A Durable Double-Layer Waterproof Coil and Its Preparation Method

Abstract

The present invention discloses a durable double-layer waterproof coiled material and a preparation method thereof, which relates to the field of building waterproof materials. The double-layer waterproof coiled material includes a first waterproof layer, a hot melt adhesive layer and a second waterproof layer; the first waterproof layer is an asphalt-based waterproof layer, and the second waterproof layer includes a sand layer, a connecting adhesive layer and a waterproof substrate arranged in sequence. Both the hot melt adhesive layer and the connecting adhesive layer are 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 basic rubber hot melt adhesive and 5-10wt% of reinforcing adhesive. 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). The waterproof and oil-resistant hot melt adhesive in the double-layer waterproof coiled material of the present application can slow down the penetration of small molecule engine oil, can extend the service life of the waterproof coiled material, and is beneficial to achieving the purpose of the same service life of the waterproof coiled material and the building.

Description

Technical Field

[0001] The present application relates to the field of building materials waterproofing materials, and particularly to a durable double-layer waterproof coiled material and a preparation method thereof. Background Art

[0002] In the construction field, waterproof projects are crucial for ensuring the structural integrity and durability of buildings. Among them, the double-layer waterproof coiled material has an additional layer of waterproof substrate compared to the single-layer waterproof coiled material, and generally has better waterproof performance than the single-layer waterproof coiled material. Therefore, the double-layer waterproof coiled material has been widely applied and promoted.

[0003] Currently, the problems encountered in the use of double-layer waterproof coiled materials are as follows: The asphalt-based waterproof layer has a low cost, so most people are keen on using the asphalt-based waterproof layer as the waterproof substrate. However, there are a large number of small molecule lubricating oils in the asphalt-based waterproof layer. These small molecule lubricating oils are easily penetrated into the hot melt adhesive layer where the second waterproof layer is bonded to the first waterproof layer. And the existing hot melt adhesive layer has limited resistance to small molecule lubricating oils. After 28 days of placement of the double-layer waterproof coiled material, the peel strength between the coiled materials will be significantly reduced, affecting the service life of the double-layer waterproof coiled material. Summary of the Invention

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

[0005] In the first aspect, a durable double-layer waterproof coiled material provided by the present application adopts the following technical solution:

[0006] A durable double-layer waterproof coiled material includes a first waterproof layer, a hot melt adhesive layer, and a second waterproof layer; the first waterproof layer is an asphalt-based waterproof layer, and the second waterproof layer includes a sand layer, a connecting adhesive layer, and a waterproof substrate arranged in sequence. The waterproof substrate of the second waterproof layer is bonded to the first waterproof layer through the hot melt adhesive layer, and both the hot melt adhesive layer and the connecting adhesive layer are made of waterproof and oil-resistant hot melt adhesive;

[0007] The raw materials of the waterproof and oil-resistant hot melt adhesive include 90-95wt% of a basic rubber hot melt adhesive and 5-10wt% of a reinforcing adhesive. The reinforcing adhesive includes an amino-terminated polyurea prepolymer, a hydroxyl-terminated polyurethane prepolymer, a blocked isocyanate crosslinking agent, and a catalyst;

[0008] Among them, 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).

[0009] This application is for improving the penetration of small-molecule engine 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 both use a waterproof and oil-resistant hot-melt adhesive. What is different between the waterproof and oil-resistant hot-melt adhesive and other hot-melt adhesives is that the preparation raw materials of the waterproof and oil-resistant hot-melt adhesive include a basic rubber hot-melt adhesive and a reinforcing adhesive. The reinforcing adhesive is prepared from a terminal amino polyurea prepolymer, a terminal hydroxyl polyurethane prepolymer, a blocked isocyanate crosslinking agent, and a catalyst in a specific ratio. 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 and prevent the reaction from being too violent, affecting the bonding stability between the first waterproof layer and the second waterproof layer. By introducing the blocked isocyanate crosslinking agent, the problem that the waterproof and oil-resistant hot-melt adhesive starts to crosslink before the second waterproof layer and the first waterproof layer are compounded can be prevented. When the second waterproof layer and the first waterproof layer need to be compounded, the blocked isocyanate crosslinking agent is deblocked by heating, and the terminal amino polyurea prepolymer and the terminal hydroxyl polyurethane prepolymer react with the isocyanate groups on the deblocked blocked isocyanate crosslinking agent to achieve crosslinking. On the one hand, it can achieve the firm compounding of the first waterproof layer and the second waterproof layer. On the other hand, it can improve the structural compactness and hydrolysis resistance of the hot-melt adhesive layer and the connecting adhesive layer through crosslinking, slow down the penetration of small-molecule engine oil, and extend the service life of the waterproof coiled material, which is conducive to achieving the purpose of the same service life of the double-layer waterproof coiled material and the building.

