Durable double-layer waterproof coiled material and preparation method thereof

Abstract

The invention discloses a durable double-layer waterproof coiled material and a preparation method thereof, and relates to the field of building waterproof materials. The double-layer waterproof roll comprises a first waterproof layer, a hot melt adhesive layer and a second waterproof layer. The first waterproof layer is an asphalt-based waterproof layer, the second waterproof layer comprises a sand layer, a connecting adhesive layer and a waterproof base material which are arranged in sequence, and the hot melt adhesive layer and the connecting adhesive layer both adopt waterproof and oil-resistant hot melt adhesives; the waterproof and oil-resistant hot melt adhesive is prepared from the following raw materials: 90 to 95 weight percent of basic rubber hot melt adhesive and 5 to 10 weight percent of reinforcing adhesive, wherein the reinforcing adhesive is prepared from an amino-terminated polyurea prepolymer, a hydroxyl-terminated polyurethane prepolymer, a blocked isocyanate cross-linking agent and a catalyst; the molar ratio of the amino-terminated polyurea prepolymer to the hydroxyl-terminated polyurethane prepolymer to the blocked isocyanate cross-linking agent is (1-2): (3.5-6): (1.5-3.5). The waterproof and oil-resistant hot melt adhesive in the double-layer waterproof coiled material can slow down permeation of small molecule engine oil, the service life of the waterproof coiled material can be prolonged, and the purpose that the service life of the waterproof coiled material is the same as that of a building is achieved.

Description

Technical Field

[0001] The present application relates to the field of building waterproof materials, and in particular to a durable double-layer waterproof roll and a preparation method thereof. Background Art

[0002] In the construction field, waterproofing is crucial to ensure the structural integrity and durability of buildings. Compared with single-layer waterproofing membranes, double-layer waterproofing membranes have an extra layer of waterproof substrate, which generally has better waterproof performance than single-layer waterproofing membranes. Therefore, double-layer waterproofing membranes are widely used.

[0003] At present, the problems encountered by double-layer waterproof membranes during use are as follows: Asphalt-based waterproof layers have low costs, so most people are keen to use asphalt-based waterproof layers as waterproof substrates. However, there will be a large amount of small molecule oils in the asphalt-based waterproof layers. These small molecule oils can easily penetrate into the hot melt adhesive layer that bonds the second waterproof layer to the first waterproof layer, and the existing hot melt adhesive layer has limited resistance to small molecule oils. After 28 days of placement, the peeling force between the double-layer waterproof membranes will be significantly reduced, affecting the service life of the double-layer waterproof membrane. Summary of the invention

[0004] In order to improve the problem in the related art that the service life of a double-layer waterproof coiled material is greatly affected by small molecule engine oil, the present application provides a durable double-layer waterproof coiled material and a preparation method thereof.

[0005] In the first aspect, the present application provides a durable double-layer waterproof membrane adopting the following technical solution: A durable double-layer waterproof coiled material, comprising a first waterproof layer, a hot melt adhesive layer and a second waterproof layer; the first waterproof layer is an asphalt-based waterproof layer, the second waterproof layer comprises a sand layer, a connecting adhesive layer and a waterproof base material arranged in sequence, the waterproof base material of the second waterproof layer is bonded to the first waterproof layer through a hot melt adhesive layer, and the hot melt adhesive layer and the connecting adhesive layer are both made of waterproof and oil-resistant hot melt adhesive; The raw materials of the waterproof and oil-resistant hot melt adhesive include 90-95wt% of a base rubber hot melt adhesive and 5-10wt% of a reinforcing adhesive, wherein the reinforcing adhesive includes an amino-terminated polyurea prepolymer, a hydroxyl-terminated polyurethane prepolymer, a blocked isocyanate crosslinking agent, and a catalyst; The molar ratio of the amino-terminated polyurea prepolymer, the hydroxyl-terminated polyurethane prepolymer and the blocked isocyanate crosslinking agent is (1-2): (3.5-6): (1.5-3.5).

