A polymer waterproof roll and its preparation method

Abstract

The present invention relates to the technical field of waterproof materials, and provides a polymer waterproof roll and a preparation method thereof. The polymer waterproof roll comprises, from top to bottom, a protective layer, an asphalt layer, a self-adhesive layer, and a diaphragm layer. The raw materials of the self-adhesive layer include the following components by weight: 60-80 parts of butyl rubber, 10-20 parts of SBS, 6-14 parts of a tackifying resin, 1-2 parts of an antioxidant, 15-25 parts of a filler, and 2-3 parts of a vulcanizing agent. The butyl rubber includes a first butyl rubber and a second butyl rubber, the first butyl rubber being of the model Yanshan Petrochemical IIR-1751, and the second butyl rubber being of the model Xinhui 532. The above technical solution solves the problem of low adhesion of polymer waterproof rolls in the related art.

Description

Technical Field

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

[0002] As a core material for building waterproofing, polymer waterproofing membranes' performance directly impacts a building's durability and safety. Currently, mainstream polymer waterproofing membranes include polyvinyl chloride, thermoplastic polyolefins, EPDM rubber, and high-density polyethylene. These materials, due to their excellent weather resistance, tensile strength, and chemical resistance, are widely used in roofing, underground engineering, and water conservancy facilities. However, long-term engineering practice has shown that insufficient adhesion between the membrane and the substrate has become a key bottleneck limiting its service life.

[0003] Traditional bonding systems have multiple inherent defects in terms of bonding stability. First, the temperature sensitivity of the self-adhesive layer is significant: at high temperatures, the self-adhesive layer softens, causing the roll to slip; at low temperatures, the self-adhesive layer becomes brittle, causing interfacial cracking. This phenomenon is particularly prominent in areas with extreme temperature differences. For example, under the alternating effects of high temperature and humidity in southern China and severe cold and dry environments in northern my country, roll bonding failure problems are frequent. Secondly, the polarity differences between polymer materials and substrates such as concrete and metal lead to poor interfacial compatibility. For example, the surface energy of EPDM rubber is much lower than that of concrete. The polarity mismatch leads to insufficient interfacial bonding strength, and the penetration of water molecules in a humid environment further weakens the bonding effect. In addition, ultraviolet radiation, ozone, and chemical media will accelerate the breakage of adhesive molecular chains, resulting in a decrease in bonding strength.

[0004] Leakage caused by insufficient adhesion can have serious consequences in real-world projects. For example, in underground utility corridors, due to the long-term exposure to groundwater pressure and dynamic loads, traditional membranes are prone to adhesive failure, leading to water leakage at joints. This is costly to repair and compromises structural safety. In the roofing of super-high-rise buildings, the combined effects of strong wind loads and temperature fluctuations further amplify the risk of membrane slippage.

[0005] As building waterproofing projects evolve towards longer-lasting, green, and intelligent technologies, the industry is placing higher demands on material performance. Key projects such as cross-sea bridges and urban subways require materials with even higher bonding stability. However, existing technologies struggle to meet these demands.

[0006] In summary, the problem of insufficient adhesion of traditional polymer waterproof membranes has become a major obstacle to the development of the industry. It is of vital importance to develop a polymer waterproof membrane with improved adhesion. Summary of the Invention

[0007] The present invention provides a polymer waterproofing coiled material and a preparation method thereof, which solves the problem of low adhesiveness of the polymer waterproofing coiled material in the related art.

[0008] The technical solutions of the present invention are as follows:

[0009] The present invention provides a polymer waterproof roll, which comprises, from top to bottom, a protective layer, an asphalt layer, a self-adhesive layer, and a diaphragm layer. The raw materials of the self-adhesive layer include the following components by weight: 60-80 parts of butyl rubber, 10-20 parts of SBS, 6-14 parts of tackifying resin, 1-2 parts of antioxidant, 15-25 parts of filler, and 2-3 parts of vulcanizing agent.

[0010] The butyl rubber includes a first butyl rubber and a second butyl rubber. The first butyl rubber and the second butyl rubber have different models. The model of the first butyl rubber is Yanshan Petrochemical IIR-1751, and the model of the second butyl rubber is Xinhui 532.

[0011] As a further technical solution, the mass ratio of the first butyl rubber to the second butyl rubber is 7-9:2.

[0012] In the present invention, when the mass ratio of Yanshan Petrochemical IIR-1751 butyl rubber to Xinhui 532 butyl rubber is 7-9:2, the adhesion of the waterproof membrane is further improved.