[0010] In addition, this application appropriately and excessively introduces the blocked isocyanate crosslinking agent, which can prompt the hot-melt adhesive layer to continuously play a crosslinking role after the waterproof coiled material is constructed, which is beneficial to further preventing the penetration of small-molecule engine oil and improving the hydrolysis resistance, and can promote the further extension of the service life of the waterproof coiled material. However, the incorporation amount of the blocked isocyanate crosslinking agent is not the more the better. When it exceeds the scope of this application, the waterproof and oil-resistant hot-melt adhesive will produce a gel phenomenon, with abnormal viscosity and uneven coating problems.

[0011] In some specific embodiments, the terminal amino polyurea prepolymer is a prepolymer product obtained by the reaction of polyoxypropylene diamine, polyoxypropylene triamine, terminal amino phenyl polypropylene glycol, terminal amino polysiloxane and polyisocyanate. Among them, the molar ratio of polyoxypropylene diamine, polyoxypropylene triamine, terminal amino phenyl polypropylene glycol, terminal amino polysiloxane to polyisocyanate is (0.3 - 0.5):(0.1 - 0.2):(0.5 - 0.7):(0.1 - 0.2):1.

[0012] In this application, the amino-terminated polyurea prepolymer is a prepolymer product obtained by reacting polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane with polyisocyanate in a specific ratio. Under the combined action of polyether ammonium segments, aromatic groups, polypropylene glycol segments and polysiloxane segments, it is beneficial to further improve the adhesion performance between layers of the waterproof and oil-resistant hot melt adhesive to the coil layers and improve the peel strength between the double-layer waterproof coil and the cast-in-place concrete, and improve the performance of the waterproof and oil-resistant sol to resist small molecule engine oil, thereby improving the adhesion durability between layers of the waterproof coil. In addition, this waterproof and oil-resistant hot melt adhesive also has excellent tensile strength, heat aging performance and hydrolysis resistance, which can promote the further improvement of the tensile strength of the waterproof coil and is beneficial to extending the service life of the double-layer waterproof coil.

[0013] 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.

[0014] 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.

[0015] By further optimizing the molecular weight range of each raw material in the above-mentioned polyamino polyurea prepolymer in this application, it is beneficial to improve 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.

[0016] In some specific embodiments, the preparation method of the amino-terminated polyurea prepolymer is as follows:

[0017] Dissolve the polyisocyanate in a solvent, and then dropwise add polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol and amino-terminated polysiloxane into the polyisocyanate under nitrogen protection, and control the temperature at 10 - 20 °C for prepolymerization reaction. After the reaction is completed, the solvent is removed by vacuum to obtain the amino-terminated polyurea prepolymer.

[0018] In some specific embodiments, the hydroxyl-terminated polyurethane prepolymer is prepared by reacting a polyether polyol with a polyisocyanate in a molar ratio of 1:(0.5 - 0.6).

[0019] In some specific embodiments, the molecular weight of the polyether polyol is 1000 - 2000.

[0020] In some specific embodiments, the preparation method of the hydroxyl-terminated polyurethane prepolymer is as follows:

[0021] After vacuum dehydrating the polyether polyol, cool it down to 40 - 50°C. Under nitrogen protection, add the polyisocyanate and control the reaction temperature at 70 - 105°C for the prepolymerization reaction. After the reaction ends, conduct vacuum degassing to obtain the hydroxyl-terminated polyurethane prepolymer.

