are stacked and hot-pressed, then cut and rolled up to obtain a polymer waterproof membrane. The intermediate layer of the waterproof layer coated with modified bentonite is in direct contact with the release membrane, while the intermediate layer of the waterproof layer not coated with modified bentonite is in direct contact with the polymer layer. The release membrane is a single-sided silicone paper release membrane, with the silicone side facing inwards towards the polymer waterproof membrane.

[0048] Example 2-14

[0049] Unlike Example 1, the preparation methods of hydroxyl-terminated polydimethylsiloxane and product intermediates have been changed, as shown in Table 1.

[0050] Table 1. Raw materials and dosages used in preparation

[0051]

[0052] Comparative Example 1

[0053] Unlike Example 1, the preparation time for the hydroxyl-terminated polydimethylsiloxane solution was 2 hours.

[0054] Comparative Example 2

[0055] Unlike Example 1, no dimethyl sulfoxide was added.

[0056] Comparative Example 3

[0057] Unlike Example 1, the reaction temperature was 250°C.

[0058] Example 15

[0059] The polymer waterproof membranes prepared in Examples 1-14 and Comparative Examples 1-3 were tested for waterproof performance. The specific test methods are as follows: After removing the release film, the polymer waterproof membrane was adhered to the surface of uncured concrete and covered for 72 hours. Its impermeability under 0.6 MPa water pressure was then tested. Parallel tests were also conducted. The examples and comparative examples were adhered to uncured concrete and cured for 72 hours. Then, they were soaked in water and the peel strength at 180° was tested after 48 hours of soaking. The final test results are shown in Table 2.

[0060] Table 2 Waterproofing Performance Test Results

[0061] Group Impermeability time at 0.6 MPa (min) Peel strength (N / mm) Example 1 96 2.9 Example 2 107 3.0 Example 3 120 3.3 Example 4 138 3.8 Example 5 143 3.6 Example 6 156 3.9 Example 7 158 4.0 Example 8 139 3.7 Example 9 91 2.8 Example 10 160 4.0 Example 11 150 3.8 Example 12 162 4.1 Example 13 170 4.3 Example 14 144 3.5 Comparative Example 1 50 1.8 Comparative Example 2 65 2.1 Comparative Example 3 41 1.5

[0062] The polymer waterproof membrane prepared by this invention exhibits an impermeability time of 91-170 min under 0.6 MPa water pressure, and a peel strength of 2.9-4.3 N / mm after water immersion. The results of Examples 1-6 show that by changing the type of siloxane, the impermeability time generally increases with increasing siloxane chain length, while the peel strength exhibits an increasing-decreasing-increasing trend. This is because the hydroxyl-terminated polydimethylsiloxane obtained from ring-opening is used as an intermediate in the synthesis of the product, increasing the molecular chain length when the amount of siloxane is the same. As shown in Example 6, the polydimethylsiloxane contained therein has a longer repeating unit structure, resulting in complete reaction with 2-sulfonic acid terephthalic acid. In contrast, short-chain siloxanes, such as D4 in Example 1, after hydrolysis and subsequent addition, have a relatively high hydroxyl content, leading to incomplete reaction with 2-sulfonic acid terephthalic acid. Excess hydroxyl-terminated and polydimethylsilane compounds remain free in the system, which is detrimental to improving the hydrophobic effect. The results of Examples 6-8 and Comparative Example 1 show that controlling the preparation process of hydroxyl-terminated polydimethylsiloxane within a reasonable time increases the impermeability time and improves the peel strength after water immersion. The polymer waterproof membrane obtained under the conditions of Example 7 has the best waterproof effect. The results of Examples 7 and 9-11 show that as the amount of hydroxyl-terminated polydimethylsiloxane in the synthesized product increases, the impermeability time tends to increase and then decrease. Within a reasonable addition range, adding hydroxyl-terminated polydimethylsiloxane can achieve a good hydrophobic effect. However, if the amount is too high, as shown in Example 11, the flexibility of the polymer waterproof membrane increases, and cracks appear on the surface of the polymer waterproof membrane under 0.6 MPa and continuous pressure, indicating a decrease in waterproof effect; the peel strength also tends to increase and then decrease. The results of Examples 11-14 show that by reasonably adjusting the amount of dimethyl sulfoxide and the reaction temperature for obtaining the intermediate product, the waterproof effect is best under the conditions of Example 13. Comparative Example 2, without the addition of dimethyl sulfoxide, showed a decrease in impermeability time and peel strength compared to the Example. The moisture generated during the reaction could not be eliminated from the reaction system, interfering with the reaction process and resulting in incomplete reaction of the raw materials for the intermediate products. Consequently, the waterproofing effect of the polymer waterproof membrane used in the waterproof layer decreased. Comparative Example 3, with its excessively high reaction temperature, damaged the material structure, causing molecular chain breakage, which manifested as a decrease in the impermeability time and peel strength of the membrane.