[0013] As a further technical solution, the tackifying resin includes one or both of phenolic resin and rosin resin;

[0014] The antioxidant includes one or both of antioxidant MB and antioxidant RD;

[0015] The filler includes one or two of calcium carbonate and kaolin;

[0016] The vulcanizing agent includes one or more of dicumyl peroxide, di-tert-butyl peroxide, and benzoyl peroxide.

[0017] In the present invention, a tackifying resin is added to the raw material of the self-adhesive layer. The tackifying resin suppresses the plastic deformation of the waterproof membrane under long-term use through the intermolecular entanglement effect, thereby maintaining the long-term adhesion of the waterproof membrane.

[0018] In the present invention, an antioxidant is added to the raw material of the self-adhesive layer, which can capture free radicals generated by rubber oxidation, terminate chain oxidation, and extend the service life of the waterproof membrane;

[0019] In the present invention, calcium carbonate or kaolin is added to the raw material of the self-adhesive layer as a filler, and the filler can fill the gaps between rubber molecules, thereby strengthening and hardening the waterproof membrane.

[0020] In the present invention, a vulcanizing agent is added to the raw material of the self-adhesive layer, and the vulcanizing agent forms a three-dimensional network structure of the rubber, thereby improving the heat resistance of the self-adhesive layer, reducing the relaxation rate of the self-adhesive layer, and maintaining the elasticity of the self-adhesive layer.

[0021] As a further technical solution, the protective layer raw material includes the following components in parts by weight: 70-80 parts of high-density polyethylene, 7-11 parts of nitrile rubber, 16-22 parts of calcium carbonate, 1-2 parts of antioxidant, and 2-3 parts of vulcanizing agent.

[0022] In the present invention, high-density polyethylene serves as a rigid skeleton of the protective layer, which can help the waterproof membrane resist stress damage, and the nitrile rubber can promote the uniform dispersion of calcium carbonate in the matrix.

[0023] As a further technical solution, the calcium carbonate is a calcium carbonate composite material;

[0024] The raw materials of the calcium carbonate composite material include calcium carbonate and m-hydroxycinnamic acid.

[0025] As a further technical solution, the preparation method of the calcium carbonate composite material comprises the following steps:

[0026] adding calcium carbonate to a solvent, adding m-hydroxycinnamic acid, stirring until uniform, and drying to obtain a calcium carbonate composite material;

[0027] During the stirring, the temperature is 60-70°C;

[0028] The solvent includes one or both of ethanol and isopropanol;

[0029] The weight-to-volume ratio of the calcium carbonate to the solvent is 1 g:2-3 mL.

[0030] In the present invention, m-hydroxycinnamic acid is used to treat calcium carbonate to obtain a calcium carbonate composite material. Polar groups in the calcium carbonate composite materials interact with each other, and the calcium carbonate composite material and polyethylene interact with each other, thereby improving the tensile strength of the protective layer.

[0031] As a further technical solution, the mass ratio of the calcium carbonate to m-hydroxycinnamic acid is 45-55:1.

[0032] In the present invention, the tensile strength of the protective layer is improved by adjusting the mass ratio of calcium carbonate to m-hydroxycinnamic acid to 45-55:1.

[0033] As a further technical solution, in the protective layer raw material, the antioxidant includes one or both of antioxidant 1076 and antioxidant 1010;

[0034] The vulcanizing agent includes one or more of dicumyl peroxide, di-tert-butyl peroxide, and benzoyl peroxide.

[0035] In the present invention, antioxidants are added to the raw materials of the protective layer, and antioxidants 1076 and 1010 are selected as the antioxidants. When the antioxidants are added, the antioxidant property of the protective layer is improved through the steric stabilization mechanism and the synergistic effect of multiple functional groups.

[0036] As a further technical solution, the material of the asphalt layer includes modified asphalt;

[0037] The material of the diaphragm layer includes polyethylene.

[0038] The present invention also provides a method for preparing a polymer waterproof roll, which is used to prepare the polymer waterproof roll, comprising the following steps:

[0039] S1. Mixing the raw materials of the self-adhesive layer and extruding the self-adhesive layer;

[0040] S2, mixing the raw materials of the protective layer and extruding the protective layer;

[0041] S3. After compounding in the order of protective layer, asphalt layer, self-adhesive layer and diaphragm layer from top to bottom, a polymer waterproof membrane is obtained.