[0022] In some specific embodiments, the blocked isocyanate crosslinking agent adopts at least one of methyl ethyl ketone oxime-blocked isocyanate, ε-caprolactam-blocked isocyanate, and p-nitrophenol-blocked isocyanate.

[0023] In some specific embodiments, the waterproof base material adopts a polymer sheet or an asphalt roll material.

[0024] In some specific embodiments, the base rubber hot melt adhesive includes rubber, tackifying resin, softening agent, and anti-aging agent. The weight ratio of rubber, tackifying resin, softening agent, and anti-aging agent is (20 - 35):(25 - 35):(5.5 - 20.5):(0.5 - 1.5).

[0025] Among them, the rubber includes but is not limited to styrene-isoprene-styrene rubber and butyl rubber.

[0026] The tackifying resin includes but is not limited to rosin resin, petroleum resin, and terpene resin.

[0027] The softening agent includes but is not limited to N4006 naphthenic oil, N4010 naphthenic oil, and polyisobutene.

[0028] The anti-aging agent includes but is not limited to antioxidant 1010 and antioxidant 168.

[0029] In a second aspect, a preparation method of a durable double-layer waterproof roll material provided by this application includes the following steps:

[0030] Put the base rubber hot melt adhesive and the reinforcing adhesive into a glue tank at a temperature of 140 - 160°C for melting the glue. Then coat the glue on the surfaces on both sides of the waterproof base material of the second waterproof layer to respectively form a hot melt adhesive layer and a connecting adhesive layer on the surfaces on both sides of the waterproof base material. The thickness of the hot melt adhesive layer and the connecting adhesive layer is 100 - 600 μm. Then evenly spray sand on the surface of the connecting adhesive layer to form a sand layer, and compound a release film on the surface of the hot melt adhesive layer. Then wind it up to obtain a single-layer waterproof roll material;

[0031] Unroll the single-layer waterproof roll material, remove the release film, and compound it with the first waterproof layer through the hot melt adhesive layer on the single-layer waterproof roll material to obtain the durable double-layer waterproof roll material.

[0032] In the glue tank, the base rubber hot melt adhesive and the reinforcing adhesive are uniformly mixed, and the blocked isocyanate cross-linking agent in the reinforcing adhesive begins to unblock, and the glue layer is cross-linked, so as to obtain a waterproof and oil-resistant hot melt adhesive with high molecular weight, micro-crosslinked structure, resistance to small molecule engine oil, and long service life. Connecting the waterproof base material and the sand layer and connecting the first waterproof layer and the second waterproof layer with this waterproof and oil-resistant hot melt adhesive can effectively improve the stability of the double-layer waterproof coiled material and greatly extend the service life of the double-layer waterproof coiled material, which is beneficial to achieving the purpose of the same service life of the double-layer waterproof coiled material and the building.

[0033] To sum up, the present application at least includes the following beneficial technical effects:

[0034] (1) The waterproof and oil-resistant hot melt adhesive of the present application includes a base rubber hot melt adhesive and a reinforcing adhesive. By introducing a specific reinforcing adhesive, the waterproof and oil-resistant performance of the waterproof hot melt adhesive is improved, the bonding stability and durability between layers of the double-layer waterproof coiled material are effectively improved, which is beneficial to extending the service life of the double-layer waterproof coiled material and achieving the purpose of the same service life as the building for the double-layer waterproof coiled material.

[0035] (2) In the present application, the amino-terminated polyurea prepolymer is preferably a prepolymer product obtained by reacting polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane and polyisocyanate in a specific ratio. Under the combined action of the polyether ammonium chain segment, aromatic group, polypropylene glycol chain segment and polysiloxane chain segment, it is beneficial to further improve the bonding performance between layers of the waterproof and oil-resistant hot melt adhesive to the coiled material layer and improve the resistance of the waterproof and oil-resistant sol to small molecule engine oil, thereby improving the bonding durability between layers of the waterproof coiled material. In addition, this waterproof and oil-resistant hot melt adhesive also has excellent tensile strength, heat aging performance and hydrolysis resistance, which can promote the further improvement of the tensile strength of the waterproof coiled material and is beneficial to extending the service life of the double-layer waterproof coiled material. Description of the Drawings

[0036] Figure 1 is a schematic structural diagram of a durable double-layer waterproof coiled material according to an embodiment of the present application.