[0063] Example 16

[0064] Except for the plasticizer, the other preparation process is the same as in Example 13.

[0065] The preparation method of the plasticizer is as follows: 2.8 parts of linoleic acid and 10 parts of toluene are placed in a four-necked round-bottom flask equipped with a Dean-Stark water separator. The temperature is raised to 60℃, then 0.1 parts of phosphotungsten heteropolyacid quaternary ammonium salt catalyst and 1.8 parts of a 30% (w / w) hydrogen peroxide aqueous solution are added, and the mixture is refluxed for 3.5 h until the epoxy value no longer changes, yielding the plasticizer precursor; 0.5 parts of 1,3,5-tris(4-hydroxyphenyl)benzene are dissolved in 10 parts of toluene to obtain 1, 3,5-Tris(4-hydroxyphenyl)benzene solution; 0.3 parts itaconic anhydride and 0.05 parts phosphoric acid were added to the plasticizer precursor, followed by the addition of 1,3,5-tris(4-hydroxyphenyl)benzene solution. The temperature was raised to 70°C and refluxed for 1 hour. Then, 0.02 parts phosphoric acid and 1.0 parts diethylphosphorylethyltriethoxysilane were added, and the reflux reaction was continued for 4 hours. During this period, water generated during the reaction was removed through a Dean-Stark water separator. Toluene was then removed to obtain the plasticizer.

[0066] Examples 17-24

[0067] Unlike Example 16, the preparation method of the plasticizer has been changed, as shown in Table 3.

[0068] Table 3 Raw material dosage for plasticizer preparation

[0069]

[0070]

[0071] Comparative Example 4

[0072] Unlike Example 16, 1,3,5-tris(4-hydroxyphenyl)benzene was not added.

[0073] Comparative Example 5

[0074] Unlike Example 16, diethylphosphorylethyltriethoxysilane was not added.

[0075] Example 25

[0076] The polymer waterproof membranes prepared in Examples 13 and 16-24 were subjected to waterproof performance tests, and the test methods were the same as in Example 15. Mechanical properties were also tested, with tensile strength and elongation at break tested according to GB / T 23457-2009 "Pre-laid / Wet-laid Waterproof Membranes" and GB / T27789-2011 "Thermoplastic Polyolefin (TPO) Waterproof Membranes". The results of the waterproof and mechanical performance tests are shown in Table 4.