[0042] The working principle and beneficial effects of the present invention are:

[0043] 1. In the present invention, two butyl rubbers, model Yanshan Petrochemical IIR-1751 and model Xinhui 532, are added to the self-adhesive layer. The two butyl rubbers work synergistically to improve the adhesion of the waterproof membrane, prevent the occurrence of adhesion failure problems, reduce the risk of slippage of the polymer waterproof membrane, and extend the service life of the waterproof membrane.

[0044] 2. In the present invention, SBS is added to the self-adhesive layer. As a thermoplastic elastomer, SBS can significantly improve the dynamic mechanical properties of the adhesive, allowing it to maintain flexibility in low-temperature environments and avoid brittle cracking. DETAILED DESCRIPTION

[0045] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0046] In the following examples and comparative examples, the model of SBS is YH-792, the model of phenolic resin is 2402, the model of rosin resin is 138 rosin glycerol ester, the particle size of calcium carbonate is 1000 mesh, and the purity is 99 wt %, the model of high-density polyethylene is HHM5502LW, the model of nitrile rubber is NBR-1704, the modified asphalt is purchased from Weifang Changxu Building Materials Co., Ltd., the model is CX-CW211, and the model of polyethylene is DFDA-7042.

[0047] Example 1

[0048] A polymer waterproofing membrane comprises, from top to bottom, a protective layer, an asphalt layer made of modified asphalt, a self-adhesive layer, and a diaphragm layer made of polyethylene. The self-adhesive layer comprises the following components by weight: 80 parts of butyl rubber, 20 parts of SBS, 14 parts of phenolic resin, 2 parts of antioxidant MB, 25 parts of calcium carbonate, and 3 parts of dicumyl peroxide.

[0049] The butyl rubber is Yanshan Petrochemical IIR-1751 butyl rubber and Xinhui 532 butyl rubber in a mass ratio of 11:2;

[0050] The protective layer material includes the following components in parts by weight: 80 parts of high-density polyethylene, 11 parts of nitrile rubber, 22 parts of calcium carbonate, 2 parts of antioxidant 1076, and 3 parts of dicumyl peroxide;

[0051] The preparation method of the polymer waterproof membrane comprises the following steps:

[0052] S1. Mixing the raw materials of the self-adhesive layer and extruding the self-adhesive layer;

[0053] S2, mixing the raw materials of the protective layer and extruding the protective layer;

[0054] S3. After compounding in the order of protective layer, asphalt layer, self-adhesive layer and diaphragm layer from top to bottom, a polymer waterproof membrane is obtained.

[0055] Example 2

[0056] A polymer waterproofing membrane comprises, from top to bottom, a protective layer, an asphalt layer made of modified asphalt, a self-adhesive layer, and a diaphragm layer made of polyethylene. The self-adhesive layer comprises the following components by weight: 60 parts of butyl rubber, 10 parts of SBS, 6 parts of rosin resin, 1 part of antioxidant RD, 15 parts of kaolin, and 2 parts of di-tert-butyl peroxide.

[0057] The butyl rubber is Yanshan Petrochemical IIR-1751 butyl rubber and Xinhui 532 butyl rubber in a mass ratio of 5:2;

[0058] The protective layer material includes the following components in parts by weight: 70 parts of high-density polyethylene, 7 parts of nitrile rubber, 16 parts of calcium carbonate, 1 part of antioxidant 1076, and 2 parts of di-tert-butyl peroxide;

[0059] The preparation method of the polymer waterproof membrane comprises the following steps:

[0060] S1. Mixing the raw materials of the self-adhesive layer and extruding the self-adhesive layer;

[0061] S2, mixing the raw materials of the protective layer and extruding the protective layer;

[0062] S3. After compounding in the order of protective layer, asphalt layer, self-adhesive layer and diaphragm layer from top to bottom, a polymer waterproof membrane is obtained.

[0063] Example 3

[0064] A polymer waterproofing membrane comprises, from top to bottom, a protective layer, an asphalt layer made of modified asphalt, a self-adhesive layer, and a diaphragm layer made of polyethylene. The self-adhesive layer comprises the following components by weight: 70 parts of butyl rubber, 15 parts of SBS, 9 parts of phenolic resin, 1.5 parts of antioxidant MB, 20 parts of calcium carbonate, and 2.5 parts of benzoyl peroxide.