[0037] Description of the reference numerals:

[0038] 1. The first waterproof layer; 2. The hot melt adhesive layer; 3. The second waterproof layer; 31. The sand layer; 32. The connecting adhesive layer; 33. The waterproof base material. Detailed Embodiments

[0039] The following further illustrates the present application in combination with specific experiments.

[0040] Preparation Examples

[0041]

Preparation Example 1-1

[0042] An enhanced glue, comprising 10 mol of an amino-terminated polyurea prepolymer, 60 mol of a hydroxy-terminated polyurethane prepolymer, 35 mol of a blocked isocyanate crosslinking agent, and 0.1 mol of a catalyst;

[0043] 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 diaminopropyl polydimethylsiloxane with 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 diaminopropyl polydimethylsiloxane, the degree of polymerization of the dimethylsiloxane segment is 50; the preparation method of the amino-terminated polyurea prepolymer is as follows:

[0044] Dissolve the diphenylmethane diisocyanate in a solvent, and then dropwise add the polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol and diaminopropyl polydimethylsiloxane into the diphenylmethane diisocyanate under nitrogen protection, control the temperature at 10 °C and react for 4 h, and after the reaction is completed, remove the solvent by vacuum to obtain the amino-terminated polyurea prepolymer.

[0045] The hydroxy-terminated polyurethane prepolymer is prepared by reacting 10 mol of polytetrahydrofuran ether glycol with 5 mol of diphenylmethane diisocyanate, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000, and the preparation method of the hydroxy-terminated polyurethane prepolymer is as follows:

[0046] Take the polytetrahydrofuran ether glycol, dehydrate it under vacuum and then cool it to 50 °C, add diphenylmethane diisocyanate under nitrogen protection, control the reaction temperature at 70 °C and react for 4 h, and after the reaction is completed, remove the bubbles by vacuum to obtain the hydroxy-terminated polyurethane prepolymer.

[0047] The blocked isocyanate crosslinking agent uses methyl ethyl ketoxime-blocked isocyanate.

[0048] The catalyst specifically uses dibutyltin dilaurate.

[0049]

Preparation Example 1-2

[0050] An enhanced glue, comprising 20 mol of an amino-terminated polyurea prepolymer, 35 mol of a hydroxy-terminated polyurethane prepolymer, 15 mol of a blocked isocyanate crosslinking agent, and 0.1 mol of a catalyst;

[0051] 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 diaminopropyl polydimethylsiloxane with 10 mol of diphenylmethane diisocyanate; wherein, the molecular weight of polyoxypropylene diamine is 2000; the molecular weight of polyoxypropylene triamine is 3000; in the amino-terminated phenyl polypropylene glycol, the degree of polymerization of the polypropylene glycol segment is 40; in the diaminopropyl polydimethylsiloxane, the degree of polymerization of the dimethylsiloxane segment is 40; the preparation method of the amino-terminated polyurea prepolymer is as follows:

[0052] Dissolve diphenylmethane diisocyanate in a solvent, and then dropwise add polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol and diaminopropyl polydimethylsiloxane into diphenylmethane diisocyanate under nitrogen protection, control the temperature at 20 °C and react for 4 h, and after the reaction is completed, remove the solvent under vacuum to obtain the amino-terminated polyurea prepolymer.

[0053] The hydroxy-terminated polyurethane prepolymer is prepared by reacting 10 mol of polytetrahydrofuran ether glycol with 5 mol of diphenylmethane diisocyanate, wherein the molecular weight of polytetrahydrofuran ether glycol is 2000, and the preparation method of the hydroxy-terminated polyurethane prepolymer is as follows:

[0054] Take polytetrahydrofuran ether glycol, dehydrate it under vacuum and then cool it to 50 °C, add diphenylmethane diisocyanate under nitrogen protection, control the reaction temperature at 105 °C and react for 3 h, and after the reaction is completed, remove the bubbles under vacuum to obtain the hydroxy-terminated polyurethane prepolymer.