[0006] In order to improve the penetration of small molecule motor oil in the asphalt-based waterproof layer, the hot melt adhesive layer between the second waterproof layer and the first waterproof layer and the connecting adhesive layer between the sand layer and the waterproof substrate are all made of waterproof and oil-resistant hot melt adhesive. The waterproof and oil-resistant hot melt adhesive is different from other hot melt adhesives in that the raw materials for preparing the waterproof and oil-resistant hot melt adhesive include basic rubber hot melt adhesive and reinforcing adhesive, and the reinforcing adhesive is made of a specific ratio of terminal amino polyurea prepolymer, terminal hydroxyl polyurethane prepolymer, blocked isocyanate crosslinking agent and catalyst. Among them, the terminal amino component is added in the form of a macromolecular terminal amino polyurea prepolymer, and the terminal hydroxyl component is added in the form of a macromolecular terminal hydroxyl polyurethane prepolymer, which can adjust the curing rate of the hot melt adhesive layer to prevent the reaction from being too violent and affecting the bonding stability of the first waterproof layer and the second waterproof layer. By introducing a blocked isocyanate cross-linking agent, the problem of the waterproof and oil-resistant hot melt adhesive starting to cross-link before the second waterproof layer is compounded with the first waterproof layer can be prevented. When the second waterproof layer needs to be compounded with the first waterproof layer, the blocked isocyanate cross-linking agent is deblocked by increasing the temperature, and the terminal amino polyurea prepolymer and the terminal hydroxyl polyurethane prepolymer react with the isocyanate group on the deblocked blocked isocyanate cross-linking agent to achieve cross-linking. On the one hand, a firm compound of the first waterproof layer and the second waterproof layer can be achieved, and on the other hand, the structural tightness and hydrolysis resistance of the hot melt adhesive layer and the connecting adhesive layer can be improved through cross-linking, which can slow down the penetration of small molecule motor oils and extend the service life of the waterproof membrane, which is conducive to achieving the purpose of the double-layer waterproof membrane having the same life as the building.

[0007] In addition, the application introduces a blocked isocyanate crosslinker in an appropriate excess, which can enable the hot melt adhesive layer to continue to play a crosslinking role after the waterproof membrane is completed, which is beneficial to further prevent the penetration of small molecule oils and improve the hydrolysis resistance, and can promote the further extension of the service life of the waterproof membrane. However, the amount of blocked isocyanate crosslinker added is not necessarily the more the better. When it exceeds the scope of this application, the waterproof and oil-resistant hot melt adhesive will produce gelation, abnormal viscosity, and uneven coating.

[0008] In some specific embodiments, the amino-terminated polyurea prepolymer is a prepolymer product of the reaction of polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane and polyisocyanate, wherein the molar ratio of polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane to polyisocyanate is (0.3-0.5):(0.1-0.2):(0.5-0.7):(0.1-0.2):1.

[0009] In the present application, the amino-terminated polyurea prepolymer is a prepolymer product of polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane and polyisocyanate in a specific ratio. Under the joint action of polyether ammonium segments, aromatic groups, polypropylene glycol segments and polysiloxane segments, it is beneficial to further improve the bonding performance of the waterproof and oil-resistant hot melt adhesive between the layers of the roll material and improve the peeling strength between the double-layer waterproof roll material and the post-cast concrete, and improve the resistance of the waterproof and oil-resistant sol to small molecule motor oil, thereby improving the bonding durability between the layers of the waterproof roll material. In addition, the waterproof and oil-resistant hot melt adhesive also has excellent tensile strength, heat aging resistance and hydrolysis resistance, which can promote the further improvement of the tensile strength of the waterproof roll material and help to extend the service life of the double-layer waterproof roll material.

[0010] In some specific embodiments, the molecular weight of the polyoxypropylene diamine is 1500-2500, and the molecular weight of the polyoxypropylene triamine is 4500-5500.

[0011] In some specific embodiments, in the amino-terminated phenyl polypropylene glycol, the degree of polymerization of the polypropylene glycol segment is 35-40, and in the amino-terminated polysiloxane, the degree of polymerization of the polysiloxane segment is 40-50.

[0012] The present application further optimizes the molecular weight range of each raw material in the above-mentioned polyamino polyurea prepolymer, which is beneficial to improving the viscosity difference between the reinforcing adhesive and the base rubber hot melt adhesive, and is beneficial to the uniform mixing of the base rubber hot melt adhesive and the reinforcing adhesive.