[0077] Table 4. Test results of water resistance and mechanical properties

[0078]

[0079] The polymer waterproof membrane prepared by this invention has a tensile strength of 14.2-17.5 MPa, an elongation at break of 530%-720%, an impermeability time of 160-200 min at 0.6 MPa, and a peel strength of 3.6-4.5 N / mm after immersion in water. The results of Examples 13 and 16-24 show that, compared with the addition of DEHP plasticizer, the addition of the plasticizer synthesized in Examples 16-19 and 21-24 to the waterproof membrane improves the mechanical properties and waterproofing effect of the waterproof membranes obtained in Examples 16, 17, and 19-23. The itaconic anhydride in the plasticizer added in this invention polymerizes with the olefin groups in the polymer layer, and the introduced diethylphosphorylethyltriethoxysilane further enhances the waterproofing effect. The results of Examples 16 and 17 show that, by reasonably adjusting the amount of linoleic acid, the obtained waterproof membrane has good tensile strength, elongation at break, and waterproofing effect. The results of Examples 16 and 18-20 show that with the increase of 1,3,5-tris(4-hydroxyphenyl)benzene content, the mechanical properties gradually decrease, the impermeability time increases, and the peel strength initially increases and then decreases. The introduced rigid benzene ring structure improves the hardness of the polymer waterproof membrane and increases its resistance to water pressure impact, but the material flexibility and tensile strength decrease. The results of Examples 19 and 21 show that with the increase of itaconic anhydride content, the mechanical properties improve, its degree of polymerization with the raw materials in the polymer layer increases, and the impermeability time increases. The results of Examples 21-24 show that with the increase of diethylphosphorylethyltriethoxysilane content, the mechanical properties improve, the impermeability time increases and then decreases, and the peel strength shows a trend of decreasing and then increasing. Comparative Examples 4 and 5, without the addition of 1,3,5-tris(4-hydroxyphenyl)benzene and diethylphosphorylethyltriethoxysilane respectively, have mechanical properties comparable to the examples, but the waterproofing effect is reduced.

[0080] Examples 26-34

[0081] Unlike Example 23, the amounts of 2-sulfonic acid terephthalic acid, biphenyl hydroquinone, bisphenol fluorene, and 4,4'-difluorodiphenyl sulfone in the product intermediate, as well as the type of hydroxyfluorene, are different, as shown in Table 5.

[0082] Example 35

[0083] The polymer waterproof membranes prepared in Examples 23 and 26-34 were subjected to heat resistance tests. After the polymer waterproof membranes were heat-aged, they were bonded to the concrete surface. After 72 hours of bonding, the peel strength was tested. The final test results are shown in Table 5.

[0084] Table 52 shows the dosage of 2-sulfonic acid terephthalic acid, biphenyl phenol, hydroxyfluorene, and 4,4'-difluorodiphenyl sulfone, as well as the types of hydroxyfluorene.

[0085]

[0086]

[0087] The polymer waterproof membrane prepared by this invention exhibits a peel strength of 2.5-4.2 N / mm after heat aging treatment. Results from Examples 23, 26, and 27 show that the highest peel strength after heat aging is achieved when the amount of 2-sulfonic acid terephthalic acid is 3.1 parts. 2-sulfonic acid terephthalic acid, along with hydroxyl-terminated polydimethylsiloxane and biphenyl, has a binding effect; increasing its amount enhances the binding and improves heat resistance. Results from Examples 27 and 28 show that the best aging resistance is achieved when the amount of biphenyl is 1.9 parts. The results of Examples 27, 29, and 30 show that changing the type of hydroxyfluorene, 4,4'-difluorodiphenyl sulfone reacts with hydroxyfluorene to form a partial unit structure of polyarylsulfone. The waterproof membrane prepared with hydroxyfluorene in Example 30 has the lowest peel strength, as its unit molecule contains only two benzene rings. In contrast, the increased benzene ring content of hydroxyfluorene in Examples 27 and 30 improves heat resistance. In Example 29, the hydroxyl group is in the para-position, resulting in a uniform distribution density of benzene rings, and the Π-Π conjugated system enhances the heat resistance of the waterproof membrane. The results of Examples 29, 31, and 32 show that the highest peel strength is achieved when the amount of hydroxyfluorene is 3.5 parts. The results of Examples 31, 3, and 34 show that by rationally controlling the amount of 4,4'-difluorodiphenyl sulfone, and by randomly alternating the reaction of 4,4'-difluorodiphenyl sulfone with bisphenol fluorene and the reactants, a product containing a polyarylsulfone structure is obtained, resulting in a polymeric waterproof membrane with high peel strength after heat aging.