[0055] The blocked isocyanate crosslinking agent uses ε-caprolactam-blocked isocyanate.

[0056] The catalyst specifically uses dibutyltin dilaurate.

[0057]

Preparation Example 1-3

[0058] An enhanced glue, which is different from

Preparation Example 1-1

[0059]

Preparation Example 1-4

[0060] An enhanced glue, which is different from [Preparation Example 1-1] in that the molar amounts of the components in the terminal amino polyurea prepolymer are different. In this preparation example, the terminal amino polyurea prepolymer is obtained by reacting 3 mol of polyoxypropylene diamine, 7 mol of polyoxypropylene triamine, 2 mol of terminal amino phenyl polypropylene glycol, 1 mol of diaminopropyl polydimethylsiloxane with 10 mol of diphenylmethane diisocyanate.

[0061]

Preparation Example 1-5

[0062] An enhanced glue, which is different from [Preparation Example 1-1] in that the amount of the blocked isocyanate crosslinking agent in the enhanced glue is different. In this preparation example, the molar amount of the blocked isocyanate crosslinking agent is 40 mol.

[0063]

Preparation Example 2-1

[0064] A waterproof and oil-resistant hot melt adhesive, comprising 90 wt% of a base rubber hot melt adhesive and 10 wt% of an enhanced glue. Among them, the base rubber hot melt adhesive consists of 35 kg of styrene-isoprene-styrene rubber (Kraton D1113), 30 kg of tackifying resin (145 rosin resin), 5.5 kg of softening agent (KN4006 naphthenic oil), and 0.5 kg of antioxidant (a composition of antioxidant 1010 and antioxidant 168 with a weight ratio of 3:1), and the enhanced glue uses the enhanced glue in [Preparation Example 1-1].

[0065]

Preparation Example 2-2

[0066] A waterproof and oil-resistant hot melt adhesive, comprising 95 wt% of a base rubber hot melt adhesive and 5 wt% of an enhanced glue. Among them, the base rubber hot melt adhesive includes 20 kg of styrene-isoprene-styrene rubber (Kraton D1113), 30 kg of tackifying resin (C5 petroleum resin Luhua A1100), 20.5 kg of softening agent (polyisobutylene PB1300), and 0.5 kg of antioxidant (a composition of antioxidant 1010 and antioxidant 168 with a weight ratio of 3:1), and the enhanced glue uses the enhanced glue in [Preparation Example 1-2].

[0067]

Preparation Example 2-3

[0068] A waterproof and oil-resistant hot melt adhesive, which is different from [Preparation Example 2-1] in that the enhanced glue uses the enhanced glue in [Preparation Example 1-3].

[0069]

Preparation Example 2-4

[0070] A waterproof and oil-resistant hot melt adhesive, which is different from [Preparation Example 2-1] in that the enhanced glue uses the enhanced glue in [Preparation Example 1-4].

[0071]

Preparation Example 2-5

[0072] A hot melt adhesive, which is different from [Preparation Example 2-1] in that: the reinforcing adhesive uses the reinforcing adhesive in [Preparation Example 1-5].

[0073]

Preparation Example 2-6

[0074] A hot melt adhesive, which is different from [Preparation Example 2-1] in that: the reinforcing adhesive is replaced with an equal mass of basic rubber hot melt adhesive. Example

[0075]

Example 1

[0076] A durable double-layer waterproof coiled material, referring to Figure 1 , the double-layer waterproof coiled material is successively from bottom to top a first waterproof layer 1, a hot melt adhesive layer 2 and a second waterproof layer 3. The first waterproof layer 1 is an asphalt-based waterproof layer. The second waterproof layer 3 is successively from top to bottom a sand layer 31, a connecting adhesive layer 32 and a waterproof base material 33. Among them, both the hot melt adhesive layer 2 and the connecting adhesive layer 32 are made of the waterproof and oil-resistant hot melt adhesive in [Preparation Example 2-1], and the waterproof base material 33 is made of an asphalt-based waterproof coiled material.