[0013] In some specific embodiments, the preparation method of the amino-terminated polyurea prepolymer is as follows: The polyisocyanate is dissolved in a solvent, and then polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol and amino-terminated polysiloxane are added dropwise to the polyisocyanate under nitrogen protection, and the temperature is controlled at 10-20° C. to carry out a prepolymerization reaction. After the reaction is completed, the solvent is removed in vacuo to obtain an amino-terminated polyurea prepolymer.

[0014] In some specific embodiments, the hydroxyl-terminated polyurethane prepolymer is prepared by reacting polyether polyol and polyisocyanate in a molar ratio of 1:(0.5-0.6).

[0015] In some specific embodiments, the molecular weight of the polyether polyol is 1000-2000.

[0016] In some specific embodiments, the preparation method of the hydroxyl-terminated polyurethane prepolymer is as follows: The polyether polyol is vacuum dehydrated and then cooled to 40-50°C, polyisocyanate is added under nitrogen protection, and the reaction temperature is controlled to be 70-105°C for prepolymerization. After the reaction is completed, vacuum degassing is performed to obtain a hydroxyl-terminated polyurethane prepolymer.

[0017] In some specific embodiments, the blocked isocyanate cross-linking agent is at least one of methyl ethyl ketone oxime blocked isocyanate, ε-caprolactam blocked isocyanate, and p-nitrophenol blocked isocyanate.

[0018] In some specific embodiments, the waterproof substrate is a polymer sheet or an asphalt roll.

[0019] In some specific embodiments, the base rubber hot melt adhesive includes rubber, tackifying resin, softener and antioxidant, and the weight ratio of rubber, tackifying resin, softener and antioxidant is (20-35): (25-35): (5.5-20.5): (0.5-1.5).

[0020] The rubber includes but is not limited to styrene-isoprene-styrene rubber and butyl rubber.

[0021] Tackifying resins include, but are not limited to, rosin resins, petroleum resins, and terpene resins.

[0022] Softeners include, but are not limited to, N4006 naphthenic oil, N4010 naphthenic oil, and polyisobutylene.

[0023] Anti-aging agents include but are not limited to antioxidant 1010 and antioxidant 168.

[0024] In a second aspect, the present application provides a method for preparing a durable double-layer waterproof roll, comprising the following steps: The base rubber hot melt adhesive and the reinforcing adhesive are put into a glue box with a temperature of 140-160° C. for gluing, and then the adhesive is coated on the surfaces of both sides of the waterproof substrate of the second waterproof layer to form a hot melt adhesive layer and a connecting adhesive layer on the surfaces of both sides of the waterproof substrate respectively, and the thickness of the hot melt adhesive layer and the connecting adhesive layer is 100-600 μm, and then the surface of the connecting adhesive layer is uniformly sandblasted to form a sand layer, and a release film is compounded on the surface of the hot melt adhesive layer, and then rolled up to obtain a single-layer waterproof roll; The single-layer waterproof membrane is unrolled, the release film is removed, and the hot melt adhesive layer on the single-layer waterproof membrane is compounded with the first waterproof layer to obtain a durable double-layer waterproof membrane.

[0025] In the glue box, the base rubber hot melt adhesive and the reinforcing adhesive are evenly mixed, and the blocked isocyanate cross-linking agent in the reinforcing adhesive begins to be unblocked, and the adhesive layer is cross-linked to obtain a high molecular weight, micro-cross-linked structure, small molecule oil resistance, and long life waterproof and oil-resistant hot melt adhesive. The waterproof substrate and the sand layer are connected, and the first waterproof layer and the second waterproof layer are connected by the waterproof and oil-resistant hot melt adhesive, which can effectively improve the stability of the double-layer waterproof membrane, greatly extend the service life of the double-layer waterproof membrane, and help achieve the purpose of having the life of the double-layer waterproof membrane be the same as the life of the building.

[0026] In summary, this application at least includes the following beneficial technical effects: (1) The waterproof and oil-resistant hot melt adhesive of the present application includes a base rubber hot melt adhesive and a reinforcing adhesive. The introduction of a specific reinforcing adhesive improves the waterproof and oil-resistant properties of the waterproof hot melt adhesive, effectively improving the bonding stability and durability between the layers of the double-layer waterproof membrane, which is beneficial to extending the service life of the double-layer waterproof membrane and achieving the purpose of the double-layer waterproof membrane having the same service life as the building.