[0088] Examples 36-47

[0089] Unlike Example 33, the preparation methods of the aggregate layer and polymer layer are changed, as shown in Table 6.

[0090] Example 48

[0091] The waterproof membranes prepared in Examples 33 and 36-47 were subjected to heat resistance tests, and their peel strength was tested after heat aging. The heat resistance test results are shown in Table 6.

[0092] As shown in Table 6, the peel strength of the polymer waterproof membrane prepared by this invention after heat aging is 3.7-4.6 N / mm. The results of Examples 33 and 36-38 show that with the increase of bisphenol A epoxy resin dosage, the peel strength after heat aging first increases and then decreases. After the epoxy groups of the bisphenol A epoxy resin undergo ring-opening, they react with the carboxyl groups of the ring-opening itaconic anhydride to form an esterification reaction. The introduced epoxy resin improves the heat resistance of the material, but excessive dosage leads to increased brittleness of the waterproof membrane, making it easy to peel, which manifests as a decrease in peel strength after heat aging. The results of Examples 37 and 39-41 show that the peel strength is highest when the dosage of 4,4'-diaminodiphenyl sulfone is 2.0 parts. The basic groups of 4,4'-diaminodiphenyl sulfone react with the ring-opening itaconic anhydride on the one hand, and crosslink with the sulfonic acid groups in the product on the other hand, improving the heat resistance. The results of Examples 39, 41, and 42 show that by reasonably adjusting the ratio of the product to modified polyethylene, the crosslinking degree between polysulfone and modified polyethylene increases, and the compatibility is improved. The waterproof membrane obtained under the conditions of Example 41 has the best heat resistance. The results of Examples 41, 43, and 44 show that by melting and mixing modified polyethylene, EPDM rubber, and thermoplastic polyolefin, and changing the component amounts, including the addition of some thermoplastic polyolefin, in which the propylene and octene copolymers are co-fused with polyethylene, and then adding EPDM rubber, the heat resistance is improved, and the polymer waterproof membrane is less prone to dimensional changes after heat aging. The results of Examples 44-47 show that by changing the composition ratio and type of hydroxide, the obtained polymer waterproof membrane has high peel strength after heat aging. Under heat aging conditions, the water produced by the hydroxide further solidifies with substances such as limestone and water glass in the cement. At the same time, the introduced magnesium, aluminum, and tungsten elements improve the heat resistance of the waterproof membrane, and it still has high peel strength after heat aging.

[0093] Table 6. Preparation methods of aggregate layer and polymer layer

[0094]

[0095]

[0096] Examples 49-58

[0097] Unlike Example 44, the preparation methods for the waterproof layer and the modified bentonite have been changed, as detailed in Table 7.

[0098] Table 7. Preparation methods of modified bentonite and waterproof layer

[0099]

[0100] Comparative Example 6

[0101] Unlike Example 44, calcium-based bentonite was replaced with sodium-based bentonite, with an SI of 31.4 mL / 2 g.

[0102] Comparative Example 7

[0103] Unlike Example 44, no nano zinc oxide was added.

[0104] Comparative Example 8

[0105] Unlike Example 44, no modified nanocellulose was added.

[0106] Comparative Example 9

[0107] Unlike Example 44, KH550 was not added.

[0108] Comparative Example 10

[0109] Unlike Example 44, no modified bentonite was added.

[0110] Example 59

[0111] The polymer waterproof membranes prepared in Examples 44, 49-58 and Comparative Examples 6-10 were tested for waterproofing, aging resistance, and mechanical properties. The final test results are as follows: Figure 1 As shown.