[0077] In this example, the preparation method of the durable double-layer waterproof coiled material includes the following steps:

[0078] Put the waterproof and oil-resistant hot melt adhesive into a glue tank at a temperature of 140-160 °C for melting, and then coat the glue on the surfaces on both sides of the waterproof base material of the second waterproof layer to form a hot melt adhesive layer and a connecting adhesive layer on the surfaces on both sides of the waterproof base material. The thickness of the hot melt adhesive layer and the connecting adhesive layer is 100 μm. Then, evenly spray sand on 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 wind it up to obtain a single-layer waterproof coiled material;

[0079] Unroll the single-layer waterproof coiled material, remove the release film, and compound it with the first waterproof layer through the hot melt adhesive layer on the single-layer waterproof coiled material to obtain a durable double-layer waterproof coiled material.

[0080]

Example 2

[0081] A durable double-layer waterproof coiled material, which is different from [Example 1] in that: both the hot melt adhesive layer and the connecting adhesive layer are made of the waterproof and oil-resistant hot melt adhesive in [Preparation Example 2-2].

[0082]

Example 3

[0083] A durable double-layer waterproof coiled material, which is different from [Example 1] in that: both the hot melt adhesive layer and the connecting adhesive layer are made of the waterproof and oil-resistant hot melt adhesive in [Preparation Example 2-3].

[0084]

Example 4

[0085] A durable double - layer waterproof coiled material, which is different from [Example 1] in that: both the hot - melt adhesive layer and the connecting adhesive layer are made of the waterproof and oil - resistant hot - melt adhesive in [Preparation Example 2 - 4].

[0086] Comparative example

[0087] [Comparative Example 1]

[0088] A double - layer waterproof coiled material, which is different from [Example 1] in that: both the hot - melt adhesive layer and the connecting adhesive layer are made of the hot - melt adhesive in [Preparation Example 2 - 5].

[0089] [Comparative Example 2]

[0090] A double - layer waterproof coiled material, which is different from [Example 1] in that: both the hot - melt adhesive layer and the connecting adhesive layer are made of the hot - melt adhesive in [Preparation Example 2 - 6].

[0091] Performance detection test

[0092] Refer to GB / T 23457 - 2017 to test the anti - water - seepage property, anti - impact property, low - temperature bending property, oil - seepage property, peel strength between coiled materials, tensile strength and peel strength between the double - layer waterproof coiled material and the post - cast concrete of the double - layer waterproof coiled materials in each example and comparative example. Among them, for the peel strength test between coiled materials, samples placed for 0 days and samples placed at 70 °C for 28 days are respectively taken for testing; for the tensile strength test, samples without treatment, heat - aged treatment (placed at 70 °C for 28 days), and water - immersion treatment (immersed in water at 23 °C for 28 days) are respectively taken for testing; in the test of the peel strength between the double - layer waterproof coiled material and the post - cast concrete, after preparing specimens according to the content recorded in Sections 6.20.1.1 and 6.20.1.2 of GB / T 23457 - 2017, the peel strength between the double - layer waterproof coiled material and the post - cast concrete of the specimens is directly tested (corresponding to the data of 0 days). In addition, after the specimens are placed in an environment of 70 °C for 28 days, samples are taken again to test the peel strength between the double - layer waterproof coiled material and the post - cast concrete (corresponding to the data of 70 °C, 28 days).