[0027] (2) In the present application, the amino-terminated polyurea prepolymer is preferably a prepolymer product of polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane and polyisocyanate in a specific ratio. Under the coordinated action of polyether ammonium segments, aromatic groups, polypropylene glycol segments and polysiloxane segments, it is beneficial to further improve the bonding performance of the waterproof and oil-resistant hot melt adhesive to the layers of the coiled material, and improve the resistance of the waterproof and oil-resistant sol to small molecule motor oils, thereby improving the bonding durability between the layers of the waterproof coiled material. In addition, the waterproof and oil-resistant hot melt adhesive also has excellent tensile strength, heat aging resistance and hydrolysis resistance, which can promote the further improvement of the tensile strength of the waterproof coiled material and help to extend the service life of the double-layer waterproof coiled material. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic structural diagram of a durable double-layer waterproof membrane according to an embodiment of the present application.

[0029] Description of reference numerals: 1. First waterproof layer; 2. Hot melt adhesive layer; 3. Second waterproof layer; 31. Sand layer; 32. Connecting adhesive layer; 33. Waterproof base material. DETAILED DESCRIPTION

[0030] The present application is further described below in conjunction with specific experiments.

[0031] Preparation Example [Preparation Example 1-1] A reinforcing adhesive comprising 10 mol of amino-terminated polyurea prepolymer, 60 mol of hydroxyl-terminated polyurethane prepolymer, 35 mol of blocked isocyanate crosslinking agent and 0.1 mol of catalyst; The amino-terminated polyurea prepolymer is obtained by reacting 3 mol of polyoxypropylene diamine, 2 mol of polyoxypropylene triamine, 7 mol of amino-terminated phenyl polypropylene glycol, 1 mol of bisaminopropyl polydimethylsiloxane and 10 mol of diphenylmethane diisocyanate; wherein the molecular weight of the polyoxypropylene diamine is 2000; the molecular weight of the polyoxypropylene triamine is 3000; in the amino-terminated phenyl polypropylene glycol, the degree of polymerization of the polypropylene glycol segment is 35; in the bisaminopropyl polydimethylsiloxane, the degree of polymerization of the dimethylsiloxane segment is 50; the preparation method of the amino-terminated polyurea prepolymer is as follows: Dissolve diphenylmethane diisocyanate in a solvent, then add polyoxypropylene diamine, polyoxypropylene triamine, terminal aminophenyl polypropylene glycol and bisaminopropyl polydimethylsiloxane dropwise into the diphenylmethane diisocyanate under nitrogen protection, control the temperature at 10°C to react for 4 hours, and remove the solvent in vacuo after the reaction to obtain a terminal amino polyurea prepolymer.

[0032] The hydroxyl-terminated polyurethane prepolymer is prepared by reacting 10 mol of polytetramethylene glycol and 5 mol of diphenylmethane diisocyanate, wherein the molecular weight of the polytetramethylene glycol is 1000. The preparation method of the hydroxyl-terminated polyurethane prepolymer is as follows: After vacuum dehydration of polytetrahydrofuran ether diol, the temperature was lowered to 50°C, diphenylmethane diisocyanate was added under nitrogen protection, and the reaction temperature was controlled at 70°C for 4 hours. After the reaction was completed, vacuum degassing was performed to obtain a hydroxyl-terminated polyurethane prepolymer.

[0033] The blocked isocyanate crosslinking agent adopts methyl ethyl ketone oxime blocked isocyanate.

[0034] The catalyst is specifically dibutyltin dilaurate.

[0035] [Preparation Example 1-2] A reinforcing adhesive comprising 20 mol of amino-terminated polyurea prepolymer, 35 mol of hydroxyl-terminated polyurethane prepolymer, 15 mol of blocked isocyanate crosslinking agent and 0.1 mol of catalyst; The amino-terminated polyurea prepolymer is obtained by reacting 5 mol of polyoxypropylene diamine, 1 mol of polyoxypropylene triamine, 5 mol of amino-terminated phenyl polypropylene glycol, 2 mol of bisaminopropyl polydimethylsiloxane and 10 mol of diphenylmethane diisocyanate; wherein the molecular weight of the polyoxypropylene diamine is 2000; the molecular weight of the polyoxypropylene triamine is 3000; in the amino-terminated phenyl polypropylene glycol, the degree of polymerization of the polypropylene glycol segment is 40; in the bisaminopropyl polydimethylsiloxane, the degree of polymerization of the dimethylsiloxane segment is 40; the preparation method of the amino-terminated polyurea prepolymer is as follows: Dissolve diphenylmethane diisocyanate in a solvent, then add polyoxypropylene diamine, polyoxypropylene triamine, terminal aminophenyl polypropylene glycol and bisaminopropyl polydimethylsiloxane dropwise into the diphenylmethane diisocyanate under nitrogen protection, control the temperature at 20°C to react for 4 hours, remove the solvent in vacuo after the reaction is completed, and obtain a terminal amino polyurea prepolymer.