[0112] like Figure 1As shown, the waterproof membrane prepared by this invention has a peel strength of 2.0-4.9 N / mm after water immersion and a peel strength of 4.0-4.8 N / mm after heat aging. A mixture is obtained by mixing bentonite and nano-zinc oxide, followed by the addition of deionized water. The nano-cellulose crystals are then modified by linking glycine to the carboxyl groups of the cellulose crystals, resulting in modified nano-cellulose containing carboxyl and hydroxyl groups. This modified nano-cellulose is introduced into the mixture, and then KH550 is added under heating and grinding conditions to obtain modified bentonite. The waterproof layer precursor is immersed in an acrylic acid solution. Under the action of ultraviolet light and a 1-hydroxycyclohexanebenzophenone catalyst, activated carboxyl groups are formed on its surface, thereby introducing modified bentonite into the surface of the waterproof layer precursor through chemical bonds. The results of Examples 44, 49, and 50 show that as the swelling index of bentonite increases, the peel strength after immersion in water decreases, while the peel strength after thermal aging remains essentially unchanged. This is because the modified bentonite is located on the outer layer of the waterproofing layer and plays the initial role in waterproofing. The introduced KH550 and the dense network structure formed with the modified nanocellulose have a water-blocking effect. However, after water breaks through this swelling layer, the bentonite begins to absorb water. The higher the swelling index, the better the water absorption effect. The surface of the polymer waterproof membrane is prone to blistering, and water then penetrates into the interior of the waterproof membrane. In Comparative Example 6, the sodium-based bentonite has an excessively high swelling index, resulting in a significant decrease in waterproofing performance. After the aging test, the peel strength was tested, and significant residual adhesive was found. The montmorillonite in the modified bentonite and the Al, Si, and Mg elements it contains improve the aging resistance of the waterproof membrane. The calcium ions in the calcium-based bentonite and the sodium ions in the sodium-based bentonite undergo cation exchange during the concrete curing process, improving the bond strength between the membrane and the concrete, and thus increasing the peel strength. The results of Examples 49, 51, and 52 show that as the amount of nano zinc oxide increases, the peel strength after immersion in water gradually decreases, while the peel strength after heat aging remains unchanged after increasing. Zinc oxide has good heat resistance, but excessive addition leads to poor mixing with modified bentonite, causing zinc oxide to easily precipitate, thus reducing the peel strength after immersion in water. Comparative Example 7, without the addition of zinc oxide, shows a significant decrease in aging resistance. The results of Examples 51 and 53 show that controlling the amount of modified nanocellulose within the range of 0.3-0.5% results in good waterproofing and aging resistance of the roll material. Comparative Example 8, without the addition of modified nanocellulose, shows a decrease in waterproofing and aging resistance. The results of Examples 53-55 show that as the amount of KH550 increases, the waterproofing and aging resistance improve. The amino groups of KH550 are chemically bonded to the surface of the waterproofing layer precursor, and the silane structure therein imparts waterproofing and aging resistance to the roll material. Comparative Example 9, without the addition of KH550, shows a significant decrease in waterproofing. Examples 55 and 56 adjusted the amount of 1-hydroxycyclohexanebenzophenone catalyst, which, under ultraviolet light irradiation, allowed acrylic acid in the acrylic acid solution to enter the structure of the waterproof layer precursor, thereby promoting the crosslinking of the waterproof layer precursor with the modified bentonite.Examples 56-58 show that adjusting the amount of modified bentonite improved the waterproofing effect and aging resistance of the polymer waterproof membrane. Comparative Example 10, without modified bentonite, showed a decrease in the waterproofing effect and reduced membrane performance.