[0065] The butyl rubber is Yanshan Petrochemical IIR-1751 butyl rubber and Xinhui 532 butyl rubber in a mass ratio of 5:1;

[0066] The protective layer material includes the following components in parts by weight: 75 parts of high-density polyethylene, 9 parts of nitrile rubber, 18 parts of calcium carbonate, 1.5 parts of antioxidant 1076, and 2.5 parts of benzoyl peroxide;

[0067] The preparation method of the polymer waterproof membrane comprises the following steps:

[0068] S1. Mixing the raw materials of the self-adhesive layer and extruding the self-adhesive layer;

[0069] S2, mixing the raw materials of the protective layer and extruding the protective layer;

[0070] S3. After compounding in the order of protective layer, asphalt layer, self-adhesive layer and diaphragm layer from top to bottom, a polymer waterproof membrane is obtained.

[0071] Example 4

[0072] The only difference between this embodiment and embodiment 3 is that the butyl rubber in this embodiment is Yanshan Petrochemical IIR-1751 butyl rubber and Xinhui 532 butyl rubber in a mass ratio of 3:1.

[0073] Example 5

[0074] The only difference between this embodiment and embodiment 3 is that the butyl rubber in this embodiment is Yanshan Petrochemical IIR-1751 butyl rubber and Xinhui 532 butyl rubber in a mass ratio of 7:2.

[0075] Example 6

[0076] The only difference between this embodiment and embodiment 3 is that the butyl rubber in this embodiment is Yanshan Petrochemical IIR-1751 butyl rubber and Xinhui 532 butyl rubber in a mass ratio of 9:2.

[0077] Example 7

[0078] The only difference between this embodiment and embodiment 6 is that the raw materials of the protective layer in this embodiment include the following components in parts by weight: 75 parts of high-density polyethylene, 9 parts of nitrile rubber, 18 parts of calcium carbonate composite material, 1.5 parts of antioxidant 1076, and 2.5 parts of benzoyl peroxide;

[0079] The raw materials of the calcium carbonate composite material include calcium carbonate and m-hydroxycinnamic acid in a mass ratio of 45:1;

[0080] The preparation method of the calcium carbonate composite material comprises the following steps:

[0081] Calcium carbonate is added to isopropyl alcohol, m-hydroxycinnamic acid is added, stirred at 70° C. until uniform, and dried to obtain a calcium carbonate composite material;

[0082] The weight-to-volume ratio of calcium carbonate to isopropyl alcohol is 1 g:2 mL.

[0083] Example 8

[0084] The only difference between this embodiment and embodiment 7 is that the raw materials of the calcium carbonate composite material in this embodiment include calcium carbonate and m-hydroxycinnamic acid in a mass ratio of 55:1.

[0085] Example 9

[0086] The only difference between this embodiment and embodiment 7 is that in this embodiment, m-hydroxycinnamic acid is replaced by p-methoxycinnamic acid.

[0087] Example 10

[0088] The only difference between this embodiment and embodiment 7 is that in this embodiment, m-hydroxycinnamic acid is replaced by mercaptopropyltrimethoxysilane.

[0089] Example 11

[0090] The only difference between this embodiment and embodiment 7 is that the preparation method of the calcium carbonate composite material in this embodiment includes the following steps:

[0091] Calcium carbonate is added to ethanol, m-hydroxycinnamic acid is added, stirred at 60° C. until uniform, and dried to obtain a calcium carbonate composite material;

[0092] The weight-to-volume ratio of calcium carbonate to ethanol is 1 g:3 mL.

[0093] Comparative Example 1

[0094] The only difference between this comparative example and Example 3 is that the butyl rubber in this comparative example is Yanshan Petrochemical IIR-1751 butyl rubber.

[0095] Comparative Example 2

[0096] The only difference between this comparative example and comparative example 1 is that the butyl rubber in this comparative example is Cenhui 532 butyl rubber.

[0097] Comparative Example 3

[0098] The only difference between this comparative example and Example 3 is that the butyl rubber in this comparative example is Yanshan Petrochemical IIR-1751 butyl rubber and JSR BUTYL 268 butyl rubber in a mass ratio of 5:1.

[0099] Comparative Example 4

[0100] The only difference between this comparative example and Example 3 is that the butyl rubber in this comparative example is BK-1675N butyl rubber and Xinhui 532 butyl rubber in a mass ratio of 5:1.

[0101] Experimental Example 1

[0102] The polymer waterproof membranes prepared in Examples 1-6 and Comparative Examples 1-4 were tested for their adhesive properties according to the test method specified in GB / T 35467-2017, "Wet-laid Waterproof Membrane." The test results are shown in Table 1.