[0036] The hydroxyl-terminated polyurethane prepolymer is prepared by reacting 10 mol of polytetramethylene glycol and 5 mol of diphenylmethane diisocyanate, wherein the molecular weight of the polytetramethylene glycol is 2000. The preparation method of the hydroxyl-terminated polyurethane prepolymer is as follows: After vacuum dehydration of polytetrahydrofuran ether diol, the temperature was lowered to 50°C, diphenylmethane diisocyanate was added under nitrogen protection, and the reaction temperature was controlled at 105°C for 3 hours. After the reaction was completed, vacuum degassing was performed to obtain a terminal hydroxyl polyurethane prepolymer.

[0037] The blocked isocyanate crosslinking agent adopts ε-caprolactam blocked isocyanate.

[0038] The catalyst is specifically dibutyltin dilaurate.

[0039] [Preparation Example 1-3] A reinforcing adhesive, which differs from [Preparation Example 1-1] in that the molar amounts of the components in the amino-terminated polyurea prepolymer are different. In this preparation example, the amino-terminated polyurea prepolymer is obtained by reacting 7 mol of polyoxypropylene diamine, 1 mol of polyoxypropylene triamine, 2 mol of amino-terminated phenyl polypropylene glycol, 3 mol of bisaminopropyl polydimethylsiloxane and 10 mol of diphenylmethane diisocyanate.

[0040] [Preparation Example 1-4] A reinforcing adhesive, which differs from [Preparation Example 1-1] in that the molar amounts of the components in the amino-terminated polyurea prepolymer are different. In this preparation example, the amino-terminated polyurea prepolymer is obtained by reacting 3 mol of polyoxypropylene diamine, 7 mol of polyoxypropylene triamine, 2 mol of amino-terminated phenyl polypropylene glycol, 1 mol of bisaminopropyl polydimethylsiloxane and 10 mol of diphenylmethane diisocyanate.

[0041] [Preparation Example 1-5] A reinforcing glue, which is different from [Preparation Example 1-1] in that: in the reinforcing glue, the amount of blocked isocyanate cross-linking agent is different. In this preparation example, the molar amount of the blocked isocyanate cross-linking agent is 40 mol.

[0042] [Preparation Example 2-1] A waterproof and oil-resistant hot melt adhesive, comprising 90wt% of a base rubber hot melt adhesive and 10wt% of a reinforcing adhesive, wherein the base rubber hot melt adhesive is composed of 35kg of styrene-isoprene-styrene rubber (Kraton D1113), 30kg of a tackifying resin (145 rosin resin), 5.5kg of a softener (KN4006 cyclohexane oil) and 0.5kg of an antioxidant (a composition of antioxidant 1010 and antioxidant 168 in a weight ratio of 3:1), and the reinforcing adhesive adopts the reinforcing adhesive in [Preparation Example 1-1].

[0043] [Preparation Example 2-2] A waterproof and oil-resistant hot melt adhesive, comprising 95wt% of a base rubber hot melt adhesive and 5wt% of a reinforcing adhesive, wherein the base rubber hot melt adhesive comprises 20kg of styrene-isoprene-styrene rubber (Kraton D1113), 30kg of a tackifying resin (C5 petroleum resin Luhua A1100), 20.5kg of a softener (polyisobutylene PB1300) and 0.5kg of an antioxidant (a composition of antioxidant 1010 and antioxidant 168 in a weight ratio of 3:1), and the reinforcing adhesive adopts the reinforcing adhesive in [Preparation Example 1-2].

[0044] [Preparation Example 2-3] A waterproof and oil-resistant hot melt adhesive, which differs from [Preparation Example 2-1] in that the reinforced adhesive adopts the reinforced adhesive in [Preparation Example 1-3].