[0113] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a polymer waterproof membrane, characterized in that: The preparation method is as follows: A cyclic siloxane was subjected to a ring-opening reaction for 2-7.5 h to obtain a hydroxyl-terminated polydimethylsiloxane; 2-3.1 parts of 2-sulfonic acid terephthalic acid, 1.5-4.0 parts of the hydroxyl-terminated polydimethylsiloxane, and 1.4-1.9 parts of biphenyl were mixed and reacted to obtain the reactant; 3.5-4.0 parts of hydroxyfluorene and 5.2-8.7 parts of 4,4'-difluorodiphenyl sulfone were dissolved in sulfolane to obtain a mixed solution; the mixed solution and 2.8-5 parts of dimethyl sulfoxide were added to the reactant, and after the reaction, the organic solvent was removed, and the temperature was raised to 180-250℃ to obtain the product; Modified polyethylene is obtained by melting and mixing high-density polyethylene, linear low-density polyethylene, 4-5 parts of bisphenol A epoxy resin and 1.5-2.5 parts of 4,4'-diaminodiphenyl sulfone. The product and the modified polyethylene are mixed in a ratio of 4-9:1-3 to obtain an aggregate layer; Modified polyethylene, EPDM rubber and thermoplastic polyolefin are melt-mixed in a ratio of 5-7:2-4:1-2, hydroxide and plasticizer are added, and after stirring, the mixture is extruded to obtain a polymer layer. The product is melted, extruded, and then immersed in an acrylic acid solution containing 0.1-0.3 parts of 1-hydroxycyclohexanebenzophenone. It is then irradiated with ultraviolet light to obtain a waterproof layer intermediate. 1.5-3 parts of modified bentonite are coated on one side of the waterproof layer intermediate, and the mixture is then hot-pressed to obtain a waterproof layer. The release film, waterproof layer, polymer layer, aggregate layer, polymer layer, waterproof layer and release film are stacked and hot-pressed, then cut and rolled up to obtain the polymer waterproof membrane.

2. The method for preparing a polymer waterproof membrane according to claim 1, characterized in that: The ring-opening reaction is as follows: the cyclic siloxane is added to a three-necked flask and the temperature is increased; a preheated potassium hydroxide aqueous solution is added to the cyclic siloxane, and the mixture is stirred and reacted for 5-7.5 hours to obtain a hydroxyl-terminated polydimethylsiloxane solution; Anhydrous sodium sulfate was added to the hydroxyl-terminated polydimethylsiloxane solution to remove moisture. The filtered liquid was then vacuum dried to obtain the hydroxyl-terminated polydimethylsiloxane. The cyclic siloxane is one of octamethylcyclotetrasiloxane, dodecylcyclohexasiloxane, hexadecylcyclooctasiloxane, octadecylcyclononasiloxane, icosylcyclodecasiloxane, and icosylcyclododecylsiloxane.

3. The method for preparing a polymer waterproof membrane according to claim 1, characterized in that: The preparation method of the product is as follows: 2-sulfonic acid terephthalic acid is added to the hydroxyl-terminated polydimethylsiloxane, sulfolane is added to it, and after uniform dissolution, phosphoric acid is added. The temperature is raised, and the reaction is stirred in a reactor to obtain the precursor of the reactant; biphenyl is added to the precursor of the reactant, sulfolane is added, and the reaction is continued with stirring to obtain the reactant; hydroxyfluorene and 4,4'-difluorodiphenyl sulfone are dissolved in sulfolane to obtain the mixed solution; the mixed solution and dimethyl sulfoxide are added to the precursor of the reactant. In the reaction, nitrogen gas is introduced into the reaction vessel, and after the air is purged, the temperature of the reaction vessel is raised and the reaction is stirred to obtain a product precursor; after removing the organic solvent from the product precursor, the temperature is raised to 180-210℃, and after the reaction, the temperature is lowered to obtain a product intermediate; the product intermediate is added to deionized water to obtain a fibrous white precipitate; the fibrous white precipitate is pulverized and repeatedly washed with water and anhydrous ethanol, and then vacuum dried to obtain the product; the hydroxyfluorene is one of bisphenol fluorene, dihydroxyfluorene, and 2,7-dihydroxy-9,9-dimethylfluorene.