[0103] Table 1 Adhesion test results

[0104]

[0105] As can be seen from Table 1, the polymer waterproofing membrane prepared in the present invention has a sustained adhesion of more than 125 minutes. Therefore, the present invention uses two types of butyl rubber, Yanshan Petrochemical IIR-1751 and Xinhui 532, to synergistically improve the sustained adhesion of the waterproofing membrane.

[0106] Experimental Example 2

[0107] The protective layers of the polymer waterproof membranes prepared in Examples 6 to 11 were tested for longitudinal tensile strength according to the method described in GB / T 328.9-2007, "Test Methods for Building Waterproofing Membranes - Part 9: Tensile Properties of Polymer Waterproofing Membranes." The test results are shown in Table 2.

[0108] Table 2 Tensile strength test results

[0109]

[0110] As can be seen from Table 2, the tensile strength of the protective layer of the polymer waterproof membrane prepared in the present invention reaches more than 30.4 MPa. In addition, the present invention uses m-hydroxycinnamic acid to treat calcium carbonate to obtain a calcium carbonate composite material, which improves the tensile strength of the protective layer of the polymer waterproof membrane.

[0111] Experimental Example 3

[0112] The protective layers of the polymer waterproof membranes prepared in Examples 1 to 3 were tested for longitudinal elongation according to the method described in GB / T 328.9-2007, "Test Methods for Building Waterproof Membranes - Part 9: Tensile Properties of Polymer Waterproof Membranes." The test results are shown in Table 3.

[0113] Table 3 Longitudinal elongation test results

[0114]

[0115] It can be seen from Table 3 that the polymer waterproof membrane in the present invention can meet the actual use requirements.

[0116] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A polymer waterproof roll, characterized in that: From top to bottom, it includes a protective layer, an asphalt layer, a self-adhesive layer, and a diaphragm layer. The raw materials of the self-adhesive layer include the following components by weight: 60-80 parts of butyl rubber, 10-20 parts of SBS, 6-14 parts of tackifying resin, 1-2 parts of antioxidant, 15-25 parts of filler, and 2-3 parts of vulcanizing agent. The butyl rubber includes a first butyl rubber and a second butyl rubber, the model of the first butyl rubber is Yanshan Petrochemical IIR-1751, and the model of the second butyl rubber is Xinhui 532; The mass ratio of the first butyl rubber to the second butyl rubber is 7-9:2; The protective layer material comprises the following components by weight: 70-80 parts of high-density polyethylene, 7-11 parts of nitrile rubber, 16-22 parts of calcium carbonate, 1-2 parts of antioxidant, and 2-3 parts of vulcanizing agent; The calcium carbonate is a calcium carbonate composite material; The raw materials of the calcium carbonate composite material include calcium carbonate and m-hydroxycinnamic acid.

2. A polymer waterproofing membrane according to claim 1, characterized in that: The tackifying resin includes one or both of phenolic resin and rosin resin; The antioxidant includes one or two of antioxidant MB and antioxidant RD; The filler includes one or two of calcium carbonate and kaolin; The vulcanizing agent includes one or more of dicumyl peroxide, di-tert-butyl peroxide, and benzoyl peroxide.

3. The polymer waterproofing membrane according to claim 1, characterized in that: The preparation method of the calcium carbonate composite material comprises the following steps: adding calcium carbonate to a solvent, adding m-hydroxycinnamic acid, stirring until uniform, and drying to obtain a calcium carbonate composite material; During the stirring, the temperature is 60-70°C; The solvent includes one or both of ethanol and isopropanol; The weight-to-volume ratio of the calcium carbonate to the solvent is 1 g:2-3 mL.

4. A polymer waterproofing membrane according to claim 3, characterized in that: The mass ratio of the calcium carbonate to m-hydroxycinnamic acid is 45-55:

1.

5. The polymer waterproofing membrane according to claim 1, characterized in that: In the protective layer raw material, the antioxidant includes one or both of antioxidant 1076 and antioxidant 1010; The vulcanizing agent includes one or more of dicumyl peroxide, di-tert-butyl peroxide, and benzoyl peroxide.

6. A polymer waterproofing membrane according to any one of claims 1 to 5, characterized in that: The material of the asphalt layer includes modified asphalt; The material of the diaphragm layer includes polyethylene.

7. A method for preparing a polymer waterproofing coiled material, for preparing a polymer waterproofing coiled material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1. Mixing the raw materials of the self-adhesive layer and extruding the self-adhesive layer; S2, mixing the raw materials of the protective layer and extruding the protective layer; S3. After compounding in the order of protective layer, asphalt layer, self-adhesive layer and diaphragm layer from top to bottom, a polymer waterproof membrane is obtained.

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