[0045] [Preparation Example 2-4] A waterproof and oil-resistant hot melt adhesive, which differs from [Preparation Example 2-1] in that the reinforcing adhesive adopts the reinforcing adhesive in [Preparation Example 1-4].

[0046] [Preparation Example 2-5] A hot melt adhesive, which differs from [Preparation Example 2-1] in that the reinforced adhesive adopts the reinforced adhesive in [Preparation Example 1-5].

[0047] [Preparation Example 2-6] A hot melt adhesive, which differs from [Preparation Example 2-1] in that the reinforcing adhesive is replaced by a base rubber hot melt adhesive of equal mass. Example

[0048] [Example 1] A durable double layer waterproof membrane, refer to Figure 1 The double-layer waterproof membrane is composed of a first waterproof layer 1, a hot melt adhesive layer 2 and a second waterproof layer 3 from bottom to top. The first waterproof layer 1 is an asphalt-based waterproof layer, and the second waterproof layer 3 is composed of a sand layer 31, a connecting adhesive layer 32 and a waterproof substrate 33 from top to bottom. Among them, the hot melt adhesive layer 2 and the connecting adhesive layer 32 are both made of the waterproof and oil-resistant hot melt adhesive in [Preparation Example 2-1], and the waterproof substrate 33 is an asphalt-based waterproof membrane.

[0049] In this embodiment, the method for preparing the durable double-layer waterproof membrane comprises the following steps: Put the waterproof and oil-resistant hot melt adhesive into a glue box with a temperature of 140-160° C. for gluing, and then apply the adhesive on the surfaces of both sides of the waterproof substrate of the second waterproof layer to form a hot melt adhesive layer and a connecting adhesive layer on the surfaces of both sides of the waterproof substrate, the thickness of the hot melt adhesive layer and the connecting adhesive layer is 100 μm, then uniformly sandblast the surface of the connecting adhesive layer to form a sand layer, compound a release film on the surface of the hot melt adhesive layer, and then roll it up to obtain a single-layer waterproof roll; The single-layer waterproof membrane is unrolled, the release film is removed, and the hot melt adhesive layer on the single-layer waterproof membrane is compounded with the first waterproof layer to obtain a durable double-layer waterproof membrane.

[0050] [Example 2] A durable double-layer waterproof roll material, which differs from [Example 1] in that: the hot melt adhesive layer and the connecting adhesive layer are both made of the waterproof and oil-resistant hot melt adhesive in [Preparation Example 2-2].

[0051] [Example 3] A durable double-layer waterproof roll material, which differs from [Example 1] in that: the hot melt adhesive layer and the connecting adhesive layer are both made of the waterproof and oil-resistant hot melt adhesive in [Preparation Example 2-3].

[0052] [Example 4] A durable double-layer waterproof roll material, which differs from [Example 1] in that: the hot melt adhesive layer and the connecting adhesive layer are both made of the waterproof and oil-resistant hot melt adhesive in [Preparation Example 2-4].

[0053] Comparative Example [Comparative Example 1] A double-layer waterproof roll material, which differs from [Example 1] in that: the hot melt adhesive layer and the connecting adhesive layer are both made of the hot melt adhesive in [Preparation Example 2-5].

[0054] [Comparative Example 2] A double-layer waterproof roll material, which differs from [Example 1] in that: the hot melt adhesive layer and the connecting adhesive layer are both made of the hot melt adhesive in [Preparation Example 2-6].

[0055] Performance testing The water penetration resistance test, impact resistance test, low temperature bending test, oil permeability test, peeling strength test between membranes, tensile strength test and peeling strength test between double-layer waterproof membrane and post-cast concrete of the double-layer waterproof membrane in each embodiment and comparative example were tested with reference to GB / T 23457-2017. Among them, the peeling strength test between the rolls was carried out on samples placed for 0 days and placed at 70℃ for 28 days respectively; the tensile strength test was carried out on samples after no treatment, heat aging treatment (placed at 70℃ for 28 days), and immersion treatment (immersed in water at 23℃ for 28 days) respectively; in the test of peeling strength with post-cast concrete, after preparing the test specimens with reference to the contents recorded in Sections 6.20.1.1 and 6.20.1.2 of GB / T 23457-2017, the test specimens were directly taken to test the peeling strength between the double-layer waterproofing roll and the post-cast concrete (corresponding to the data of 0 days). In addition, after the test specimens were placed in an environment of 70℃ for 28 days, samples were taken again to test the peeling strength between the double-layer waterproofing roll and the post-cast concrete (corresponding to the data of 70℃, 28 days).