4. The method for preparing a polymer waterproof membrane according to claim 1, characterized in that: The preparation method of the aggregate layer is as follows: the high-density polyethylene and the linear low-density polyethylene are melted in a reaction vessel, and then the bisphenol A epoxy resin, itaconic anhydride and the 4,4'-diaminodiphenyl sulfone are added to it. After melting and mixing, a mixture is obtained. 2,2'-azobisisobutyronitrile and boron trifluoride complex are added to the mixture, and after stirring and reacting, concentrated sulfuric acid is added to it. The reaction is continued, and after cooling to room temperature, the modified polyethylene is obtained. The product and the modified polyethylene are mixed to obtain a spinning raw material; the spinning raw material is dissolved in DMF and stirred to obtain a spinning solution; the spinning solution is electrospun, woven, and dried to obtain the aggregate layer.

5. The method for preparing a polymer waterproof membrane according to claim 1, characterized in that: The preparation method of the polymer layer is as follows: the modified polyethylene, the EPDM rubber and the thermoplastic polyolefin are mixed in a ratio of 5-7:2-4:1-2, and then co-melted and mixed evenly to obtain a polymer layer precursor; the polymer layer precursor and the hydroxide are mixed and stirred to obtain a polymer layer intermediate; the plasticizer is added to the polymer layer intermediate, stirring is continued, and then the polymer layer is extruded.

6. The method for preparing a polymer waterproof membrane according to claim 5, characterized in that: The hydroxide is two of aluminum hydroxide, magnesium hydroxide, and tungsten hydroxide.

7. The method for preparing a polymer waterproof membrane according to claim 5, characterized in that: The plasticizer is prepared as follows: 2.0-2.8 parts of linoleic acid and toluene are placed in a four-necked round-bottom flask equipped with a Dean-Stark water separator. The temperature is raised, and a phosphotungsten heteropoly acid quaternary ammonium salt catalyst and an aqueous solution of hydrogen peroxide are added. The mixture is refluxed until the epoxy value no longer changes, yielding a plasticizer precursor. 0.5-1.5 parts of 1,3,5-tris(4-hydroxyphenyl)benzene are dissolved in the toluene to obtain a 1,3,5-tris(4-hydroxyphenyl)benzene solution. 0.3-0.5 parts of itaconic anhydride and phosphoric acid are added to the plasticizer precursor, followed by the 1,3,5-tris(4-hydroxyphenyl)benzene solution. The temperature is raised and the mixture is refluxed. Then, the phosphoric acid and 1.0-4.0 parts of diethylphosphonylethyltriethoxysilane are added, and the mixture is refluxed again. During this process, water generated is removed through the Dean-Stark water separator. Toluene is then removed to obtain the plasticizer.

8. The method for preparing a polymer waterproof membrane according to claim 1, characterized in that: The modified bentonite is prepared as follows: First, the bentonite is dried in a vacuum drying oven. Then, the bentonite and 2-2.5 parts of nano zinc oxide are mixed evenly with deionized water to obtain a mixture. Nanocellulose crystals and glycine are dispersed in the deionized water. Then, concentrated sulfuric acid is added, the temperature is raised, the mixture is stirred and reacted, filtered, and dried to obtain modified nanocellulose. 0.3-0.5 parts of the modified nanocellulose are added to the mixture, the temperature is raised, and the mixture is ball-milled using a star ball mill and dried. Then, 1.5-3.6 parts of KH550 are added, and the mixture is ball-milled again to obtain the modified bentonite.

9. The method for preparing a polymer waterproof membrane according to claim 8, characterized in that: The bentonite is one of calcium-based bentonite and sodium-based bentonite; the swelling index of the bentonite is 7.0-31.4 mL / 2g.

10. A polymer waterproof membrane, characterized in that: The structure of the polymer waterproof membrane, from the outside to the inside, consists of a release film, a waterproof layer, a polymer layer, an aggregate layer, the polymer layer, the waterproof layer, and the release film; the polymer waterproof membrane is prepared by the preparation method according to any one of claims 1-9.

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