[0093] Table 1

[0094]

[0095] Table 2

[0096]

[0097] Table 3

[0098]

[0099] Table 4

[0100]

[0101] Combined with the detection data recorded in Table 1 - Table 4 above, it can be seen that: the double - layer waterproof coiled material in Examples 1 - 4 of this application has excellent anti - water - channeling, anti - impact, low - temperature bending and anti - oil - penetration properties. At the same time, after the double - layer waterproof coiled material is placed at 70°C for 28 days, the peel strength between the coiled materials can still reach more than 1.2 N / mm. When testing the peel strength between the coiled material and the post - cast concrete, after the specimen is placed at 70°C for 28 days, the peel strength between the double - layer waterproof coiled material and the concrete can still reach more than 1.6 N / mm. This shows that the hot - melt adhesive layer and the connecting adhesive layer in the double - layer waterproof coiled material have good resistance to small - molecule engine oil. Moreover, the tensile strength of the double - layer waterproof coiled material can remain above 20 MPa after heat aging or immersion in water. That is, the double - layer waterproof coiled material in this application has excellent comprehensive performance and a long service life, which is conducive to achieving the goal of the same service life as the building for the double - layer waterproof coiled material.

[0102] 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 this application. Combined with the detection results recorded in Table 1 - Table 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 anti - water - channeling, anti - impact, low - temperature bending and anti - oil - penetration properties of the double - layer waterproof coiled material. Moreover, the peel strength between the coiled materials and the peel strength between the double - layer waterproof coiled material and the post - cast concrete decrease significantly after heat treatment. At the same time, the tensile strength, heat - aging resistance and water - resistance of the double - layer waterproof coiled material in Comparative Example 1 are also worse than those in Example 1.

[0103] The difference between Comparative Example 2 and Example 1 is that: in the hot - melt adhesive used in Comparative Example 2, the reinforcing adhesive is not added. Combined with the detection results recorded in Table 1 - Table 3 above, it can be seen that when the reinforcing adhesive is not added to the hot - melt adhesive in Comparative Example 2, the anti - water - channeling and anti - oil - penetration properties of the double - layer waterproof coiled material both decrease, and the peel strength between the coiled materials and the peel strength between the double - layer waterproof coiled material and the post - cast concrete decrease significantly after heat treatment, indicating that the performance of the hot - melt adhesive layer and the connecting adhesive layer in resisting small - molecule oil is significantly reduced. At the same time, the tensile strength, heat - aging resistance and water - resistance of the double - layer waterproof coiled material in Comparative Example 2 are also worse than those in Example 1.

[0104] The difference between Example 3-4 and Example 1 lies in that in the waterproof and oil-resistant hot melt adhesive used in Example 3-4, the molar ratios of polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane to diisocyanate in the amino-terminated polyurea prepolymer are not within the preferred range of this application. Combining the test results recorded in Tables 1-3, it can be seen that when the molar ratios of polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane to diisocyanate in the amino-terminated polyurea prepolymer are within the range of (0.3-0.5):(0.1-0.2):(0.5-0.7):(0.1-0.2):1, it is beneficial to further improve the bonding strength between the coils and the peel strength of the double-layer waterproof coil and the post-cast concrete, and can reduce the influence of small molecule engine oil on the bonding performance between the coils and the peel strength of the double-layer waterproof coil and the post-cast concrete. At the same time, it further improves the tensile strength, heat aging performance and water resistance of the double-layer waterproof coil.

[0105] This specific implementation manner is only an interpretation of this application and does not limit this application. After reading this specification, those skilled in the art can make modifications to this specific implementation manner without creative contributions as needed, but as long as they are within the scope of the claims of this application, they are protected by the patent law.

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 basic rubber hot melt adhesive and 5-10wt% of a reinforcing adhesive, and the reinforcing adhesive includes an amino-terminated polyurea prepolymer, a hydroxyl-terminated polyurethane prepolymer, a blocked isocyanate crosslinking agent and a catalyst; wherein 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); 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.

2. A durable double-layer waterproofing membrane according to claim 1, characterized in that: The molar ratio of the polyoxypropylene diamine, polyoxypropylene triamine, amino-terminated phenyl polypropylene glycol, amino-terminated polysiloxane and 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: 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, the temperature is controlled at 10-20° C. to carry out a prepolymerization reaction, and the solvent is removed in vacuo after the reaction is completed to obtain the 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, and after the reaction is completed, vacuum degassing is performed to obtain the 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 at 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 100-600μm, 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 membrane; 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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