[0056] Table 1

[0057] Table 2

[0058] Table 3

[0059] Table 4

[0060] Combined with the test data recorded in Tables 1 to 4 above, it can be seen that the double-layer waterproof membrane in Examples 1 to 4 of the present application has excellent water resistance, impact resistance, low-temperature bending resistance and oil penetration resistance. At the same time, the peel strength between the double-layer waterproof membrane and the membrane can still reach more than 1.2N / mm after being placed at 70°C for 28 days. When testing the peel strength between the membrane and the post-cast concrete, the peel strength between the double-layer waterproof membrane and the concrete can still reach more than 1.6N / mm after the sample is placed at 70°C for 28 days, indicating that the hot melt adhesive layer and the connecting adhesive layer in the double-layer waterproof membrane have good resistance to small molecule motor oil, and the tensile strength of the double-layer waterproof membrane after thermal aging or immersion in water can be maintained at more than 20MPa, that is, the double-layer waterproof membrane in the present application has excellent comprehensive performance, and the double-layer waterproof membrane has a long service life, which is conducive to achieving the purpose of the double-layer waterproof membrane having the same life as the building.

[0061] The difference between Comparative Example 1 and Example 1 is that in the hot melt adhesive used in Comparative Example 1, the blocked diisocyanate contained in the reinforcing adhesive exceeds the scope of the present application. Combined with the test results recorded in Tables 1 to 3 above, it can be seen that when the blocked diisocyanate contained in the reinforcing adhesive in Comparative Example 1 is seriously excessive, the waterproof and oil-resistant hot melt adhesive will produce gelation, abnormal viscosity, and uneven coating, resulting in a decrease in the water resistance, impact resistance, low-temperature bending and oil penetration resistance of the double-layer waterproof membrane, and the peel strength between the membranes and the peel strength between the double-layer waterproof membrane and the post-cast concrete are significantly reduced after heat treatment. At the same time, the tensile strength, heat aging resistance and water resistance of the double-layer waterproof membrane in Comparative Example 1 are also worse than those in Example 1.

[0062] The difference between Comparative Example 2 and Example 1 is that no reinforcing adhesive is added to the hot melt adhesive used in Comparative Example 2. Combined with the test results recorded in Tables 1 to 3 above, it can be seen that when the hot melt adhesive in Comparative Example 2 is not added with reinforcing adhesive, the water penetration resistance and oil penetration resistance of the double-layer waterproof roll are both reduced, and the peeling strength between the rolls and the peeling strength between the double-layer waterproof roll and the post-cast concrete are significantly reduced after heat treatment, indicating that the performance of the hot melt adhesive layer and the connecting adhesive layer against small molecule oil is significantly reduced. At the same time, the tensile strength, heat aging resistance and water resistance of the double-layer waterproof roll in Comparative Example 2 are also worse than those in Example 1.

[0063] The difference between Example 3-4 and Example 1 is that in the waterproof and oil-resistant hot melt adhesive used in Example 3-4, the molar ratio of polyoxypropylene diamine, polyoxypropylene triamine, terminal aminophenyl polypropylene glycol, terminal amino polysiloxane to diisocyanate in the terminal amino polyurea prepolymer is not within the preferred range of the present application. Combined with the test results recorded in Tables 1 to 3, it can be seen that the molar ratio of polyoxypropylene diamine, polyoxypropylene triamine, terminal aminophenyl polypropylene glycol, terminal amino polysiloxane to diisocyanate in the terminal amino polyurea prepolymer is not within the preferred range of the present application. The molar ratio is in the range of (0.3-0.5): (0.1-0.2): (0.5-0.7): (0.1-0.2): 1, which is beneficial to further improve the bonding strength between the membranes and the peeling strength between the double-layer waterproof membrane and the post-cast concrete, and can reduce the influence of small molecule motor oil on the bonding performance between the membranes and the peeling strength between the double-layer waterproof membrane and the post-cast concrete, while further improving the tensile strength, heat aging resistance and water resistance of the double-layer waterproof membrane.

[0064] This specific implementation manner is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the specific implementation manner as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A durable double-layer waterproof membrane, characterized by: It comprises a first waterproof layer, a hot melt adhesive layer and a second waterproof layer; the first waterproof layer is an asphalt-based waterproof layer, the second waterproof layer comprises a sand layer, a connecting adhesive layer and a waterproof base material which are arranged in sequence, the waterproof base material of the second waterproof layer is bonded to the first waterproof layer through a hot melt adhesive layer, and the hot melt adhesive layer and the connecting adhesive layer are both made of waterproof and oil-resistant hot melt adhesive; The raw materials of the waterproof and oil-resistant hot melt adhesive include 90-95wt% of a base rubber hot melt adhesive and 5-10wt% of a reinforcing adhesive, wherein the reinforcing adhesive includes an amino-terminated polyurea prepolymer, a hydroxyl-terminated polyurethane prepolymer, a blocked isocyanate crosslinking agent, and a catalyst; The molar ratio of the amino-terminated polyurea prepolymer, the hydroxyl-terminated polyurethane prepolymer and the blocked isocyanate crosslinking agent is (1-2): (3.5-6): (1.5-3.5).

2. A durable double-layer waterproofing membrane according to claim 1, characterized in that: The amino-terminated polyurea prepolymer is a prepolymer product of the reaction of polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane and polyisocyanate, wherein the molar ratio of the polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane to polyisocyanate is (0.3-0.5):(0.1-0.2):(0.5-0.7):(0.1-0.2):

1.

3. A durable double-layer waterproofing membrane according to claim 2, characterized in that: In the amino-terminated phenyl polypropylene glycol, the polymerization degree of the polypropylene glycol chain segment is 35-40.

4. A durable double-layer waterproofing membrane according to claim 2, characterized in that: In the amino-terminated polysiloxane, the degree of polymerization of the polysiloxane chain segment is 40-50.

5. A durable double-layer waterproofing membrane according to any one of claims 2 to 4, characterized in that: The preparation method of the amino-terminated polyurea prepolymer is as follows: The polyisocyanate is dissolved in a solvent, and then polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol and amino-terminated polysiloxane are added dropwise to the polyisocyanate under nitrogen protection, and the temperature is controlled at 10-20° C. to carry out a prepolymerization reaction. After the reaction is completed, the solvent is removed in vacuo to obtain an amino-terminated polyurea prepolymer.

6. A durable double-layer waterproofing membrane according to any one of claims 1 to 4, characterized in that: The hydroxyl-terminated polyurethane prepolymer is prepared by reacting polyether polyol and polyisocyanate in a molar ratio of 1:(0.5-0.6).

7. A durable double-layer waterproofing membrane according to claim 6, characterized in that: The molecular weight of the polyether polyol is 1000-2000.

8. A durable double-layer waterproofing membrane according to claim 6, characterized in that: The preparation method of the hydroxyl-terminated polyurethane prepolymer is as follows: The polyether polyol is vacuum dehydrated and then cooled to 40-50°C, polyisocyanate is added under nitrogen protection, and the reaction temperature is controlled to be 70-105°C for prepolymerization. After the reaction is completed, vacuum degassing is performed to obtain a hydroxyl-terminated polyurethane prepolymer.

9. A durable double-layer waterproofing membrane according to claim 1, characterized in that: The blocked isocyanate cross-linking agent is at least one of methyl ethyl ketone oxime blocked isocyanate, ε-caprolactam blocked isocyanate and p-nitrophenol blocked isocyanate.

10. A method for preparing a durable double-layer waterproofing membrane according to any one of claims 1 to 9, characterized in that: The following steps are involved: The base rubber hot melt adhesive and the reinforcing adhesive are put into a glue box with a temperature of 140-160° C. for gluing, and then the adhesive is coated on the surfaces of both sides of the waterproof substrate of the second waterproof layer to form a hot melt adhesive layer and a connecting adhesive layer on the surfaces of both sides of the waterproof substrate respectively, and the thickness of the hot melt adhesive layer and the connecting adhesive layer is 100-600 μm, and then the surface of the connecting adhesive layer is uniformly sandblasted to form a sand layer, and a release film is compounded on the surface of the hot melt adhesive layer, and then rolled up to obtain a single-layer waterproof roll; The single-layer waterproof membrane is unrolled, the release film is removed, and the hot melt adhesive layer on the single-layer waterproof membrane is compounded with the first waterproof layer to obtain a durable double-layer waterproof membrane.

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